Beruflich Dokumente
Kultur Dokumente
Nanomaterials Science
Contents
Page
Introduction
9
3
23
Nanophotonics
75
91
101
117
Theoretical Chemistry
143
Author Index
147
Techniques Index
151
Introduction
L.S.,
In this book you will find a summary of the postgraduate research projects performed in the
various groups belonging to the Debye Institute for Nanomaterials Science (DINS); a part of
Utrecht University. The purpose of this book is to give you an overview of the research performed
by the PhD-students and post-docs of our institute as well as to encourage collaboration between
the different research groups of the DINS itself. Each contribution gives a brief summary of the
research performed by a specific person along with the names of the techniques frequently used
by that person. In the back of the book, an author index can be found, allowing easy access to
research performed by a specific person. Additionally, there is a techniques index, allowing you to
easily identify and contact people proficient in a specific technique.
This book has been edited by the Debye PhD Committee (Debye AiO Commissie, DAC), which
is a representative body for the PhD-students and post-docs of the institute. It is presented each
year at the Debye Spring School or the DO! Days. These meeting days are organized by the
DAC for the postgraduate researchers of the DINS. Additionally, the book is available online:
http://www.uu.nl/faculty/science/EN/research/researchinstitutes/debye/DAC
In this years book the contributions of 125 PhD students and post-docs of the Debye institute
are presented.
On behalf of the Debye PhD Committee,
Bas Reijers
Supervisor:
10
The great strength of scanning tunneling microscopy (STM) is the ability to simultaneous measure
structural and electrical information in real space down to the atomic scale. An inherent drawback
however is that the structural and electrical information is mixed: the tunneling current between
tip and sample depends both on the local density of states near the Fermi level and on the distance
between tip and sample.
Therefore it is often very informative to study the same sample with both atomic force microscopy
(AFM) and STM. In the AFM the change in resonance frequency of the tip due to the interaction
with the sample is used as image parameter. By changing the distance between tip and sample we
can measure local interaction curves giving us chemical information about the sample.
Combining these two techniques gives us a toolbox to image atoms, molecules, graphene and
quantum dots while simultaneously allowing us to obtain local chemical and electrical information
at the atomic scale. An example is shown below.
Figure 1: a) atomically resolved images of graphene grown on Ir(111). The atomic contrast changes from repulsive (bright)
to attractive (dark) upon an increase of the tip sample distance. b) model showing the graphene buckling due
to the lattice mismatch with the Ir(111). This buckling locally affects the distance between tip and sample, as
can be observed by the protruding domes in a). c) frequency shift as a function of the distance between tip and
sample recorded on top of a carbon atom and on a hollow site. The crossing of the curves indicates the distance
between tip and sample at which the atomic contrast changes from repulsive (bright) to attractive (dark). Image
reprinted with permission from [1].
[1]
Boneschanscher, M.P.; Lit, J. van der; Sun, Z.; Swart, I.; Liljeroth, P.; Vanmaekelbergh, D.; ACS Nano 2012, 6, 10216-10221.
Supervisor:
Chemical colloidal synthesis, UV-VIS-NIR absorption spectroscopy, Luminescence spectroscopy, Time resolved
laser spectroscopy
Luminescent solar concentrators (LSCs) are a promising solution in the race to produce more
economical photovoltaic energy. The system, which concentrates spectrally converted sunlight
on solar cells at the edges of the LSC, greatly reduces the required area of expensive photovoltaic
cells. Moreover, the ability of LSCs to collect both direct and diffuse sunlight allows the system to
be used without expensive tracking devices. The main reasons why, at present, LSCs are not being
used at any significant scale are the low efficiency and limited stability of the current systems. In
this project we try to address both of these problems.
11
Both the efficiency and the stability in the current systems are limited by the dyes used for the
spectral conversion. It is our goal to develop efficient and stable phosphors that strongly absorb
photons from incoming sunlight and convert them to a narrow band or line emission in the
NIR (700-1000 nm) that can efficiently be absorbed by crystalline silicon solar cells. To achieve
this goal, we investigate a variety of colloidal nanocrystals doped with efficiently luminescing
transition metal or lanthanide ion activators. The size of the colloidal nanocrystals allows them to
be incorporated in a LSC polymer without causing scattering.The combination of absorption by a
the nanocrystalline host or a co-doped sensitizer with energy transfer to the activator ions provides
the opportunity to minimize re-absorption.
We have shown a proof of principle: ZnTe Magic Size Nanocrystal (MSNCs)[1] and ZnTe
Quantum Dots (QDs) have been doped with Mn2+ ions by cation exchange and shown to exhibit
energy transfer from the excited particle to the dopant upon excitation of the particle resulting
in a Mn2+ 4T16A1 emission. Currently we are investigating a range of different dopants and are
optimizing the host materials to make them more suitable for the cation exchange reactions.
Figure 1: Schematic representation of doping a magic sized nanocrystal through cation exchange.
[1]
Eilers, J.J.; Groeneveld, E.; Donega, C.D.M.; Meijerink, A. Optical properties of Mn-Doped ZnTe Magic Size Nanocrystals. J.
Phys. Chem. Lett., 2012, 3 (12), pp 16631667
Supervisor:
Prof. dr. R.E.I. Schropp, dr. W.G.J.H.M. van Sark and dr. C. de Mello Doneg
12
Luminescent solar concentrators are low cost photovoltaic devices, which reduce the amount of
necessary semiconductor material per unit area of a solar collector by means of concentration.
The device is comprised of a thin plastic plate in which luminescent species (fluorophores) have
been incorporated. The fluorophores absorb the solar light and radiatively re-emit part of the
energy. Total internal reflection traps most of the emitted light inside the plate and wave-guides
it to a narrow side facet with a solar cell attached, where conversion into electricity occurs.
The efficiency of such devices is as yet rather low, due to several loss mechanisms, of which selfabsorption is of high importance.
This project studies self-absorption behaviour in various luminescent species, e.g. organic dyes
and semiconductor nanocrystals. Results obtained so far show, that semiconductor heteronanostructures of type II have the potential to solve the self-absorption problem.
At present stage a quantity for evaluation of self-absorption self-absorption cross section has
been proposed. The relation between this self-absorption cross section and the losses due to selfabsorption is currently being investigated.
Figure 1: Principle (top) and single ray trace with one self-absorption event (bottom).
[1]
[2]
Supervisor:
Atomic Force Microscopy, Scanning Tunneling Microscopy/Spectroscopy, Organic Synthesis, Density Functional
Theory
Organic chemistry has recently proven a valuable tool in constructing unique nanostructures
on solid supports. By various surface synthesis procedures a large variety of covalent organic
frameworks can be obtained [1]. Using this technique we hope to be able to synthesize and study
graphene-like nanostructures.
To investigate the obtained nanostructures we use Atomic Force Microscopy (AFM) and Scanning
Tunneling Microscopy (STM). The AFM can provide detailed information about the exact atomic
structure of the obtained nanostructures while the STM allows for the visualization of their
electronic structure.
Subsequently, small modifications can be made on the nanostructures by either changing the
molecules used in the preparation or induce changes controllably with the STM. The effect of
these changes can then be studied as described before.
Figure 1: The molecular precursor on the right can be used to synthesize nanoribbons, shown on the left, of up to 50 nm
long. The atomic structure of these ribbons was identified using the AFM.
[1]
13
Supervisor:
14
Upconversion (UC) materials, which are able to emit higher-energy light after the absorption of
two or more lower-energy photons, have regained attention due to their potential to enhance the
efficiency of solar cells. In particular, for crystalline silicon (c-Si) solar cells (Eg = 1.1 eV) around
32% of the incident solar energy is lost due to photons with energy below the bandgap, which are
not absorbed by the solar cell [1]. An upconverting layer mounted beneath a bifacial solar cell can
increase the maximum theoretical efficiency up to ca. 47% for a c-Si solar cell for un-concentrated
terrestrial solar spectrum (AM1.5) [2]. Insulating materials doped with rare-earth (RE) ions are
very suitable for this purpose.
The main concept of the NanoSpec European project in which we are involved is the combination
of nanocrystal quantum dots (NQDs) (PbSe or PbS) and UC materials for harvesting sub-bandgap
photons by UC processes, in order to increase silicon solar cells efficiency (see Fig. 1). The NQD
are used for spectral concentration, and the RE-doped UC material transforms low energy
photons into high energy photons which can be used by the silicon solar cell. In particular, my
project is focused on the optimization of the UC material by combining different RE impurities
and host lattices. We have demonstrated very efficient UC luminescence in Er3+-doped Gd2O2S
under monochromatic excitation around 1.5 m into the 4I13/2 Er3+ state. An internal UC quantum
yield of 121% was achieved for Gd2O2S: 10%Er3+ upon 700 Wm-2 excitation.We also study Ho3+doped materials since the excitation in the 5I7 and 5I6 Ho3+ levels absorbs a region of the solar
spectrum transparent to silicon solar cells, around 2 and 1.15 m.
Figure 1: Scheme of the UC system. The NQD absorb photons between the silicon bandgap and the absorption range of
the UC material (2), and emit in the absorption range of the upconverter (3). The upconverter transforms these
low energy photons (3) into high energy photons which can be used by the solar cell (1).
[1]
[2]
B. M. van der Ende, L. Aarts, A. Meijerink, Phys. Chem. Chem. Phys. 11 (2009) 11081.
T. Trupke, M.A. Green, P. Wrfel, J. Appl. Phys. 92 (7) (2002) 4117.
Supervisor:
Colloidal nanocrystals of semiconductor, metallic, and magnetic compounds are of large interest
in current nanoscience. Semiconductor nanocrystals, also known as quantum dots (QDs), are
inorganic-organic hybrid nanomaterials which show a size-dependent optical transition due
to confinement of the exciton wave function. QDs of lead chalcogenides (PbSe, PbS or PbTe)
due to strong absorption in near infra-red, are one of the basic materials of modern infrared
optoelectronics. These truncated nanoparticles possess large exciton Bohr radii of for instance 150
nm for PbSe.
Colloidal semiconductor nanocrystals can be considered as building blocks for novel materials,
based on nanocrystal superlattices, obtained by colloidal crystallization of a suspension.
The aim of the project is to fabricate and optimize superlattices of semiconductor nanocrystals for
efficient light absorption, charge separation, transport and carrier collection. In a first step, wetchemistry synthesis of Pb-chalcogenide colloidal nanocrystals is conducted. Resulting nanoparticles
are submitted for an optical characterization (absorption and photoluminescence spectroscopy)
and Transmition Electron Microscopy to determine electronic structure, concentration, size, shape
and crystalline structure. In a second step, preparation of low dimensional superlattices of lead
chalcogenide quantum dots (QDs) attached via specific crystal facets occurs on an immiscible
liquid surface on which QDs suspension is drop casted whereby the solvent evaporates [1]. The
geometry of the superlattices is controlled by the temperature at which the solvent evaporates and
initial nanocrystal concentration. The symmetry of the supercrystals can be varied from linear to
ultra-thin sheets with a cubic and honeycomb superlattice structure (Figure 1).
15
Supervisor:
16
The physical properties of semiconductor Quantum Dots (QDs) are strongly influenced by their
size and shape. Therefore, control over these properties in the synthesis of QDs is crucial, especially
in nanoscience and nanotechnology. By changing the size of the quantum dot, the bandgap is
changed and thereby the optical en electronic properties [1,2].
Quantum dots can be formed by ions from group II and group VI [3]. Their wide use in different
fields relates to their particular photo-physical properties, such as broad absorption spectra, very
narrow emission spectra, long fluorescence lifetimes and high photo stability [4].
As the technician of the FOM-FNPS project I support the PhD-students and Postdocs within the
project concerning all synthesis issues.This year my work was focused on four topics (see Figure 1):
building a library of quantum dots (PbSe, PbS, CdSe, CdS, and CdS in different sizes), and synthesis
of PbS/CdS/CdOH, silica coated quantum dots [5], and core-shell structures (PbSe/CdSe, PbS/
CdS and CdSe/CdS/CdZnS/ZnS).
Figure 1: a-c) Different sizes and shapes of PbSe. d) CdSe/CdS/CdZnS/ZnS; e) PbSe in silica. F) CdSe/CdS rods in silica.
[1]
[2]
[3]
[4]
[5]
Supervisor:
17
Supervisor:
Single particle spectroscopy, Time-resolved laser spectroscopy, Small angle x-ray scattering (SAXS)
18
The optical properties of colloidal nanocrystals (NCs) can be tuned by control over size, shape, and
composition. As a result, NCs find application as light generators and/or absorbers for a variety
of devices and techniques. My research has focused on two topics: (a) the fundamental optical
properties of single NCs, and (b) the self-organization of NCs into superstructures. Until now, I
have mainly studied rod-shaped NCs (~4 nm x 20 nm) of CdS with a spherical CdSe core (~3 nm
diameter). Our optical studies have revealed that the negatively charged state of these nanorods
is much brighter than for their spherical CdSe/CdS counterparts (Fig. 1a). This is an important
property, since in high-intensity and single-photon applications random switching occurs
frequently to charged states with a low emission intensity. Moreover, using grazing incidence
small angle x-ray scattering (GISAXS) we have been able to follow the self-organization of the
nanorods into ordered membranes in real-time (Fig. 1b and Ref. 1). Based on our observations, we
have proposed that the orientation of the nanorods (i.e. lying or upright) in the final membrane
can be controlled by tuning the inter-nanorod interaction.
In the coming year, I intend to perform additional optical measurements on the nanorods at
higher excitation energies, as well as on different single fluorescent nanosystems. Furthermore,
new GISAXS experiments will be done on the nanorods to further test the self-organization
model we proposed.
h
200
=
100
0
10
Time (s)
random blinking
h
20
Scattering pattern
=
liquid
8.6 nm
Figure 1: a) We investigate the optical properties of single fluorescent nanorods which randomly switch between a highintensity neutral state and a lower-intensity charged state. b) We study the self-organization of nanorods at the
liquid/air interface in real-time using grazing incidence small angle x-ray scattering.
[1]
Supervisor:
Colloidal synthesis, Transmission Electron Microscopy (TEM), UV-Vis-NIR spectroscopy, X-ray powder
diffraction (XRD)
Over the past few years a lot of research has been performed on semiconductor nanocrystals and
their use in applications such as solar cells, batteries, LEDs and drug delivery. One of the major
drawbacks of the investigated materials is that they consist of toxic, heavy and/or scarce elements,
such as Cd, Pb, Te and Se. Subsequently, quite some research has already been performed on
ternary and quaternary compounds, such as CuInS2 (CIS) and CuInxGa1-xSe2 (CIGS) [1]. These
materials show exciting properties and performance in solar cells, but unfortunately still contain
the expensive and scarce elements Indium and Gallium. Due to this and other reasons, the interest
has shifted towards semiconductor nanocrystals that exhibit the same properties as CdTe, PbSe
and the relatively new CIS/CIGS compounds, but that consist of earth-abundant and non-toxic
elements. One example of such a material is Cu2ZnSnS4 (CZTS), a quaternary semiconductor
compound with a direct bandgap of about 1.5 eV, which is actually ideal for solar cells.
In this project the chemistry and physics behind the formation of ternary and quaternary
compounds are investigated in order to obtain control over size and shape of these nanocrystals.
For some years it has been possible to synthesize colloidal CZTS nanocrystals that are nearlyspherical but unfortunately very polydisperse in size and shape [2,3]. The synthetic methods used
to obtain these nearly spherical CZTS NCs are almost completely based on the hot injection
method, where the metal-precursors are dissolved in a coordinating solvent and the anion source
is rapidly injected into the hot solution. This method has been successfully applied to the synthesis
of different kinds of quantum dots of binary semiconductors, such as CdSe, PbSe, Cu2S, and
ZnSe, but for ternary and quaternary compounds this has proven to be much more difficult.
Therefore different synthesis strategies will be explored in order to obtain ternary and quaternary
semiconductor nanocrystals with a narrow size and shape distribution. Some of the synthetic
methods that will be investigated are the heating-up method, cation exchange, and core/shell
syntheses. The main characterization techniques that will be used are Transmission Electron
Microscopy (TEM), UV-Vis-NIR spectroscopy, Inductively Coupled Plasma Optical Emission
Spectroscopy (ICP-OES) and X-ray powder diffraction (XRD).
[1]
[2]
[3]
19
Supervisor:
Chemical vapour deposition (CVD), Luminescence spectroscopy, Focused ion beam, Confocal fluorescence
microscopy
20
The goal of this project is to demonstrate electrically driven ZnO based nanolasers with low
power requirements. Due to its high exciton binding energy of 60 meV, bandgap of 3.3 eV,
low cost, bio-compatibility and friendliness to the environment, nanolasers made of ZnO form
attractive candidates for applications in (bio)sensing, optical computing, white light emission
and high density storage. This project presents major challenges in the fields of semiconductor
synthesis and doping, as well as in the area of optical nanocavity formation. These challenges will
be met by using chemical vapour deposition (CVD) methods for the highly controlled synthesis
and doping of ZnO nanowires and thin films. ZnO nanowire crystals naturally form FabryProt and whispering gallery optical cavities whereas suitable optical resonators can be made
from thin films by consecutive lithography and focussed ion beam (FIB) etch steps. Intrawire p-n
junctions enabling electrical injection will be formed by either impurity or electrostatic doping.
Characterization of as grown wires entail spatially resolved single wire optical measurements such
as excitation spectroscopy and spectrally resolved Fourier microscopy, as well as (cryogenic) optical
measurements in the presence of on-chip applied fields. These measurements provide critical
information on light-matter coupling and polaritonic effects in these systems that can guide cavity
optimization and could potentially elucidate novel gain mechanisms such as polariton lasing.
Figure 1: Photograph of the laser emission from an optically pumped ZnO nanowire ( 200 nm, length 4 m). The
interference pattern is caused by the coherently emitted light from both ends of the nanowire which acts as a
Fabry-Prot optical cavity.
Supervisor:
Inorganic synthesis, X-ray powder diffraction (XRD), Optical spectroscopy (luminescence, absorption and
time resolved)
Luminescent materials with quantum yield (QY) exceeding unity are expected to play an important role in
future concept such as lighting,display,better utilization of solar energy and so on [1,2].In a photoluminescence
process, QY exceeding unity requires that, following excitation, more photons are emitted than those
originally involved in the excitation process. For instance, NIR quantum cutting (QC) refers to a process
where a high-energy ultraviolet (UV) or visible photon is cut into two or more NIR photons.
With respect to state-of-the-art Si-based solar cells,NIR-QC may enable a great increase in energy conversion
efficiency [3]. As of today, even for the most advanced technologies, this efficiency is physically (ShokleyQueisser) limited to about 30% for single-junction architectures.The reason for this lies in the fact that c-Si
solar cells effectively convert only photons with energy close to band gap of Si (~1.12 eV, corresponding to a
wavelength of 1.1 m) and that, additionally, even in the ideal case (e.g., no recombination), only one electron
can be generated from one photon, regardless the actual photon energy. Using down-conversion materials
to modify the high-energy part of solar spectrum is therefore of significant interest for various aspects. E.g.,
for the case of cutting one UV or blue photon into two NIR photons, the Shockley-Queisser limit can be
increased to about 40% for a single junction solar cell.
Down-conversion phenomena have been investigated in numerous materials co-activated by Ln3+Yb3+
(Ln=Tb,Tm, Pr, Nd and Er). However, in most of these cases NIR emission originates fromYb3+ only through
a first-order energy transfer from Ln3+ so that QC does actually not occur. Despite the importance of this issue,
it appears that there is presently no report on ultra-efficient three-photon NIR-QC in lanthanide ions singleand co-activated phosphor.Accordingly, the main mechanisms responsible for NIR-QC not well understood.
By means of hydrothermal reaction and the melting-and-quenching technique, we synthesize Ho3+
or Tm3+ doped NaYF4 phosphors and oxyfluoride glass ceramics containing CaF2 nanocrystals [4,5],
respectively. In terms of photoemission, monitored excitation and time resolved fluorescence spectra, it
can be demonstrated that: i) upon excitation with a UV photon, cascadic emission of three NIR photons
at 850, 1015 and 1180 nm takes place efficiently with 3K8,5F2 and 5I6 in Ho3+ serving as intermediate
levels; ii) as a blue photon of ~470 nm excites Tm3+ into the level 1G4, triply-cut NIR emissions at
1165, 1466 and 1800 nm occur with 3H4 and 3F4 acting as intermediate states. Notably, for Ho3+-doped
three-photon NIR-QC materials [6], codoping Yb3+ can increase the NIR emissions significantly
through the first- and second-step cross-relaxation, and an internal QY of 246% for the Yb3+ codoped
-NaYF4:Ho3+ is estimated on the basis of experimental data and theoretical considerations.
[1]
[2]
[3]
[4]
[5]
[6]
21
Supervisor:
Prof. dr. Andries Meijerink, dr. Celso de Mello Doneg, dr. Willem Mulder
22
Figure 1: a) Schematic representation of a quantum dot core and Cy5.5-lipid dual labeled micelle. b) Emission spectra
for QD-Cy7-PEG particles with increasing Cy7 dye lipids. c) In vivo Fluorescent imaging of tumor bearing mice
injected intravenously with QD-Cy7-PEG particles, observed in QD and FRET channel.
23
Supervisor:
24
The amount of bio-ethanol produced is increasing yearly, mainly for its use in fuels or as a fuel
additive. Furthermore, its importance as solvent and substrate makes ethanol a key chemical for
industrial and laboratorial applications.
1,3-butadiene is an important monomer in polymer chemistry, used for the production of e.g.
polybutadiene, ABS (Acrylonitrile-Butadiene-Styrene) and SBR (Styrene-Butadiene-Rubber),
the main component of car tires.
Currently, butadiene is obtained by steam cracking of fossil hydrocarbons. The Lebedev process
(Scheme 1) could constitute an important and environmentally friendly alternative way to produce
butadiene [1]. The recent increase in bioethanol availability if coupled with improvements in
catalyst design can make the Lebedev process an attractive alternative for butadiene production.
Screening studies show SiO2-MgO systems to be promising catalysts for this process. A strong
influence of catalyst preparation on morphology and performance was furthermore noted. In
addition, the addition of CuO (1 wt. %) led to a remarkable increase in the activity and selectivity
towards butadiene (see CuO / WK-MOD and CuO / WK-AER in Figure 1).
Figure 1: a) Butadiene yield with differently prepared CuO-containing catalysts with time on stream; b) product distribution
at the start and after 4 h reaction.
Main goals of this research are to be found in the elucidation of the relationship between structure
and function and thus to further improvement of the catalyst design.
[1]
Supervisor:
Nanoconfinement of MgH2 is a promising way to improve the hydrogen sorption kinetics and
reversibility [1]. Nanosizing enhances the surface area to volume ratio, favoring nucleation and
decreases the diffusion distance for H-atoms through Mg. Confinement of the nanoparticles
prevents sintering, so that the enhanced kinetics are maintained. We have synthesized Mg confined
in carbon aerogel (CA) by meltinfiltration. A similar system was studied with the addition of Ni and
Cu as catalysts to improve the kinetics [2]. We have used CAs with different pore size distributions
to investigate the effect of different particles sizes on the hydrogen sorption properties of MgH2
[3].
The hydrogen desorption profile of the Mg/CA composite (Fig. 1) shows multiple hydrogen
release events. This indicates that different types of Mg particles were obtained. After exposing the
sample to air, the peak at the lowest temperature shifted to a higher temperature, suggesting rapid
oxidation of small particles. Both peaks at the lowest and highest temperature remained upon
cycling.
Therefore, we have shown that Mg nanoparticles are present in the sample. These particles showed
faster hydrogen desorption kinetics. The properties are also maintained during cycling.
[1]
[2]
[3]
25
Supervisor:
The synthesis of methanol from a mixture of CO, CO2 and H2 is a large scale industrial process.
The produced methanol is mainly used as a building block for valuable products, like methyl tertbutyl ether (MTBE), acetic acid, methyl methacrylate (MMA), dimethyltryptamine (DMT) and
formaldehyde1). Methanol can also be converted into olefins via the methanol to olefins (MTO)
process. In turn, these olefins can then be used to produce polymers and related products. Methanol
can also be used to store energy2). The volumetric energy density of methanol is higher than of
hydrogen and methanol is easier to store and distribute since it is a liquid at ambient conditions.
26
Figure 1: a) Samples at different stages of a catalyst preparation process. From left to right we go from the bare support
to the active supported metal catalyst. b) Structural characterization on the nanoscale is done with electron
microscopy. c) The performance of the catalyst is determined at realistic industrial conditions.
[1]
[2]
[3]
[4]
Supervisor:
Zeolite HZSM-5 is a very relevant molecular sieve, used in many important conversion processes
in petroleum refineries. An example is the fluid catalytic cracking (FCC) process, where HZSM-5
is an additive to boost the octane rating in gasoline and propylene formation. Besides, HZSM5 is also used as a catalyst for the alkylation of aromatics with oxygenates, methanol and DME
conversion to light olefins, aromatics and fuels, and the dehydration of (bio-) alcohols. Therefore,
HZSM-5 is not just a catalyst for present day oil refining purposes, but also an important catalyst
for future green/clean fuel production processes.
Many of these catalytic processes are performed under severe hydrothermal conditions. In these
conditions, dealumination of the zeolite catalyst is favored. Dealumination leads to a rapid
deactivation of the catalyst. Therefore, it is of paramount importance that zeolites used in these
processes are hydrothermally stable or stabilized.
To prevent permanent deactivation, modification of zeolites by the addition of phosphorous is an
effective route to provide hydrothermal stability. Phosphorous modified HZSM-5 samples retain
their acidity and activity to a significant higher degree than their non-treated counterpart after
steam treatment and allows an enhanced temperature range for catalytic applications. This suggests
that phosphorous species formed in the treatment reinforce the zeolite HZSM-5 structure and
prevent dealumination.
During the course of this PhD research, a combination of spectroscopic techniques will be used to
follow different preparation routes of phosphorous modified zeolites in-situ and ex-situ. Operando
spectroscopy is applied in catalytic testing. Ultimately we hope to gain fundamental insight in the
structure-performance relationship of phosphorous modified zeolites.
Figure 1: a) Optical density map of Al K-edge X-ray absorption maps, corresponding to the particles thickness. Chemical
map of a cluster of P/HZSM-5 (60x60 nm spatial resolution, constructed from the Al K-edge spectra and P K-edge
stacks. b) Phosphorous K-edge spectra as found in different regions in the cluster. It can be observed that relative
higher amounts of phosphorous are in the thinner parts of the particle.
27
Supervisor:
28
The overall increase in global energy demand has resulted in increasing concern about climate
change. Consequently, finding alternative and more sustainable routes for energy production from
e.g. biomass has become more and more important.
Hydrogen has emerged as an attractive alternative energy carrier, for instance in hydrogen fuel
cells. Hydrogen can be sustainably produced from biomass-derived oxygenates by steam reforming,
partial oxidation, autothermal reforming, aqueous-phase reforming (APR) and supercritical water
reforming. Among these methods APR is very promising due to its low energy cost and suppressed
CO formation as a by-product. The production of hydrogen by APR of oxygenated hydrocarbons
over supported metal catalysts comes with significant challenges with regards to selectivity. The
products CO2 and H2 are unstable at low temperatures and readily give alkane and water by
Fischer-Tropsch and methanation reactions. Therefore, hydrogen selectivity plays a role of utmost
importance in the APR of oxygenated hydrocarbons.
In this PhD work, various renewable oxygenates including ethylene glycol, glycerol and sorbitol
have been used. The aim of the project is to study hydrogen generation from low temperature
reforming of oxygenated hydrocarbons derived from biomass.
Prof. dr. ir. Bert M. Weckhuysen and dr. ir. Javier Ruiz-Martinez
High prices of crude oil have generated great interest in the development of new catalytic
technologies that can be used for the conversion of natural gas, coal or biomass to transportation
fuels as well as bulk and fine chemicals. Alcohol-to-olefins can be an alternative way to produce
ethylene and propylene, which are important products for the chemical and petrochemical industry.
29
During the alcohols-to-olefins process the catalysts deactivated rapidly due to the formation of
aromatics and paraffins/coke compounds and their precursors in the pore system and on the
surface [1]. These compounds block the access of the reactants to the catalyst active sites as well as
products diffusion out of the pores. Therefore they influence the catalytic activity and selectivity
and this is a main reason of catalyst deactivation. Understanding and determining the factors,
which affect coke formation phenomena still remain ambiguous.
This research is towards the understanding of the coke formation phenomena, catalyst deactivation
and selectivity during the methanol-to-olefins (MTO) and ethanol-to-olefins (ETO) conversion.
UV Vis spectroscopy, confocal fluorescence (micro)spectroscopy, Raman spectroscopy techniques
will be applied in this project (Fig. 1).They will allow determining the type, rate of coke formation
and deactivation of catalysts. Formation of products using a variety of catalysts (i.e., H-SAPO-34,
SSZ-13 and ZSM-5) will be monitored by the simultaneous use of UV-Vis spectroscopy and GC
(Fig 1). The combination of both techniques will give the opportunity to establish a relationship
between the conversion, catalyst deactivation and selectivity.
[1]
Supervisors:
30
Many different materials have been studied with the aim of producing a material for reversible
hydrogen storage under practicable conditions for widespread application. One such material is
lithium nitride, Li3N, and its decomposition products, which initially garnered interest in 2002 [1].
This work will focus on producing carbon supported nanoparticles of Li3N or its decomposition
products with the aim of investigating the interactions within the Li-N-H system. Hopefully this
would help give further clarity as to the decomposition pathways involved. At the same time it
has been shown that nano-sizing has had beneficial effects on the thermodynamics of the systems
investigated by provoking decomposition at more mild conditions.
The first stage of this work is to devise a method for the preparation of a Li3N/carbon nanocomposite,
a feat which has only been documented in one instance to date [2]. However, this method makes
use of an explosive azide precursor which gives rise to obvious safety concerns. A promising
alternative route is by solution impregnation with butyllithium and subsequent decomposition at
around 150 C under hydrogen to produce LiH. Further decomposition under nitrogen to form
lithium metal followed by Li3N would hopefully yield the desired product. A similar method has
been successfully applied to the analogous dibutylmagnesium in the past [3].
The second stage would be to use the carbon-supported nanoparticles to investigate the
interactions between lithium, nitrogen and hydrogen in order to better understand mechanisms of
each decomposition step. Next to lithium-based systems, other light metals such as magnesium are
also of interest, as well as various alloys involving light metals.
P. Chen, Z. Xiong, J. Luo, J. Lin and L. Tan, Nature, 2002, 420, 302.
R. Demir-Cakan, W. S. Tang, A. Darwiche and R. Janot, Energy Environ. Sci., 2011, 4, 3625.
S. Zhang, A. F. Gross, S. L. Van Atta, M. Lopez, P. Liu, C. C. Ahn, J. J. Vajo and C. M. Jensen, Nanotechnology, 2009, 20, 204027.
Supervisor:
AFM-Raman, Tip Enhanced Raman Spectroscopy, Atomic force microscopy, Colloidal Synthesis
Scanning Probe Microscopy has become a very powerful analytical field for many research areas
ranging from UHV low temperature surface science to biological experiments. Atomic Force
Microscopy (AFM) and its derivatives are however not very well explored in heterogeneous
catalysis research. Combination of AFM and Raman scattering, which could give more insight on
for example the chemical nature of catalyst surfaces, could be one of the possibilities to change
this. Because Raman scattering often only yields very weak signals, signal enhancement is a vital
point. This enhancement is induced by local (strong) electric fields which can be generated by
the interaction of light with the electron cloud on the surface of nanoscaled noble metal surfaces
(Au, Ag, Cu): a plasmonic effect. In this way the signal is predicted to be enhanced by a factor
103 till even 1014 [1]. When used in spectroscopy the technique is named after the effect: SERS
(Surface Enhanced Raman Spectroscopy). In so-called Tip Enhanced Raman Spectroscopy (TERS) one
makes use of this effect by coating the AFM-tip with one of the previously mentioned metals
with nanoscaled corrugation. Because the enhanced Raman signal is a very local effect - in this
case determined by the diameter of the metal colloid on or near the tip apex (down to ~10 nm
[2])- the spatial resolution of the Raman signal is also brought down well below the diffraction
limit. Although this spatial resolution is certainly not higher than that of AFM on its own, which
has shown to be able to even distinguish bond orders of single atoms [3], the combination gives
the possibility to monitor for example reactions by tracking the changes in e.g. morphology, phase
(AFM) and/or the spectra (Raman) [4]. This project is focused on the possibilities to use the
combination of techniques under in-situ conditions for example for catalyzed reactions and crystal
growth of (thin films of) porous materials such as Metal Organic Frameworks MOFs (so called
surMOFs). This would yield a real extension into the field of heterogeneous catalysis.
Figure 1: A schematic representation for a combined AFM and Raman experiment, assuming the sample to be transparent.
[1]
[2]
[3]
[4]
Blackie, E. J., Le Ru, E. C., Meyer, M., Etchegoin, P. G., J. Phys. Chem. C 2007, 111, 13794;. K. Kneipp, Y. Wang, H. Kneipp, et
al., Phys. Rev. Lett. 1996, 76, 2444.
Yang, Z., Aizpurua, J., Xu, H., J. Raman Spectrosc. 2009, 40, 1343.
Gross, L., Mohn, F., Moll, N., et al., Science 2012, 337, 1326.
Schrojenstein Lantman, E., Deckert-Gaudig, T., Mank, A.J.G., Deckert, V. and Weckhuysen, B.M., Nature Nanotechnology
2012, 7 583.
31
32
The Fischer-Tropsch synthesis is a powerful route for the direct conversion of synthesis gas
into hydrocarbons, which is a highly demanded process in industry for the production of fuels
and chemicals. Iron-based catalysts are promising candidates for the production of lower olefins
under FTO (Fischer-Tropsch to olefins) conditions, since they show good activity and sufficient
selectivity towards C2-C6 olefins. Nevertheless, the actual development of commercial processes
requires improved performances of the catalyst in terms of mechanical stability at temperatures
above 300 C. In addition, understanding of key mechanisms, like promotor- and deactivation
effects, are strongly needed.
In this work we aim at fabricating iron-based catalysts consisting of iron/ iron carbide nanocrystals
(NCs) supported by carbon nanotubes (CNTs). Nanoparticles with controlled size, shape and
composition in the active carbide phase are fabricated by colloidal synthesis approach, while
NC-CNT composites are obtained by replacement of NC surface ligands with the CNT, both in
situ and post-synthesis.
For optimal performance particles must be uniformly distributed and maximally spaced at the
C-support surface, in order to improve the mechanical stability of the catalyst and avoid NC
sintering and attrition which take place at the high temperatures required under FTO conditions.
Optimization can be done by combining colloidal synthetic expertize with nano-composite
characterization by TEM, electron tomography, XRD.
The use of carbon-supported catalysts with fine distribution of small (2-5 nm) iron particles is
expected to strongly reduce the catalyst deactivation by decreasing the rate of carbon deposition
under FTO conditions.
Supervisor:
The Fischer-Tropsch process is an attractive way to convert synthesis gas (a mixture of CO and H2)
to hydrocarbons. As such, it is an important step in the conversion of biomass, coal or natural gas
to high-quality fuels and chemicals. Industrially, the Fischer-Tropsch can be done over a supported
cobalt catalyst.
However, deactivation of the cobalt catalyst is an obstacle for industrial application. One of the
main causes for cobalt catalyst deactivation is sintering, the growth of supported cobalt nanocrystals
into bigger crystals. This decreases the surface area of the cobalt particles that is available for
catalyzing the reaction. Unfortunately, the mechanism for the sintering process is currently only
poorly understood. As a consequence, our possibilities for increasing the stability of the catalyst
are limited.
We are trying to improve the understanding of the sintering process by studying the catalyst with
synchrotron-based X-ray microscopy techniques. Recent advances in full-field Transmission X-ray
Microscopy allow us to study the catalyst under industrial reaction conditions [1]. The microscope
gives 2-dimensional chemical information via spatially resolved X-ray Absorption Near-Edge
Spectroscopy. Additionally, it is possible to do element specific X-ray nanotomography. This will
allow us to visualize the 3-dimensional distribution of cobalt over the catalyst support (see Figure
1). This gives us insight into the mechanism of sintering.
Figure 1: 3-dimensional representation of a Fischer-Tropsch catalyst particle. Contributions from the support are shown
in red; contributions from cobalt are shown in blue. The surrounding box is 9.4 m by 8.6 m by 11.3 m.
[1]
I. D. Gonzalez-Jimenez, K.H. Cats et al., Angewandte Chemie International Edition, 2012, 124, 12152
33
Supervisor:
34
Figure 1: PE chain growth (upper path) and PE chain termination (lower path) [2].
[1]
[2]
[3]
E. Groppo, C. Lamberti, S. Bordiga, G. Spoto, A. Zecchina, Chem. Rev. 105 (2005) 115
M.P. McDaniel, Adv. Catal. 53 (2010) 123-606
B.M. Weckhuysen, I.E. Wachs, R.A. Schoonheydt, Chem. Rev. 96 (1996) 3327
Supervisor:
The Fischer-Tropsch (FT) reaction, the catalytic conversion of syngas into higher hydrocarbons,
has been an intense area of research against the background of depleting crude oil resources.[1]
Catalytic performance, physical and chemical properties, promoters and particle size effects of
supported Co-FT-catalysts have been studied extensively in this group before and highly active
catalysts have been developed.[2]
Supported catalysts can be prepared by Incipient Wetness Impregnation (IWI), where the pores
of a support material are filled with a solution of the metal precursor. After removing the solvent
and a suitable calcination procedure, this method can lead to highly dispersed metal nanoparticles.
However, clustering of metal nanoparticles is observed and the maximum loading is limited by
pore volume of the support material and solubility of the metal salt. In Homogeneous Deposition
Precipitation (HDP), the support material is suspended in a solution of the metal precursor. By
changing the pH of the solution, e.g. by hydrolysis of urea[3] or by evaporating ammonia[4],
interfacial deposition of metal species can be induced. These methods are suitable for the
preparation of highly dispersed supported nanoparticles and high metal loadings.
In this project, we study the influence of different preparation methods and metal loadings on
the structure and catalytic performance of Co/TiO2 catalysts. The properties of the catalysts are
analyzed using TEM, TPR, H2-chemisorption and XRD. The Fischer-Tropsch performance of the
catalysts in the under industrially relevant conditions is tested in an Avantium Flowrence 16reactor
system, while our special focus is on studying the longterm stability of the prepared systems.
Figure 1: Co/TiO 2 catalyst prepared using different methods. IWI (left), urea hydrolysis HDP (middle) and ammonia
evaporation HDP (right).
[1]
[2]
[3]
[4]
35
Supervisor:
36
Solid bases are currently investigated for several applications such as heterogeneous catalysts or
CO2 capture materials. CO2 is a greenhouse gas which at the moment is gaining much interest
due to environmental concerns. CO2 free chemicals and fuels are of huge interest for the future
society. However, the currently ever increasing use of fossil energy in the world brings about the
emission of large amounts of carbon dioxide into the atmosphere which is a problem that should
be address here and now. Carbon Capture and Storage is one option to mitigate CO2 emissions [1].
CO2 capture can be divided in two classes. One method is pre-combustion capture which involves
CO2 trapped at high temperatures (523- 773 K) accompanied by the production of hydrogen, for
example via the water-gas shift reaction (CO + H2O CO2 + H2). The other method is removal
of CO2 from flue gas streams, e.g. from power plants, at low temperatures (373- 423 K) which
is referred to as post-combustion capture. For the latter, amine based scrubbers are currently the
commercial option [2, 3]. The use of amines, however, requires the use of special reactor materials
due to their corrosive nature [2]. Other drawbacks of amines are their limited stability during
operation, toxicity and need of a solvent (water) to prevent foaming and to keep the viscosity low
[3]. The use of water as solvent makes the regeneration (desorption of CO2) energy intensive, since
a considerable amount of energy is used for evaporating the water to release the entrapped CO2. In
this study we want to develop novel regenerable solid bases as sorbents for the CO2 capture being
attractive alternatives to the amine based materials.
Figure 1: Schematic picture of possible CO2 capture and storage systems, adapted from Courtesy of CO2CRC.
[1]
[2]
[3]
IPCC, Climate Change 2007: The Physical Science Basis (Cambrigde Univ. Press, Cambridge, 2007).
Fauth, D. J.; Frommell, E. A.; Hoffman, J. S.; Reasbeck, R. P.; Pennline, H. W. Fuel Processing Technology 2005 86, 1503.
Rinker, E. B.; Ashour, S. S.; Sandall, O. C. Industrial & Engineering Chemistry Research 2000, 39, 4346.
Supervisor:
Assoc. Prof. dr. Petra E. de Jongh and Prof. dr. Krijn P. de Jong
Complex light metal hydrides have attracted much attention as hydrogen storage alternatives,
owing to the relatively safe operation conditions and high hydrogen content. However, the
sluggish H2 release kinetics and poor reversibility limit the practical application. Recent studies
showed that nanosizing and confining complex metal hydride in a porous matrix improved the H2
release kinetics and enabled partial reversibility of H2 desorption under moderate rehydrogenation
conditions [1]. The enhanced H2 sorption properties in nanoconfined hydrides are proposed to be
partly related to a catalytic effect of matrix, e.g. graphitic carbon [2].
In the present study, we discuss the impact of the nature of interface between carbon and NaAlH4
(LiBH4) on the H2 sorption properties of nanoconfined hydrides.The carbon surface was modified
either to apolar and hydrophobic by removing oxygen-containing groups or to polar and acidic
by introducing extra oxygen-containing groups. If a true catalytic effect is present, H2 sorption
properties is expected to be influenced by the nature of surface. However, no significant change
on the H2 release temperature from NaAlH4 is observed. Importantly, a large impact on the
reversibility is found: in the case of NaAlH4, almost full reversibility (95%) is achieved if most
oxygen-containing surface groups are removed, while the reversibility is only 66% for surface
oxidized carbon. The low reversibility is attributed to the loss of active phase due to reaction
with oxygen-containing surface groups [3]. Our study clearly shows the importance of the purity
of carbon matrix for the reversibility. Full reversibility of H2 desorption of confined hydrides is
possible by purifying the carbon matrix or compensating the loss by the addition of extra active
phase.
[1]
[2]
[3]
37
Supervisor:
Prof. dr. ir. Krijn P. de Jong and dr. Johannes Hendrik Bitter
38
Aqueous phase reforming (APR) of renewable carbohydrates is an attractive process for the
sustainable and economical production of H2. The generated H2 can be used for efficient power
generation in a PEM fuel cell. In collaboration with the TUE we aim for the development of
a compact power producing unit for portable applications by using APR with microreactor
technology and an integrated fuel cell.
In the APR process biomass derived oxygenated hydrocarbons are converted into H2 and CO2 at
around 500 K using heterogeneous metal catalysts.
So far the process has been most successful using expensive platinum based catalysts and glycols
as feedstock [1]. This research focuses on the development of a stable, non noble metal catalyst
for the efficient and selective production of H2 from various biomass feeds. The most promising
catalyst can be integrated in the microreactor system at the TUE to demonstrate the applicability.
We have investigated Carbon Nanofiber (CNF) supported nickel catalysts with a focus on the
effect of the reaction conditions on their hydrothermal stability.
These catalysts were tested for the APR of ethylene glycol (EG) both in the presence and absence
of KOH with an initial Ar or H2 atmosphere in a high pressure batch autoclave at 230 C for
6 hrs. XRD analysis of the fresh and spent catalysts (fig. 1) shows that when KOH is added
to the EG feed no growth of nickel crystallites occurs while at the same time the amount of
soluble nickel species is negligible. Contrary, a significant increase in the crystallite size is found
in the experiment without KOH addition. This also corresponds to high amounts of leached
nickel. Furthermore chemisorption experiments (fig. 1) show that the amount of activate sites of
a spent catalyst for the reactions under Ar atmosphere is considerably less than the fresh catalyst
(160 m_mol H2/g). With the addition of KOH the loss of active sites in the spent catalyst is
very limited. Thus, suppressing formation of soluble nickel species and thereby preventing nickel
particle growth is key in stabilizing nickel catalyst under hydrothermal conditions.
Figure 1: H2 uptake (left) and crystallite sizes (right) for spent catalysts after aqueous phase reforming of 1 and 10 wt%
EG at 230 C with initial Ar and H2 (6 bar) atmosphere and the addition of 0.5 M KOH.
[1]
R.R. Davda, J.W. Shabaker, G.W. Huber, R.D. Cortright, J.A. Dumesic, Appl. Catal. B 2005, 56, 171.
Supervisor:
Raman Spectroscopy, Atomic Force Microscopy (AFM), AFM-Raman, Surface Enhanced Raman Scattering
(SERS)
Supported metal nanoparticles are important heterogeneous catalysts in many industrial processes.
A thorough understanding of which specific surfaces have the highest catalytic activity is required
in order to tune the shape and size of nanoparticles to reach the maximum catalytic activity. [1]
Raman spectroscopy has proven to be a powerful and versatile tool for the study of chemical
reactions, but lacks sensitivity under normal measurement circumstances. The use of surface
enhancement makes Raman spectroscopy a much more sensitive and versatile tool for the study of
chemical reactions. Surface Enhanced Raman Scattering (SERS) occurs principally on roughened
noble metal surfaces or noble metal NPs, and allows chemical imaging of adsorbate-surface
interactions with high sensitivity. This makes it uniquely suited for investigations of reactions at a
catalytic surface. The integration of Atomic Force Microscopy (AFM) with Raman spectroscopy
forms a powerful new tool for nano-scale chemical imaging of catalytic solids, allowing nano-scale
morphological features to be correlated directly to chemical information.[2,3]
My studies are currently focusing on using integrated AFM-Raman measurements to study the
Surface Enhanced Raman Scattering (SERS) phenomena of supported nanoparticles under in-situ
conditions, and investigating methods of increasing the applicability of SERS for heterogeneous
catalysis investigations.
Figure 1: Overlapping AFM and Raman images of agglomerations of Ag NCs and Rhodamine-6G (Rh6G) on an Al2O3 wafer;
(A) AFM height image of surface; (B) AFM magnification of an area over which Raman intensity was followed
(scale bar = 200 nm); (C) Raman spectra followed over time from (B); (D) Raman intensity map of the Rh6G band
at 1512 cm-1.
[1]
[2]
[3]
39
Supervisor:
Prof. dr. ir. Bert M. Weckhuysen and dr. Pieter C.A. Bruijnincx
Hydroisomerization is an important process in refining that is used to increase the octane number
of hydrocarbons. For fuels, a higher octane number improves combustion properties while for
waxes physical properties are improved. For this purpose, bifunctional catalysts are used, consisting
of a zeolite loaded with a noble metal such as palladium or platinum. The noble metal provides
the hydrogenation-dehydrogenation functionality while the zeolite provides the acid functionality.
40
The mechanism by which hydroisomerization takes place is generally accepted to consist of alkane
dehydrogenation over a noble metal site to form an alkene, followed by alkene protonation by an
acid site to form a carbenium ion which can undergo skeletal rearrangement to form isomerized
alkene products. Finally, hydrogenation leads to the isomerized products. This mechanism implies
diffusion of intermediates between active sites. There is, however, no direct evidence that this is
indeed taking place.
In this project, fluorescent acetylene-derived molecules will be used to probe the two types of active
sites simultaneously (Figure 1). Figure 1A shows the hydrogenation of substituted diphenylacetylene
(a) over metal sites, giving fluorescent stilbene derivatives (b).[1] Figure 1B depicts phenylacetylene
(c) hydrogenation to styrene derivatives (d) which can undergo dimerization to form fluorescent
dimers (e).[2] These probes will be visualized using UV-vis microspectroscopy as well as confocal
fluorescence microscopy.
B.M. Choudary, M.L. Kantqam, N.M. Reddy, K.K. Rao, Y., Haritha, V. Bhaskar, F. Figueras, A. Tuel, Appl. Catal. A: General 1999,
181, 139.
I.LC. Buurmans, E.A. Pidko, J.M. de Groot, E. Stavitski, R.A. van Santen, B.M. Weckhuysen, Phys. Chem. Chem. Phys. 2010,
12, 7032.
Supervisor:
Figure 1: Left: Positive ion intensity maps of a large H-ZSM-5 crystal after repeated Cs+-sputter/Bi3++-imaging cycles. Upper
right: High resolution ToF-SI mass spectrum of H-ZSM-5. Lower right: Cumulated relative enhancement of CxHy+
fragment ions after MTH reaction, influence of MTH reaction temperature (350 C, blue diamonds; 500 C, green
triangles) and ageing (MTH reaction at 350 C, ageing for 14 h at 350 C under N2, red squares).
41
Supervisors:
Prof. dr. ir. Bert Weckhuysen and dr. Pieter C.A. Bruijnincx
42
Lignin is a major (18-40 wt%) component of lignocellulosic biomass and will thus form an
important process stream in future biorefineries that can provide society with a sustainable source
of fuels and chemicals. The structure of lignin is best described as a three-dimensional cross-linked
polymer of oxygenated phenylpropane units. Although this is a potentially valuable source of
aromatics and other functionalised hydrocarbons, the complex structure also poses problems with
depolymerisation and further processing of the product mixture. [1]
My project aims to develop new catalytic systems for the depolymerisation of lignin and
converting the products into value-added bulk chemicals and fuel components. Emphasis will
be on convergent conversion of depolymerisation products into a limited number of platform
molecules and value-added bulk chemicals. One potential route for the valorisation of catechol,
which can be readily obtained from lignin, is intradiol dioxygenation towards muconic acid. This
acid is readily hydrogenated over a Pt/C catalyst to obtain adipic acid, an important bulk chemical
consumed on a billion kg/year scale for the production of nylon.
Intradiol catechol dioxygenases are a class of enzymes containing a non-heme ferric center, which
catalyse the intradiol dioxygenation in nature. The dioxygenation of various ferric catecholato
complexes has therefore been extensively studied as functional models for these enzymes. However,
the catalytic conversion of catechol has so far received little attention. [2] Recently we have shown
that the catalytic dioxygenation of catechol proceeds readily using a ferric tris(2-pyridylmethyl)
amine (tpa) catecholato complex at 50 C and ambient pressure, to obtain O-methyl-cis,cismuconic acid as the primary product (figure 1). Although the activity still is rather low, the
regioselectivity is excellent as only the C1-C2 bond is cleaved. With further improvements in
activity, the catalytic dioxygenation of catechol may thus provide a promising method for the
valorisation of lignin depolymerisation products.
Figure 1: The dioxygenation of catechol (left) with the ferric tpa catecholato complex (centre) in methanol yields O-methylcis,cis-muconic acid (right) as the main product.
[1]
[2]
J. Zakzeski, P.C.A. Bruijnincx, A.L. Jongerius, B.M. Weckhuysen, Chem. Rev. 2010, 110, 3552
P.C.A. Bruijnincx, G. Van Koten, R.J.M. Klein Gebbink, Chem. Soc. Rev. 2008, 37, 2716
Supervisor:
[1]
[2]
[3]
43
Supervisor:
44
X-ray absorption spectroscopy (XAS) is a powerful tool for fundamental studies on isolated
molecules as well as for the characterization of solid materials. XAS has the advantage of site
specificity, allowing the selection of different core level edges of interest, and detailed information
on the electronic and structural environment of a particular element in a given compound can
be obtained [1]. The advances in the experimental field have enabled the measurement of the
transition metal absorption edges with great accuracy. However, the theoretical description
of the spectra at the ab initio level is still a challenge. The single particle description of X-ray
absorption works well for all K edges and calculations based on multiple scattering [2] and band
structure approaches [3] are applied to systems such as transition metal oxides with excellent
agreement, whereas for the other edges, in particular the metal L2,3 edges, the agreement is poor.
The reason for this discrepancy is the strong overlap of the core wave function with the valence
wave functions [1]. A successful method to analyze these 2p-3d transitions is based on a ligandfield multiplet model [1,4,5,6]. Recently this approach has been used to compare the calculated
Fluorescence YieldXAS (FY-XAS) spectra, which are obtained from the integrated 2p3d resonant
x-ray emission spectra, with the normal XAS spectra for a series of transition metals and we
have obtained a significant deviation of the FY-XAS signal [7]. This implies that the assumption
that the FY-XAS spectrum identifies with the XAS spectrum is disproved. This has important
implications, for example for Magnetic Circular Dichroism (MCD) and we are working on its
analysis. This study will have inferences on the FY-MCD sum rules for estimating the magnetic
and spin moments of materials.
The focus of the project also include 1) understanding the role of core-hole on the oxygen K
edge of transition metal oxides within the scope of band structure calculations, 2) validating
the newly developed multi-reference approach for XAS [8] for transition metal systems and
potentially linking this approach to the charge transfer multiplet program, in order to reduce its
semi empirical nature.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
Core level Spectroscopy of Solids (Taylor & Francis, New York, 2008).
Rev. Modern Phys. 2000, 72, 621.
Phys. Rev. B 2002, 66, 195107.
Chem. Phys. Lett. 1988, 149, 295.
Phys. Rev. B 1990, 42, 5459.
Micron 2010, 41, 687.
J. Phys. Cond. Matt. 2012, 24, 452201.
J. Phys. Chem. Lett. 2012, article in press.
Supervisor:
The emission of nitrogen oxides (NOx), produced through the combustion of fossil fuels, is a major
concern for todays society, and is subject to stringent environmental and public health protection
regulations. During the last years, Selective Catalytic Reduction (SCR) of NOx with NH3 has
emerged as a very efficient technology for the abatement of NOx emissions in diesel vehicles.
Furthermore, several zeolite materials of varying topology and with different transition metal ion
(TMI) components have been investigated as catalyst materials for the NH3-SCR reaction, with
Cu-SSZ-13 exhibiting a very high activity and stability under SCR conditions.
The overall objective of this project is the elucidation of the identity and nuclearity of active Cusites, as well as the study of the influence of pore dimensions in the catalytic activity.To tackle these
issues UV-Vis, synchrotron-based IR and luminescence micro-spectroscopy at the single particle
level will be used to investigate the influence of zeolite topology (small, medium and large pore
zeolites), chemical composition and preparation method on the catalytic chemistry, to understand
the spatiotemporal heterogeneities within an active zeolite catalyst particle and to elucidate the
interfacial cooperation between Cu centers and acid functionalities.
45
Supervisors:
46
Ordered mesoporous silica has large surface area, uniform pore size and tunable periodic structure.
These properties make these materials attractive in various fields, for example: drug delivery,
sensors, separation and catalysis. Mesoporous silica is a promising material as support for nanoreactors in catalysis because silica is able to form many different pore structures, such as 2D and
3D mesostructures[1]. Nano-reactors are small involucres, cavities or partially blocked pores where
chemical reactions can take place. This physical barrier selects molecules which an appropriate size
for entering and leaving the reactor.
In catalysis, many efforts have been spent to disperse and stabilize metal nanoparticles inside
mesoporous silica. The synthesis of metal nanoparticles with good dispersion and a high thermal
stability has been showed extremely difficult. The stabilization of these particles is very important
to avoid mobility and leaching of metal and as consequence growth of particles and loss on catalyst
activity[2].
In this research project, we are investigating the synthesis of SBA-15 and Plugged SBA-15. Plugged
SBA-15 is a mesoporous silica in which the mesopores are partially closed[3], producing nanocavities
inside of its structure.This mesoporous material has a higher mechanical strength and thermal stability
than MCM-41 and SBA-15, this fact makes them a good candidate for industrial applications.
In these materials, we deposit nanoparticles of palladium (Figure 1) for application in carboncarbon coupling reaction, for example the Heck and Suzuki reactions. These particles present in
nanoconfined spaces are more resistant for leaching and mobility avoiding the formation of large
particles and loss of catalyst activity after performance.The characterization of these materials will be
done using techniques, such as electron microscopy, N2 physisorption, X-ray diffraction and others.
Supervisor:
TEM, STXM
Catalysts containing cobalt oxides are important for low temperature carbon monoxide oxidation,
nitrogen monoxide reduction and water splitting reactions. The mechanisms of these reactions,
although been researched for many years, still leave many uncertainties.
Cobalt oxides will be prepared both with chemical routes on oxide supports and also with
colloid synthesis routes. We aim to understand the morphology, geometric and electronic
structure information by applying Scanning Transmission X-ray Microscopy (STXM). STXM is
a combination of X-ray microscopy and X-ray Absorption Spectroscopy (XAS). STXM allows
the study of the morphological and chemical information of the cobalt containing catalyst under
reaction conditions (in-situ), at elevated temperature and under reactive gas atmosphere. In addition
we will apply Transmission Electron Microscopy in combination with STXM using the same
nanoreactor cells.
47
Supervisors:
GC, GC-MS, ATR-IR, XRD, TEM, BET, TPD-NH3, N2 Physisorption, AAS, NMR
Levulinic acid (LA) has been identified as a promising, renewable platform molecule that can
be converted by catalytic hydrogenation/deoxygenation to other valuable chemicals, such as
-valerolactone (GVL), methyltetrahydrofuran (MTHF), 1, 4-pentanediol (PD) and pentanoic acid
(PA) or its esters (PE) [1, 2]. The products can be used as renewable fuels, additives, solvents and
chemical building blocks (Figure 1).
Angelicalactone (AL)
O
-H2O
48
-H 2O
H2
H2
O
OH
OH
OH
Methyltetrahydrofuran
(MTHF)
1,4-Pentanediol (PD)
O
Levulinic acid (LA)
O
H2
OH -H 2O
Valerolactone
(GVL)
OH
4-Hydroxy-pentanoic acid (HPA)
H2
O
OH
OH
Pentenoic acid isomers
(PEA)
Pentanoic acid
(PA)
J. Q. Bond, D. M. Alonso, D. Wang, R.M. West, J. A. Dumesic, Science 327, 1110 (2010).
J.-P. Lange, R. Price, P. M. Ayoub, J. Louis, L. Petrus, L. Clarke, H. Gosselink, Angew. Chem. Int. Ed. 49, 4479 (2010).
ERC (FP-7; Marie Curie Intra European Fellowship), since May 2011
Supervisor:
The principal goal of this project is to develop efficient supported bimetallic nanoalloy based
catalysts for the valorisation of biomass to produce bulk/speciality chemicals effectively in
an environmentally benign route.[1] As a part of this project, we use catalysed oxidative
dehydrogenation of bio-renewable benzylic alcohols (e.g., veratryl alcohol, vanillyl alcohol and
cinnamyl alcohol) as a substrate activating strategy for the synthesis of amines, benzimidazoles,
and as a general strategy for the N-alkylation of amines in a single pot without using any external
hydrogen or any soluble base [Scheme 1]. [2]
49
[1]
[2]
J. Zakzeski, P. C. A. Bruijnincx, A. L. Jongerius and B. M. Weckhuysen, Chem. Rev. 110 (2010) 3552-3599.
G. Guillena, D. J. Ramon, M. Yus, Chem. Rev. 110 (2010) 1611-1641.
Supervisor:
50
While the current world economy is highly reliant on crude oil for the production of fuels and
chemicals, the natural oil reserves are dropping and will eventually run out. Moreover, there is
an increased demand in high quality products free of contaminants like nitrogen, sulphur and
aromatics. For this reason, converting other feedstocks such as coal, natural gas and biomass into
hydrocarbons and other chemicals is an important field of research. These feedstocks can be easily
converted to syngas, H2 and CO, which can then be used as reactants in the Fischer-Tropsch
synthesis. In this process, the syngas is converted into clean hydrocarbons ranging from methane
to hard waxes through the use of a heterogeneous catalyst.
Highly loaded cobalt catalysts supported on silica or alumina have been found to be highly active
and selective towards long paraffinic chains for this reaction. However, inhomogeneous cobalt
distributions are often obtained after catalyst preparation, and as a result sintering of the cobalt
particles during the Fischer-Tropsch synthesis is a major cause of catalyst deactivation. Our goal
is to gain full control of the cobalt particle dispersion and distribution by studying synthesis
conditions such as drying, calcination, cobalt precursor and support-precursor interactions in
order to make the most stable and active catalysts.
By creating cross-sections of as-synthesized catalyst particles using ultramicrotomy we study the
distribution of the cobalt phase throughout particles on both the nano- and microscale using
TEM, STEM and 3D-TEM. In-situ spectroscopic techniques are used to study the decomposition
of cobalt precursors treated under different conditions, and catalysts are tested under industrially
relevant conditions to elucidate the effect of different cobalt distributions on the activity, selectivity
and stability of the catalysts.
Figure 1: 50 nm cross-sections of catalyst particles showing different degrees of 10 nm Co3O4 nanoparticle clustering
(black) on -Al2O3 (grey).
Nanoconfined borohydrides
Angeloclaudio Nale, ac.nale@uu.nl, phone: (+31)622736392
Sponsor:
Supervisor:
The possibility of a safe and effective storage for hydrogen gas is a key requirement for its
implementation as energy carrier in everyday life applications.
Complex hydrides are a promising class of materials for solid state storage; among these
lithiumborohydride shows a high H2 content but the elevated temperatures required to release the
gas and cycle are an important obstacle for practical application [1].
Nanosizing is a well known technique to reduce the decomposition temperatures and enhance
reactions kinetics of metal hydrides, thanks to large fraction of surface atoms and to reduced
diffusion distances [2].
Taking advantage of the low melting temperature of LiBH4 we can infiltrate it into porous scaffolds
[3]; DSC allowed us to observe that nanosizing decreased not only the melting temperature
and enthalpy of LiBH4 but also the LiBH4 solid-solid phase transition. The temperature of this
transition is important, as it marks the change from a low-temperature orthorhombic structure to
a hexagonal phase which is characterized by high ionic and hydrogen mobilities.
The transition temperature depends strongly on pore size, but also on the chemical nature of the
porous scaffold (e.g. the use of scaffolds of different materials, carbon or silica, in Figure 1). Quasi
Elastic Neutron Scattering (at PSI,Villigen, Switzerland in collaboration with EMPA) highlighted
changes in hydrogen dynamics due to nanoconfinement. NMR performed at Radboud University
(Nijmegen, The Netherlands) shows increased Li+ mobility for nanoconfined LiBH4 even at low
temperatures.
Understanding the effect of confining materials in nanopores allows tuning physicochemical
properties, relevant for a range of applications such as in reversible hydrogen storage, and Libattery solid state electrolytes.
Figure 1: Calorimetric measurements of phase transitions for LiBH4 confined in thenanopores of silica and carbon materials
with different diameters during heating. Dashed lines indicate phase transitions temperatures for bulk LiBH4.
[1]
[2]
[3]
51
Supervisor:
Selective catalytic reduction (SCR) using ammonia or hydrocarbons as reducing agents is a very
effective way to remove NOx from the exhaust of engines. Small pore zeolites loaded with Cu2+
-ions are extremely active in the SCR of NO with NH3 at low reaction temperatures. [1] The
newly discovered catalyst materials (that is, Cu-SAPO-34 and Cu-SSZ-13, both having CHA
structure) clearly outperform the earlier investigated catalysts, involving Cu2+ -containing medium
(e.g. Cu-MFI) and large pore (e.g. Cu-BEA) zeolites. [2]
52
Unfortunately, no mechanistic insight is yet available on the identity and nuclearity of these active
Cu2+ sites and the influence of the zeolite acidity and porosity on the overall catalytic performance.
The aim of this research project is to develop a new combined in-situ UV-Vis and luminescence
micro-spectroscopy set-up to explain in space and time the identity, redox behavior (Cu+ possesses
luminescence character) and nuclearity of the active centers in micron-sized Cu-zeolite crystals
at the single particle level.
By combining this approach with the recently developed methods of in-situ synchrotron-based
IR micro-spectroscopy we aim to identify reaction intermediates and correlate activity/selectivity
with zeolite architecture and pore accessibility. [3]
Insight into the zeolite topology and their hydrothermal stability will be obtained by comparing
Cu-CHA, Cu-MFI and Cu-BEA zeolites after synthesis, lean hydrothermal ageing and severe
hydrothermal ageing.
[1]
[2]
[3]
U. Deka, I. Lezcano-Gonzalez, S. J. Warrender, A. Lorena Picone, P. A. Wright, and B. M. Weckhuysen, and A. M. Beale,
Microporous and Mesoporous Materials, 166, 144152 (2013).
J. H. Kwak, R. G. Tonkyn, D. H. Kim, J. Szanyi, and C. H. F. Peden, Journal of Catalysis, 275, 187190 (2010).
E. Stavitski, E. A. Pidko, M. H. F. Kox, E. J. M. Hensen, R. A. van Santen, and B. M. Weckhuysen, Chemistry A European Journal,
16, 93409348 (2010).
Supervisor:
The present industry mainly relies on the limited reserves of crude oil for the production of
transportation fuels and other chemicals. Depleting oil reserves and the call for cleaner fuels stimulate
the development of methods to synthesize liquid hydrocarbons from other sources than crude oil.
Natural gas reserves are reported to be large but are, due to their remote location, not always exploited
while associated gas might even be flared. However, using steam reforming or partial oxidation of
methane, natural gas can be converted to synthesis gas, a mixture of CO and H2.
Using the Fischer-Tropsch process, synthesis gas can be converted into liquid hydrocarbons. [1]
These liquid hydrocarbons can be used for the production of chemicals and, due to the low
concentration of contaminations like nitrogen, sulfur and aromatics, for fuels like ultra-clean-diesel.
The Fischer Tropsch reaction is typically catalyzed by supported Co or Fe catalysts. Extensive
research has been performed on alumina, silica, carbon and titania supported Fischer-Tropsch
catalysts. Only a limited number of studies was performed on niobia supported catalysts. However,
in these studies very promising selectivities towards liquid hydrocarbons were reported for niobia
supported cobalt catalysts. [2, 3] In this research, these high selectivities were confirmed and at
industrially relevant conditions selectivities superior to alumina supported catalysts were found
(Figure 1).
Figure 1: Selectivity towards liquid hydrocarbons in Fischer Tropsch synthesis at 20 bar, H2/CO=2 for 5% Co-Nb2O5 and
25% Co--Al2O3.
Niobia however, has a low porosity compared to conventional catalyst support materials like
alumina and silica. This low porosity complicates catalyst preparation and limits the possible cobalt
loading. Main challenges of this research are to overcome or compensate for the low porosity
of niobia in order to develop niobia supported cobalt catalysts with superior selectivity and
competing activity compared to conventional catalysts.
[1]
[2]
[3]
53
Supervisor:
54
The possibility to design porous, crystalline materials with desired properties has turned the
attention of scientists to the Metal Organic Frameworks (MOFs) during the last decade. This
possibility can be attributed to their inorganic/organic hybrid structures, which allow bulk
MOFs to be used in many applications such as catalysis, sensing and gas adsorption. However,
the knowledge concerning the early stages of growth of MOFs has remained rather limited.
Therefore, there has been an increasing interest recently in growing MOF materials on a surface,
in the form of a thin layer, namely surface mounted metal organic frameworks, SURMOFs. In
layer-by-layer liquid epitaxy growth of SURMOFs, particularly functionalized substrates, are of
great importance for directing the nucleation, orientation and the structure of the growth MOFs
[1]. This functionalization of the substrate can be achieved by the use of self-assembled organic
monolayers (SAMs), having well defined molecular arrangement and a high structural quality.
The goal of this research project is to prepare SURMOFs in a controlled and reproducible way
by using stepwise layer-by-layer liquid epitaxy method with suitable SAMs. Scanning probe
microscopy-optical spectroscopy combinations will be used in order to give insight in the early
growth stages of SURMOF materials.
[1]
D. Zacher, K. Yusenko, A. Betard, S. Henke, M. Molon, T. Ladnorg, O. Shekhah, B. Schpbach,T. de los Arcos, M. Krasnopolski,
M. Meilikhov, J. Winter, A. Terfort, C. Wll, R. A. Fischer, Chem. Eur. J. 2011, 17, 1448 1455.
Department of Energy U.S.A. (DoE), Energy Frontier Research Center (Atomic Level Catalyst
Desing), since February 2010
Supervisors:
Synthesis gas or syngas (CO+H2) can be obtained from of oil-alternative carbon resources such
as natural gas and lignocellulosic biomass. It serves as feedstock for a number of catalytic routes
towards fuels and platform chemicals. Supported metal catalysts are employed in syngas conversion
routes but metal sintering is a prominent cause of catalyst deactivation. Rationally designing and
assembling novel catalysts with improved stability remains as a major challenge.
This project aims at gaining fundamental insight into the factors governing the stability of metalbased supported catalysts in syngas conversion processes, e.g. methanol synthesis. To accomplish
this goal, our approach combines material synthesis, catalytic testing and advance electron
microscopy characterization (namely electron tomography [1]). Due to their industrial relevance,
the research is focused on synthesis procedures such as impregnation-drying using inexpensive
metal precursors such as nitrates. Different aspects such as support pore size/morphology, metal
particle size/composition as well as the spatial distribution of the active phases at the nanoscale are
currently being studied.
Figure 1: a) 3D segmentation of individual Cu nanoparticles in the pores of SBA-15 from an electron tomogram to evaluate
interparticle distances; b) evolution of catalytic activity with run-time for CuZn/SBA-15 catalysts with markedly
different spatial distributions of the supported Cu nanoparticles, as shown in the tomographic cross-sections,
and a reference Cu/ZnO/Al2O3 catalyst.
As illustrated in Fig.1, CuZn/SBA-15 catalysts can be synthesised with similar overall (bulk)
properties but vastly dffering in the nanospatial distribution of the catalytic Cu nanoparticles, as
quantitatively accessed by electron tomography (panel a in Fig. 1). Near-maximum interparticle
55
56
[1]
[2]
H. Friedrich, P.E. de Jongh, A.J. Verkleij, K.P. de Jong, Chem. Rev. 109 (2009) 1613.
G. Prieto, J. Zecevic, H. Friedrich, K.P. de Jong, P.E. de Jongh, Nature Mater. (2012); DOI: 10.1038/NMAT3471.
Supervisor:
The selective conversion of alcohols into hydrocarbons has attracted large interest as these
processes are considered alternative processes to bypass crude oil as a feedstock for the production
of refinery products, such as propene [1]. Among these processes, Methanol-To-Olefins (MTO)
process is one of the most studied processes and there is a consensus that it follows the so-called
hydrocarbon pool (HCP) mechanism. The active species in HCP are mostly attributed to single
ring aromatic cations, which are also simultaneously the precursors of large coke species. However,
very few papers have been focused on the in-situ evolution of the HCP species and their kinetic
behaviors, which can be crucial in the assessment of the performance of the catalysts.
Our study is focused on SAPO-34, the archetypal MTO catalyst, which has the CHA-topology
with large cavities (0.65 nm 1.1 nm) connected through small channels (0.42 nm 0.37 nm).
In this work, a thorough comparison between MTO and ethanol-to-olefins (ETO) reactions on
large SAPO-34 crystals are described with respect of formation of HCP species by using in-situ
micro-spectroscopy. More specifically, the intensity of the 400 nm band, ascribed to poly-alkylated
benzene (PAB) cations, has been monitored with in-situ UV-Vis micro-spectroscopy and fitted
with first-order kinetics as illustrated in Fig. 1a. At low temperature region, the calculated activation
energy (Ea) for MTO shows a strong correlation with the theoretical rates for methylation of
aromatics [2]. While for ETO, the Ea value is comparable to the one for the condensation of light
olefins into aromatics [3]. Confocal fluorescence microscopy (CFM) demonstrates that during
MTO the formation of fluorescent species is initially limited to the outer rim of the crystal, and at
high temperatures larger HCP species are gradually formed inwards the crystal. In the case of ETO,
the observed egg-white HCP distribution at 509 K suggests that the ETO process is controlled by
the reaction rate, while the square shaped HCP distribution at 650 K is indicative for a diffusion
controlled process (Fig. 1b). IR micro-spectroscopy revealed a higher degree of alkylation in the
aromatics for MTO as compared to ETO, while high temperatures favor dealkylation processes for
both the MTO and ETO.
Figure 1. a) Arrhenius plot of the fitted curves
corresponding to 400 nm UV-Vis band
deconvoluted from MTO and ETO processes.
Insertions show IR spectra taken at
corresponding points. b) CFM images taken
at indicated temperature and time points.
[1]
[2]
[3]
57
Supervisor:
Atomic absorption spectroscopy, In-situ UV-Vis spectroscopy, Inorganic Synthesis, Gas Chromatography
58
The oxidation of basic organic industrial feedstocks comprises an important share in chemical
industry for the production of key intermediates to supply all sorts of chemicals, from drugs
and fine chemicals to bulk and high-performance materials. A persistent challenge in the field
is the development of recyclable, selective and less energy intensive catalysts for the oxidation
of hydrocarbons, catalysts that can be truly heterogeneous in nature and spare the use of the
large industrial battery of energy-intensive strong oxidants (H2O2, strong mineral acids). We
are particularly interested in exploring the possibilities to develop transition metals as truly
heterogeneous catalysts, shifting away from classical supports (alumina, silica, zeolites) and towards
non-conventional systems able to provide enhanced stability and thus reduce their environmental
impact while improving the efficiency of the processes.
Supervisor:
Single molecule fluorescence microscopy, Confocal fluorescence microscopy, Synchroton based -XRD
Numerous bulk characterization methods have been involved in measuring and describing the
nature of Brnsted acidity in zeolite materials. However, the information from these measurements
is averaged over many acid sites, while the localization and quantification of individual acid sites
still remains a formidable challenge. Single molecule fluorescence microscopy has proven to be a
valuable tool in accomplishing this task.[1] Development of new super-resolution techniques based
on fluorescence, in combination with high sensitivity and excellent spatiotemporal resolution (10
nm and 30 ms), allows detecting single turnovers of organic molecules on acid sites of zeolites.
In this project, wide-field fluorescence microscopy has been used as a powerful tool to quantify
in 3-D the accessible and active Brnsted acid sites within large H-ZSM-5 zeolite crystals.[2]
Furfuryl alcohol and styrene derivates are used as reporter probe molecules for Brnsted acid
sites (Fig. 1a). The approach reveals the effect of steaming post-treatments on the distribution of
accessible Brnsted acid sites (Fig. 1b). Intracrystalline defects and aluminium zoning can also be
quantified and imaged with high resolution and sensitivity (Fig. 1c).
Figure 1. a) Oligomerization of 4-methoxystyrene on parent H-ZSM-5 zeolite crystals recorded in a 100 ms frame with single
turnover sensitivity; b) Super-resolution image of catalytic activity over the surface of steamed ZSM-5 crystal; c)
Single molecule reactivity map of 4-methoxystyrene recorded close to the surface of parent ZSM-5 crystal.
59
NWO-STW, Albemarle, Shell global solutions, BASF and DOW Chemicals, Since October
2011
Supervisor:
Prof. dr. ir. Frank M. F. de Groot and Prof. dr. ir. Bert M. Weckhuysen
60
Figure 1: A: Optical scheme of the STXM imaging mode. Synchrotron radiation is used as the x-ray source. B: The 20 nm
resolved elemental ratio Mo/(Mo+S) of a fresh alumina-supported CoMoS catalyst.
Supervisor:
In the last few decades the use of in-situ spectroscopic techniques has become commonplace for
studying catalytic materials in a lab-scale environment. However, these systems are not always
representative for the processes taking place inside large-scale industrial reactors. Therefore, it is
important to implement these spectroscopic techniques in industrially relevant systems. For this
work, UV-Vis spectroscopy was used to study the deactivation of a CrOx/Al2O3 catalyst used
for the propane dehydrogenation in a pilot plant scale reactor. CrOx/Al2O3 catalysts have been
extensively studied by UV-Vis spectroscopy in the past. A schematic drawing of this system is
presented in Fig. 1a. Critical to the design are two UV-Vis probes, which have been designed to
operate at high temperatures and to remain clear of carbon deposits.
UV-Vis spectra obtained during the dehydrogenation step show that the buildup of coke is a
continuous process, as is shown in Fig. 1b. When comparing the UV-Vis spectra obtained by the
top and the bottom probe, (Fig. 1c) it can be seen the buildup of coke is more rapid at the top of
the reactor as compared to the bottom. Furthermore, the oxidation of carbon deposits is a rapid
event, travelling down the length of the reactor as a front over time. The few catalyst particles
measured by the probe are representative for all catalyst particles at that height of the catalyst bed.
Finally, the results, obtained by GC-analysis, show that the catalyst performs similarly as those in
an industrial setting.
Figure 1: Schematic of the pilot scale plant designed and constructed. With both probes UV-Vis spectra are obtained
during the catalytic dehydrogenation of propane, (b) in which the catalyst darkening due to coke formation is
clearly visible. When comparing the normalized and averaged darkening as measured by the two probes, it is
clear that coking is faster at the top () as compared to the bottom () of the reactor.
61
Supervisor:
Tip-enhanced Raman scattering (TERS), Raman spectroscopy, Atomic Force Microscopy (AFM), colloidal synthesis
62
Figure 1: Schematic overview of a TERS experiment. The object of study is a monolayer of pNTP, assembled on a Au
nanoplate. The Ag-coated TERS tip acts both as TERS-probe and as the photo-catalyst of pNTP when the sample
is illuminated with green light.
[1]
[2]
Figure 1: Schematic overview of entrapped Co(III)-Salen complexes in nano-cavities of mesoporous materials (x= -OAc).
[1]
[2]
[3]
Breuer, M.; Ditrich, K.; Habicher, T.; Hauer, B.; Kebeler, M.; Sturmer, R.; Zelinski, T. Angew. Chem. Int. Ed. 2004, 37, 788-824.
Song, C.E.; Lee, S.; Chem. Rev. 2002, 102, 3495-3524.
Van der Voort, P.; Ravikovitch, P.I.; de Jong, K.P.; Benjelloun, M.; van Bavel, E.; Janssen, A.H.; Neimark, A.V.; Weckhuysen,
B.M.; Vansant, E.F. J. Phys. Chem. B 2002, 106, 5873-5877.
63
Supervisor:
64
Aromatics are important building blocks for all kinds of products, such as medicines, coatings and
plastics (e.g. PET bottles). The current production of aromatics from petroleum, is not sustainable
and alternative routes are needed.The aim of the project is to develop an efficient chemo-enzymatic
route for aromatic acids production, using substituted furans as the feedstock. The catalytic route
will consist of a combination of heterogeneously-catalyzed steps and a biocatalytic conversion.The
main goal is to design highly efficient, selective and stable heterogeneous catalysts. Stability studies
will focus on deactivation by coke deposition. In situ measurements techniques and thorough
catalyst characterization will allow us to establish clear structure-activity relationships and also give
insight into intermediates being formed during reaction.
Supervisor:
Fluid catalytic cracking (FCC) is of great industrial importance in crude oil refinery. The
FCC catalyst particles are a complex mixture of various components. Locating those various
components in a catalyst particle is challenging and may involve the degradation of the particle.
Confocal fluorescence microscopy (CFM) is non-destructive and has been proven to selectively
image zeolite crystals within the matrix of FCC particles by selective staining.
In preliminary experiments with large ZSM-5 crystals, employed as a model system, the absorption
of visible light and the emission of fluorescence light were found to depend on the polarisation
plane of the incoming excitation light, with respect to the orientation of the crystal. This is linked
to the orientation of the oligomerisation products within this crystal, hence, their transition dipole
moment vectors for the absorption of light. This knowledge was applied to an industrial FCC
catalyst, containing ZSM-5 zeolite crystals of 1 3 m in size as active component. Figure 1 shows
four images of a rotation sequence of a FCC particle. The illustrated fluorescence signal appears/
disappears at different orientations due to extinction. Hence, this signal has a polarization and, thus
originates from a crystalline (anisotropic) material. In this case the zeolite crystals.
Figure 1: FCC catalyst particle containing ZSM-5 at 453K after 4-fluorostyrene oligomerisation; the fluorescence images
were taken at orientations of (a) 0, (b) 90, (c) 180, and (d) 270 with respect to the allowed vibrational path
of the polariser. The images were rotated back to the initial position for better comparison. The arrows/pointer
1 - 4 highlight exemplified areas where fluorescence signal appears/disappears.
Confocal fluorescence microscopy visualizes the zeolite component within the matrix of an industrial catalyst.
This method views the intact catalyst particle and is selective to (anisotropic) crystalline material and allows
its location, size distribution, and orientation in three dimensions.
65
Supervisor:
66
Current industrial biodiesel production is based on the transesterification process, yielding fatty
acid methyl esters (FAME) and glycerol from triglyceride feeds (figure 1). This process can be
catalyzed using either acid or base catalysts.While the base catalyzed reaction is faster, acid catalysts
have high tolerance for free fatty acids and water present in low grade triglyceride feeds (e.g. waste
cooking oil, animal fat, or non-edible oils), creating opportunities for the use of acid catalysts in
the biodiesel production process. [1]
Many different types of heterogeneous acidic catalysts have been examined for the transesterification
reaction. Among these, sulfonated carbons are promising materials due to the affinity of the carbon
support with the reactant molecules and the presence of strongly acidic sulfonic acid groups on
the catalyst surface. Other areas of interest include acidic metal oxides, as these are able to retain
their structure and activity at higher reaction temperatures. However, in all cases fundamental
challenges in catalyst design related to either accessibility, activity or stability of the acid sites still
need to be addressed.
The focus of this project is the development of acidic mesoporous carbons that are stable
under typical biodiesel production process conditions. Other work is related to synthesis and
characterization of acidic transition metal oxide catalysts.
[1]
J.A. Melero, J. Iglesias, G. Morales, Heterogeneous acid catalysts for biodiesel production - current status
and future challenges, Green Chem. (2009) 11, 1285.
Supervisor:
The drive to establish a natural alternative fuel source to alleviate our dependence on fossil fuels
has led to a lot of attention being placed on biodiesel. Although this is an attractive green fuel,
it also produces large amounts of glycerol as a by-product. The valorisation of this will allow
biodiesel production to become a more valuable and competitive process. One such value-added
product is glycerol carbonate, which has been produced by a wide range of catalytic systems,
both hetero- and homogeneous, utilising a number of different CO sources.[1] Glycerol can
also easily undergo etherification to produce di- and triglycerol using simple alkaline earth metal
mixed oxides.[2]
67
Two different catalytic routes have been utilised to produce diglycerol dicarbonate (DGDC) from
diglycerol and dimethyl carbonate, as shown in Scheme 1. Both heterogeneous and organocatalytic
systems have been shown to successfully produce DGDC in high yields under relatively mild,
solventless conditions.
[1]
[2]
Takagaki, A., Iwatani, K., Nishimura, S. and Ebitani, K. Green Chem., 12 (2010) 578
Ruppert, A.M., Meeldijk, J.D., Kuipers, B.W.M, Ern, B.H. and Weckhuysen, B.M. Chem. Eur. J. 14 (2008) 2016
Higher alcohols from (bio) alcohols via gas phase Guerbet reaction
Selvedin Telalovi, S.Telalovic@uu.nl, phone: (+31)622736090
Sponsor:
Supervisor:
Prof. dr. ir. Krijn P. de Jong, dr. Johannes H. Bitter and dr. Jaap W. Van Hal (ECN)
X-ray powder diffraction (XRD), N2-Physisorption,Gas chromatography (GC), Transmission electron microscopy
(TEM)
68
Refineries based on crude oil feedstock provide most of our chemicals and fuels. Due to the
depletion of oil reserves and an increase in anthropogenic gasses (CO2) in to the atmosphere
causing climate change we need to use other resources such as biomass. Biorefineries based on
sustainably feedstocks such as (bio) ethanol, among others, are one of solutions for a sustainable
future. In particularly, in our research we focus on the Guerbet reaction that converts (bio) ethanol
to higher alcohols (Guerbet alcohols) that find they use as lubricants, plasticizers, cosmetics or even
as fuels. The Guerbet reaction is thought to proceed via the dehydrogenation of the alcohol, the
condensation of formed aldehydes or ketones, the dehydration of the condensation product and
subsequent hydrogenation of the double bond and the aldehyde/ketone group (see Figure 1). One
of the aims of the project is to design a catalyst for this challenging reaction.
Supervisor:
Confocal fluorescence microscopy, Integrated light and electron microscopy (iLEM), Scanning transmission
X-ray microscopy (STXM), Diagonally offset Raman micro-spectroscopy (DORS).
One of the main goals of chemical industries employing the use of catalysts, is to maintain
catalytic activity, selectivity and stability, in order to operate an economically attractive process.
A major factor influencing the criteria mentioned, is catalyst deactivation, which is caused by
number of processes, one of which is poisoning, i.e. strong sorption of feed impurities such S,
N, O and metals, hence, blocking potential active sites. There is a need therefore, to develop
catalysts which are able to operate in the presence of poisons and resist deactivation. Zeolites are
a group of solid catalysts which are vastly used in the petrochemical and refining industries, and
are prone to deactivation with metal contaminants and feed impurities. Gaining insight into the
deactivation of zeolites is highly valuable to such industries, and a large quantity of research has
focused on bulk characterization methods, under un-realistic process conditions. The aim of this
project is to use spatiotemporal chemical imaging techniques to study zeolite catalyst deactivation/
poisoning, discriminating between binder and active material contributions. The use of UV-Vis,
confocal fluorescence and integrated light and electron (iLEM) microscopy, accompanied by a
selective staining reaction such as thiophene oligomerization[1], will be employed to visualize
zeolite aggregates within the catalyst material in 2-D and 3-D. Investigating the changes in acidity
upon deactivation/poisoning will also be studied, by analyzing the series of thiophene derivatives
differing in their relative reactivity. The development of a suitable probe reaction to highlight the
property changes in the binder component upon deactivation/poisoning, will also be investigated.
By using highly sensitive X-ray-based imaging methods such as (scanning)transmission X-ray
microscopy (STXM and TXM)[2], it could be possible using the selective staining method, to
visualize specific poisons in 3-D, with nanometer spatial resolution. The capabilities of diagonally
offset Raman micro-spectroscopy (DORS) will also be explored, to study extrudates containing
zeolite active material and binder, at the surface, sub-surface and bulk, before and after poisoning/
deactivation.
[1]
[2]
M.H.F. Kox, A. Mijovilovich, J.J.H.B. Sattler, E. Stavitski and B.M. Weckhuysen, ChemCatChem, 2010, 2, 564-571.
L.R. Aramburo, S. Wirick, P.S. Miedema, I.L.C. Buurmans, F.M.F. de Groot
and B.M. Weckhuysen, Phys.Chem.Chem.Phys. 2012, 14, 6967-6973.
69
Supervisors:
70
Branched-chain fatty acids (bc-fas) are used extensively as a lipid raw material for production
of e.g. lubricants, cosmetics and surfactants, where they provide a unique combination of lowtemperature liquidity, excellent thermal and oxidative stability and useful interfacial properties.
The current commercial process for making bc-fas from oleic acid (cis-9-octadecenoic acid)
yields only 50% or less, the balance of the reaction products being mainly polymerised acids.
Montmorillonite clay is used as heterogeneous catalyst [1,2].
Isomerisation of oleic acid using zeolites represents the most promising route to isolation of bcfas in high yields and has been investigated by several groups. Recently, a research group at the
USDA reported a step change in both yield and selectivity using commercial zeolites from the
ferrierite group [3]. Selectivity has been further improved by the use of a Lewis base as co-catalyst
[4]. However, the cost of the ferrierite, and its loss of activity with successive re-use, still make it
an uneconomic option for large-scale application in price-sensitive markets.
Our research is aimed at understanding the specificities of ferrierite in bc-fas processing with
regard to both activity and selectivity. In a first phase, we are investigating the deactivation of the
catalyst during isomerisation of oleic acid. The nature and formation rate of coke-like species was
studied by a combination of techniques, including UV-Vis and in-situ FT-IR, complimented with
NMR and GC-MS analyses of the coke-like deposits after HF dissolution of the zeolite.
[1]
[2]
[3]
[4]
Y. Nakano; T.A. Foglia; H. Kohashi; T. Perlstein; S. Serota, J. Am. Oil Chem. Soc., 62 (1985) 888.
R.M. Koster; M. Bogert; B. de Leeuw; E.K. Poels; A. Bliek, J. Mol. Catal. A: Chemical 134 (1998) 159.
H.L. Ngo; A. Nunez; W. Lin; T.A. Foglia; Eur. J. Lipid Sci. Technol. 108 (2007) 214.
H.L. Ngo; E. Hoh; T.A. Foglia; Eur. J. Lipid Sci. Technol. 114 (2012) 213.
Supervisor:
The production of chemicals and fuels using renewable energy sources is a grand challenge.
Previously our group has developed an elegant catalytic system (supported iron catalyst with
sodium and sulfur as promoters) for the production of lower olefins from synthesis gas (CO + H2).
[1,2] Synthesis gas can be produced from all carbon-containing sources, also from biomass. Lower
olefins are basic building blocks which are used to produce a wide variety of products, ranging
from plastics to pharmaceuticals. Therefore, these inexpensive supported iron catalysts provide an
exciting solution for the chemical industry to produce lower olefins from alternative feedstock,
which brings tremendous economic and environmental benefits.
My research involves synthesis and characterization of the supported iron catalysts, so as to gain
a deeper understanding of the catalytic system. These fundamental studies will ideally result in
better control of the catalytic system which allows us to optimize activity and selectivity of lower
olefins product. Subsequently, scale-up of catalyst synthesis can be attempted which may lead to
commercialization of the optimized catalytic system.
[1]
[2]
H. M. T. Galvis, J. H. Bitter, C.B. Khare, M. Ruitenbeek, A. I. Dugulan, K. P. de Jong, Science 235, 835 (2012).
H. M. T. Galvis, J. H. Bitter, T. Davidian, M. Ruitenbeek, A. I. Dugulan, K. P. de Jong, J. Am. Chem. Soc. 134, 16207 (2012).
71
Supervisor:
72
The majority of the chemicals and fuels are currently derived from fossil crude oil. Limited
availability of crude oil and current high prices makes it mandatory to look for sustainable
feedstock for future generations. Biomass is the only renewable option for the manufacture of
carbon containing (bulk)-chemicals. Carbohydrates, the major components of lignocellulosic
biomass, have been identified as important feedstock for biobased (bulk)-chemicals. A wide
variety of intermediates such as HMF, sorbitol, lactic acid, succinic acid and levoglucosan can be
synthesized from carbohydrates.[1]
A major issue when using carbohydrates is the formation of large amounts of low value
carbonaceous waste by-products known as humins.[2,3] To make carbohydrate-based routes to
sustainable chemicals economically more viable, it is essential to valorise these humins. In this project
we aim to valorize the humin by-product by converting it into valuable chemicals (Figure 1).
Figure 1: Schematic representation of the formation, characterization (SEM and solid state NMR) and catalytic conversion
of humin by-products.
[1]
[2]
[3]
Supervisor:
Supported noble metal catalysts are of great importance to various industrial processes. In
particular, the industrially relevant bifunctional zeolite supported Pt catalyst has been the subject
of numerous studies. Assessing particle size distribution and their location within zeolite support is
crucial for understanding the reaction mechanisms as well as for optimizing preparation procedures.
To characterize such catalysts, usually bulk techniques are being used (EXAFS, NMR, H2chemisorption), while TEM is the most direct technique which enables visualization and manual
measurement of Pt particles [1]. However, size measurement using common TEM micrographs is
limited by low sampling and detection difficulties caused by overlapping features in 2D projections
i.e. TEM micrographs. Therefore, we use electron tomography (3D-TEM) [2] coupled with image
processing for a detailed characterization of industrially relevant, Pt on mesoporous zeolite Y,
catalyst.
Electron tomography enabled us to visualize, locate and measure thousands of Pt particles as small
as 1 nm, extract valuable information (Figure 1) and compare the impact of preparation procedures
(loading techniques, reduction temperatures) on particle sizes, particle locations and particleparticle distances. It has been found that the Pt size distribution is narrow in case of samples that
were calcined and reduced. The averaged Pt diameter is 1.0-1.3 nm, which matches the size of the
zeolite Y micropore cavities. Careful observation of the reconstructed volumes suggests that most
of the Pt particles were located inside the microporous crystalline regions, while only few of the
largest (>4 nm) were in the mesopores. A homogeneous distribution of Pt particles was observed
in all of the imaged zeolite crystals, however, calculated Pt loading varied tremendously among
crystals from 0.2 to 7.1 wt%. This remarkable loading variation of up to factor of 35, might have
a great impact on catalyst performance, hence, this study stresses the need for detailed nanoscale
characterization along with the bulk measurements.
Figure 1. An example of a overloaded zeolite Y crystal with 7.1 wt% Pt: a) Virtual cross-section through the reconstructed
volume, b) Volume rendered representation of the reconstructed crystal (green) with mesopores (white) and Pt
particles (blue), c) Pt size distribution.
[1]
[2]
73
Nanophotonics
74
Nanophotonics
75
Nanophotonics
Nanophotonics
FOM
Supervisor:
Spin currents, well known in spintronics, are subject to strong damping due to collisions between
spin species, a phenomenon known as spin drag. We have performed spin drag experiments for
ultra-cold atoms [1]. We prepare an equal mixture of pseudo spin up and down atoms and apply a
force on one of the species. As a result a constant drift velocity between the spin species develops,
which is a measure of spin drag. Close to the phase transition to BEC we observe a strong increase
of spin drag due to Bose stimulation, in agreement with recent theory [2], acting as a precursor
for Bose-Einstein condensation. Our results pave the way for studies of transport properties of
degenerate bosons that are very different from fermionic systems.
76
Figure 1: Two ultra-cold atomic Bose-gases of different spin. The line profiles show an asymmetry and a relative
displacement of the centers of mass (vertical lines), which are indications of spin drag.
1
2
S.B. Koller, A. Groot, P.C. Bons, R.A. Duine, H.T.C. Stoof, P. v.d Straten, Spin drag in a Bose Gas (submitted).
R.A. Duine, H.T.C. Stoof, Spin Drag in Noncondensed Bose Gases, PRL 103, 170401 (2010).
Nanophotonics
Supervisor:
AFM, Nanoimprint Lithography, Cluster Deposition, Finite Difference Time Domain (FDTD) modeling
This research is part of the quest to improve one of the energy conversion technologies of the
future, namely solar cells. This technology gives optimal performance in terms of CO2 emission,
power potential, and scalability compared to the current methods of electricity generation. For
some places on earth solar cells are already cost competitive. We have to bring down costs even
further to enable power generation in the order of terawatts. I contribute to the realization of this
by optimizing the photovoltaic energy conversion: converting photon energy in electron energy.
The current solar cell market is predominantly based on cells made of crystalline silicon wafers. In
the past decades the cost per Watt-Peak were reduced significantly. This was partially achieved by
reducing the wafer thickness from ~400 to ~200 m. Reducing the thickness even further faces
industrial problems as the wafers are brittle. The absorber layer thickness can be reduced three
orders of magnitude by using amorphous silicon (a-Si). a-Si has a relatively high optical absorption
because of its direct band gap nature. The essential cost reduction can be achievable by reducing
the fabrication time. This can be done by reducing the cell thickness even further.
Generally, cells become more transparent as the thickness is reduced and thus the total absorption
decreases. Metal nanostructures, with their plasmonic properties, can be integrated to enhance
the optical performance. For example, these structures can increase the optical path length by
scattering.
In our group we try to find the optimal nanostructure by using nanoscale imprint technology and
by nanoparticle deposition. Small metal nanoparticles (1-50 nm) can be deposited by magnetron
sputtering in a state-of-the-art nanocluster source. Using this system metal nanoparticles with a
tunable size can be deposited at an arbitrary position in the solar cell. Theory predicts that these
particles behave as plasmonic scatterers. Placing them on top of the solar cell is expected to result
mainly in forward scattering into the silicon as is shown in the figure. Our aim is the exploitation
of these plasmonic effects to make high quality thin film amorphous silicon solar cells at low cost
with an absorber layer thickness less than 100 nm. This will result in a significant cost reduction.
Figure 1: Graphical representation of light scattering in a photovoltaic cell with metal nanoparticles on top.
77
Nanophotonics
Supervisor:
Hot wire CVD (HWCVD), Very high frequency plasma enhanced CVD (VHF PECVD), Reflection/transmission
spectroscopy, Conductivity measurements
Silicon heterojunction (SHJ) solar cells hold the potential for high efficiency devices at low
manufacturing costs. Their main part consists of amorphous silicon layers (a Si:H) deposited on
top of a crystalline silicon wafer (c-Si).
The essential aspect of a SHJ solar cell is the exploitation of the difference in band gap of
amorphous and crystalline silicon. Amorphous silicon has a wider band gap than crystalline silicon.
Therefore, it is used to electronically separate the metal contacts from the silicon wafer, which acts
as absorber material.
78
Figure 1: Layer structure and band diagram of a silicon heterojunction solar cell in the design developed by SANYO/
Panasonic [1].
Figure 1 shows the structure and band diagram of a typical SHJ solar cell. The transparent
conductive (TCO) layer on top of the cell functions as window layer for the incoming light and
transports the generated current to the front contact of the cell. Commonly used TCOs have
several drawbacks such as a narrow range of refractive index and work function. This does not
allow for much tuning in order to optimize the carrier collection and transport. Therefore, the
goal of this project is to develop a novel two-phase transparent doped nanocrystalline silicon oxide
(nc-SiOx:H) layer. It will be deposited by chemical vapor deposition, the same technique used
for the underlying layer, and replace the TCO layer. For better antireflective effects and/or band
alignment grading of the nc-SiOx:H layer is possible. In general, the SHJ cell structure and its
fabrication process will thereby be simplified.
[1]
Nanophotonics
FOM
Supervisor:
First and second sound are the hallmarks of two-fluid hydrodynamics [1]. These sound modes
consist of density and temperature modulations in the non-condensed and condensed fractions
of an ultra-cold bosonic gas. By periodically modulating the trap potential a Faraday wave, or
standing sound wave, is induced in the condensate [2,3]. First, we have investigated the dispersion
relation of this excitation, which can be used to extract the speed of sound with high accuracy.
Secondly, our measurements give insight into the emergence and time evolution of these highly
excited collective modes. Our analysis suggests the non-linear interactions and hydrodynamicity
of the condensate allow for coupling between the radial driving and the emerging Faraday waves
in the axial direction.
79
Figure 1: Faraday waves in a Bose-Einstein condensate. Linear relation between (from top to bottom) the increasing radial
frequency and the increasing wavenumber can be seen clearly in the above image.
[1]
[2]
[3]
Nanophotonics
80
Thin film silicon solar cells can be deposited on many types of substrates, which include plastics and
paper-like foils. To be able to do this, deposition temperatures will have to be decreased drastically.
The challenges encountered when decreasing the deposition temperature are (i) deterioration of
the optoelectronic properties of the layers, (ii) severe mechanical stress, which results in curling of
the substrates or the layers peeling off, and (iii) the formation of dust in the plasma, which can result
in electronic defects in the deposited layers and shunting of solar cells.The aim of this research is to
obtain a better understanding of the growth processes involved and elimination of these problems.
For this we monitor the plasma using Optical Emission Spectroscopy (OES), Retarding-Field
Ion Energy Analysis (RFEA) and Energy Resolved Mass spectrometry and correlate the plasma
properties with the layer quality.
In collaboration with the Wageningen UR Glastuinbouw (WUR) we developed solar cells on hot
embossed pyramid-like structured polycarbonate substrates.WUR performs research on structured
plastics for the design of greenhouse roofs that are extremely transparent for sunlight. As a spin off,
we use the same structures to develop substrates that can provide an optimal light confinement
in a thin film silicon solar cell. We investigate layer growth on these structures and optimize the
shape and size of the structures. We have succeeded in fabricating amorphous silicon (a-Si) solar
cells at 130C with a conversion efficiency of around 8% on a glass substrate. On polycarbonate,
not exceeding 130C, using 10 m base pyramids, we achieved an initial conversion efficiency
of 6.4% whereas with 400 nm base pyramidal structure, we obtained a conversion efficiency of
7.4%. This is the highest reported efficiency of p-i-n a-Si cell on a cheap plastic substrate. As proof
of the concept we have demonstrated a high conversion efficiency of 9.5% using amorphous/
nanocrystalline silicon tandem cell structure, with a maximum processing temperature of 130C.
Figure 1. (a) Current Voltage (I-V) curves and (b) Spectral Response (SR) curves for low (<130oC) temperature a-Si solar cells
deposited on flat glass (blue), on microstructured polycarbonate (black) and on nanostructured polycarbonate
(red).
Nanophotonics
Supervisor:
Hot wire chemical vapor deposition (HWCVD), plasma enhanced CVD (PECVD), chemical bath deposition
(CBD), focused ion beam scanning electron microscopy (FIB-SEM)
We present a simple, low-cost and scalable approach for ultrathin nanostructured threedimensional (nano-3D) solar cells[1-2]. ZnO nanorods (NRs) are synthesized as the building
blocks by chemical bath deposition. With a 100 nm thick hydrogenated amorphous Si (a-Si:H)
intrinsic layer, the nano-3D cell deposited by PECVD demonstrates an initial efficiency of 7.1%,
with 5.7% for the flat reference deposited simultaneously. A relative current enhancement of ~46%
is achieved in the nano-3D cell with respect to the flat reference cell thanks to the advanced light
trapping. When a 200 nm thick a-Si:H absorber layer is applied, the initial efficiency goes up to
8.4%, compared to 6.4% for its flat counterpart. The advanced light trapping in the nano-3D cells
is based on several mechanisms: (1) light scattering due to the textured interface, (2) reduced light
reflection at the front side, (3) internal reflection between individual nanorods which results in
multiple absorption opportunities, (4) orthogonalization of light path and carrier extraction path
and (5) possible waveguiding.
Figure 1: ZnO NRs prepared by CBD with different aspect ratios and the completed nano-3D a-Si:H n-i-p solar cells. (a)
A schematic diagram of the ultrathin nano-3D cell (not to scale). SEM images of low aspect ratio (b) and high
aspect ratio NRs(c). (d) A FIB-SEM image of the cross-section of a completed nano-3D cell on the low aspect
ratio NRs with i-layer deposited by HWCVD.
[1]
[2]
Y. Kuang, K. H. M. van der Werf, Z. S. Houweling, and R. E. I. Schropp, Appl. Phys. Lett., 2011, 98, 113111.
Y. Kuang, K. H. M. van der Werf, Z. S. Houweling, M. Di Vece, and R. E. I. Schropp, J. Non-Cryst. Solids, 2012, 358, 2209.
81
Nanophotonics
Role of ion energy and gas phase transients in the plasma on the
interface of c-Si and a-Si:H
Kees Landheer, c.landheer@uu.nl, phone: 088-5154723
Funded by:
Supervisor:
In this project we want to reduce the loss of energy conversion efficiency of silicon heterojunction
solar cells (SHJ) due to electron-hole recombination by improving interface passivation. The
record efficiency today is 23.7% and has been achieved by the Japanese company Sanyo with
their HIT (heterojunction with intrinsic thin layer) solar cell [1]. The best efficiency achieved at
Utrecht University is 16.7% without the use of light trapping geometries [2]. Achieving a high
efficiency at low processing and material costs is the strategy followed to make the HIT solar cell
a cost competing energy resource.
82
The fabrication of a SHJ starts with an n-type crystalline wafer (see figure). After a wet chemical
etch, a-Si:H layers are deposited on top and backside of the wafer. In our group the intrinsic a-Si:H
films are deposited either by VHF PECVD or Hot Wire CVD. The top and bottom stack consist of
an intrinsic amorphous Si layer, a doped a-Si layer, a transparent conducting oxide (TCO) layer for
anti-reflection and current collection and metal contacts for current collection. The thin intrinsic
a Si layer reduces surface recombination and boosts the open circuit voltage. Sanyo/Panasonic
achieved an open circuit voltage of 0.745 V for a 98 m thick wafer (area 100.7 cm2) [1]. The
high open circuit voltage gives the HIT solar cell a good temperature coefficient (-0.23%/C) of
efficiency. All processing steps in the SHJ fabrication are performed at temperatures below 200C.
Moreover, this enables the use of thinner wafers (< 100 m) which reduces material costs.
In this project we investigate the relation between PECVD plasma properties and the c-Si /
a-Si:H interface passivation. We will initially focus on studying the effect of ion bombardment
involved in PECVD deposition. The ion energies will be analyzed in situ by a retarding field
energy analyzer (RFEA), which can measure the ion flux and ion energy distribution function.
Additionally we will detect the ions (and radicals) with an energy resolved mass spectrometer.
These techniques will give us insight into the plasma behavior during the transient start-up phase
in the batch reactor and also in the static phase. The transient PECVD and film growth phase is
important because the crucial layers are about 5 nm thick. The film growth will be investigated
by spectroscopic and kinetic ellipsometry. The experimental research will be supported by plasma
simulations with a 2D fluid model. In order to simulate the ion energy distribution at the electrode
a kinetic Monte Carlo code is being developed that uses the output of the 2D fluid model for
tracing ions through the plasma sheath.The effect of PECVD ion bombardment on the passivation
Nanophotonics
properties of an a-Si:H film is still under discussion. Generally, high ion energies (> 15 eV) are
considered detrimental for the solar cell, since they create defects (a.o. crystal lattice deformation,
formation of silicon dangling bonds). Low ion energies (< 15 eV) are considered beneficial for
film growth since they provide energy for the diffusing species on the low temperature substrates
and make the deposited film compact. Subsequently, we will study the interface passivation ex situ
with photoconductance (PC) measurements. Also the effect of post-deposition annealing will be
analyzed in order to optimize the surface passivation.
83
Figure 1. The configuration of the hetero junction silicon solar cell and its (possible) development steps.
[1]
[2]
T. Kinoshita et al., The approaches for high efficiency hit solar cell with very thin (< 100 m) silicon wafer over 23%, 26th
European Photovoltaic Solar Energy Conference and Exhibition, September 5 and 6, (2011) p.871.
Jan-Willem Schttauf, Amorphous and crystalline silicon based heterojunction solar cells, PhD Thesis, Utrecht University
(2011).
Nanophotonics
Supervisor:
84
Light-matter interactions become increasingly more important. The emission and absorption
of light is inherently quantum mechanical, because transitions between quantum eigenstates of
atoms are involved. The quantum nature of light becomes apparent in an optical cavity. Therefore,
the simplest system in which to investigate the quantum nature of light-matter interaction, is an
atom interacting with light inside an optical cavity.
We trap an atom in the light field of a photonic crystal nanocavity. The mode volume of the cavity
is comparable to the polarization volume of the atom. Therefore the proximity of an atom changes
the cavity resonance frequency. In case of fixed frequency laser pumping of the cavity, the distance
of the atom to the cavity affects the cavity light intensity and thereby the optical force on the
atom. The atom will be trapped at ~ 100 nm from the surface for proper choice of frequencies.
Remarkably, the light intensity required to trap the atom corresponds to only a fraction of a
photon [1].
In the experimental setup (figure 1a) a cold rubidium atom is trapped above the surface of a
nanocavity in a photonic crystal waveguide. Calculations on the photonic crystal waveguide
cavity resonance frequency, mode profile and quality factor are performed using the MPB and
Meep packages of MIT. The photonic crystal will be produced using e-beam lithography and
characterized in a scanning near-field optical microscope.
The rubidium atoms are laser-cooled to a temperature below 50 K. After evaporative cooling the
cloud of remaining atoms is transported to the sample in an optical elevator (a 1D optical lattice).
When the optical power of the dipole trap is lowered, atoms can spill out of the trap and into the
evanescent field of the cavity. As a result, the transmission of the cavity changes. By monitoring the
transmission the dynamics of the cavity-atom system can be followed.
Figure 1: (a) Illustration of the experimental setup. A rubidium atom is trapped in the evanescent field of the cavity in a
photonic crystal bridge waveguide. The optical dipole trap (vertical red beam) is used to transfer atoms to the
cavity. (b) Schematic representation of the atom-cavity system. The atom and the cavity are coupled by a vacuum
Rabi frequency g(z) which depends on the atom-cavity separation z. The maximum vacuum Rabi frequency gmax
2 18.5 GHz. The spectral linewidth of the cavity is c 2 3.85 GHz and of the atom a 2 5.89 MHz.
[1]
Nanophotonics
Supervisor:
Enhancing the performance of thin film silicon solar cells by using a wider range of the solar
spectrum is the aim of this project, which we intend to achieve by means of quantum dot (QD)
silicon (Si) based multijunction solar cells. Si and silicon-germanium (SiGe) nanodots are the
materials of interest. The nanodots are made in a plasma enhanced chemical vapor deposition
(PECVD) process by two methods, namely, (1) through gas phase creation of nanodots controlled
by a pulsed plasma in a dusty regime and (2) layer by layer (LBL) growth process. One of the
objectives will be to find which process has an advantage over the other as far as control of particle
size, homogeneity of the particle sizes, doping efficiency of the impurities and control of the
defects are concerned. By a judicious combination of nanodots produced in the two methods we
will be constructing a tandem solar cell with the structure as shown in Fig 1.
The design of the reactor for gas phase production of quantum dots (QD) was optimized and
assembled with the electrodes. A set up for in-situ dust diagnostic, LLS (laser light scattering), was
developed and tested. Prior to fabricating QDs in the reactor, optical and electrical diagnostics
was done on CW (continuous wave) plasma. A stable and reproducible fluctuation was observed
in plasma emission, detected by OES (optical emission spectroscopy) and current (measured by VI
probe) in dusty hydrogen diluted silane plasma. This fluctuation originates from plasma dynamics
caused by growing dust particles.
85
Nanophotonics
Supervisor:
Nanofabrication, Focused Ion Beam Milling (FIB), Electron Beam Lithography, Ultra-High Vacuum (UHV),
Laser Cooling, Magneto-Optical Traps (MOT), Optical Tweezers, White Light and Doppler Free Spectroscopy
86
Figure 1: Graphical representation of the hole array and the trapped atoms. The vertical image on the left is a Scanning
Near-field Optical Microscope (SNOM) measurement of the electric field of the light above the array.
Extraordinary transmission through nano-hole arrays is a plasmonics related effect that aroused
interdisciplinary interest in the past few years. It is exploited for chemical sensing, plays a role
in the development of metamaterials and is a practical tool for fundamental research. It causes
strongly localized, highly intense electromagnetic fields that are structured at a sub-wavelength
scale. The very high energy density of these fields poses also excellent means to investigate nonlinear optics. We will use this effect to trap rubidium atoms and to analyze the interaction between
nano-hole arrays and the captured atoms.
The nano-hole arrays are fabricated by Focused Ion Beam milling (FIB): A 90nm thick film of
gold is evaporated on a glass substrate. With a focused Gallium ion beam the desired structure is
then milled into the gold film; in this case it is an array of square holes with diameters ranging
from 50nm to 600nm.
The structure is then inserted into a vacuum chamber. Clouds of rubidium atoms, precooled in a
three dimensional magneto-optical trap (3D-MOT), are positioned in the proximity of the nanohole arrays in the gold surface. Incident laser light is focused onto the structure. The extraordinary
transmission through the hole array elicits an array of optical tweezers, capable of capturing the
rubidium atoms very close to the gold surface. We will investigate the influence of the plasmons in
the gold on the electron configuration of the rubidium atoms, as well as the change of plasmonic
properties of the gold, evoked by the presence of these atoms.
Nanophotonics
Supervisor:
Quantum Dots (QDs) are considered a possible solution to overcome the ShockleyQueisser
efficiency limit of 31% for single junction solar cells by efficiently absorbing above band gap energy
photons through Multiple Exciton Generation (MEG) or sub band gap energy photons using an
Intermediate Band Solar Cell structure (IBSC). For the latter absorption process, tin sulphide (SnS)
is a promising candidate, having several advantages compared to the other nanoparticles studied
extensively so far, such as CdS, CdSe, PbS, and PbSe; namely it is non-toxic and environmentally
benign and thus will be most suitable in consumer products such as solar panels.
We have developed a new colloidal synthesis method for SnS QDs. We have obtained monodispersive SnS and SnS/In2S3 core-shell nanoparticles with a size of ~4 nm. Energy dispersive
X-ray spectroscopy (EDX) elemental analysis revealed that the particles are indeed SnS and not
SnS2. Furthermore, the conductive nature of the nanoparticles has been inferred by conductivity
mapping (Fig.1) using a relatively new contactless technique, Torsional Resonance Tunneling
AFM (TR-TUNA)[1]. These results confirm that the SnS QDs possess all the requirements to be
applied as photoactive layers in photovoltaic devices.
Figure 1: Topography (a) and current map (b) of SnS/In2S3 core-shell nanoparticles acquired by TR-TUNA AFM.
[1]
C. Prastani, A. Vetushka, A. Fejfar, M. Nanu, D. Nanu, J.K.Rath, and R.E.I. Schropp, Appl. Phys. Lett. 101, 083107 (2012)
87
Nanophotonics
Supervisor:
88
Thin film water and oxygen barrier layers will facilitate a large variety of sensitive electronic
devices, such as solar cells on foil, OLEDs and rollable displays. A combination of SiNx and
polymer layers, in our case poly-glycidyl-methacrylate (PGMA), is very suitable for this. SiNx
layers are very impermeable to water and oxygen, however beyond a certain thickness the barrier
properties do not improve any further due to defects (pinholes) propagating through the layers. By
stacking these layers with polymer layers in alternating order, the chance of pinholes in different
SiNx layers on exactly the same spot will be very small and an impermeable layer is created.
The innovation that we bring to this field is that both polymer and inorganic materials can be
deposited in a continuous process: SiNx using hot wire chemical vapor deposition (HWCVD)
and PGMA using initiated chemical vapor deposition (iCVD), where an initiator is activated at a
hot filament and starts the polymerization process. Since in both techniques no energetic ions are
present, these barrier layers can even be deposited on delicate organic layers. Our research on the
one hand concentrates on depositing stable PGMA layers to enable the deposition of SiNx on top
of it. The stability is expected to increase with increasing average chain length of the polymer and
a decreasing amount of defects in the polymer layer. On the other hand our goal is to lower the
process temperature for the SiNx and the amount of highly reactive atomic hydrogen during the
SiNx deposition process. Recent experiments at 60C and 90% relative humidity, show that the
water vapor transmission rate of a 3-layer stack is as low as 5 x 10-6 g/m2/day, suitable for even the
most sensitive OLED devices[1]. This excellent performance resulted in a patent[2].
D.A. Spee, C.H.M. van der Werf, J.K. Rath and R.E.I. Schropp, Phys Status Solidi RRL 6 (2012) p.151
WO 2012/165944
PCT/NL2011/050601
Nanophotonics
Nanocrystalline silicon (nc Si:H) is a highly absorbing, low band-gap semiconductor that can be
used in thin film tandem solar cells. In order to increase the throughput and power output of a thin
film silicon tandem solar cell production line, the deposition rate of nc Si:H needs to be increased
beyond the presently industrially used deposition rate of ~2 /s. The challenge of this research
is to enable the deposition of nc Si:H at high rate using very high frequency plasma-enhanced
chemical vapor deposition (VHF PECVD) and hot wire chemical vapor deposition (HWCVD)
while minimizing the negative effects that the high deposition rate can have on the material
quality and uniformity.
In this research particularly the effects of nc Si:H deposited at high rate on randomly or
periodically textured surfaces on the nano scale that increase the path length of light in solar cells
are investigated. Previous work showed that crystal growth of nc Si:H on steep textures gives rise to
grain boundary formation and cracks [1] due to the collision of columnar growth, compromising
the solar cells performance [2].This research aims to mitigate this effect as well as other effects that
decrease the quality of nc Si:H layers deposited at high rate by introducing incubation layers and
profiling methods and by optimizing deposition techniques and surface textures.
Figure 1: Cross sectional Transmission Electron Microscopy image of a nc-Si:H n-i-p solar cell deposited on a rough Ag/
ZnO coating. The white arrows point to the cavities and cracks, which appear not to be completely filled with
silicon [1].
[1]
[2]
R.E.I. Schropp, J.K. Rath, H. Li, Growth mechanism of nanocrystalline silicon at the phase transition and its application in
thin film solar cells, Journal of Crystal Growth 311 (2009) 760.
H. Yamamoto, M. Isomura, M. Kondo and A. Matsuda: Proc. 11th PVSEC (PVSEC, Hokkaido, 1999) p. 231.
89
Nanophotonics
Supervisor:
Ultrashort pulse lasers have proven to be efficient for precise micromachining of metals, semiconductors and dielectric materials. Due to the nature of ultra short pulse duration, laser energy is
delivered in a time shorter than electron-phonon relaxation time. This advantage over pico/nano
pulse lasers makes precise material removal possible.
90
To study the physics involved in the fs laser ablation process, weve built an automated, precise
and easily repeatable fs laser ablation setup. The self reflectivity changes due to strong optical
excitation is measured in-situ. The 3D topography of the ablated craters is measured by the AFM.
We developed a computer program which fits the AFM data automatically to extract the single
shot ablation rate (nm/pulse). The experiments have been done in several samples such as siliconon-insulator (SOI), C-Si, A-Si, indium tin oxide (ITO) and gold. An model mainly focus on the
excitation stage is developed to reproduce the ablation rates, the self reflectivity changes and to
study the effects of interference on ablation if a layered structure is used, for example, the SOI.
Figure 1: A sketch of the automated ablation setup (left). The single shot ablation rate on SOI extracted by the fitting
program (right).
Fig.1 shows a sketch of the automated ablation setup (left). The data acquisition, the focusing of
the objective, the recording of the reflected focal image, the movements of the sample stage and
the rotation of the half lambda plate are all made automated. The firing of the laser is synchronized
with the movements of the sample. The figure on the right in Fig.1 plots the single shot ablation
rate in SOI measured by the AFM and extracted by the fitting program.
91
Supervisor:
Organometallic synthesis, NMR, Gas Chromatography, X-Ray Crystallography, UV-Vis, IR, Cyclic Voltammetry
92
Over the years, pincer metal complexes have become very important in catalysis as trapping
the metal atom in a pincer ligand provides a powerful tool to tune and manipulate the catalytic
properties of the metal center. Modulating the properties of the pincer metal complexes can be
achieved by a) changing the heteroatom attached directly to the metal center, e.g. S, P, N, etc., b)
adding an electron donating or electron withdrawing substituent on the pincer arene ring para to
the metal center, and c) modifying the substituents on the heteroatoms.
Previous results in our laboratory have shown that the arene ring of a pincer ligand can be
simultaneously 6 and 1-coordinated to Ru and Pd, respectively, to form bimetallic complexes
with significant metal-to-metal interaction.[1] It has also been shown that the presence of the
RuCp* moiety has a significant effect on the electronic as well as catalytic properties of the metal
complex.[2]
Our current efforts aim at the synthesis of bimetallic complexes in which there is more than one
phenyl ring available. SCS-pincer complexes with phenyl rings attached to the sulfur form a statistical
mixture of all possible 6-coordinated products upon treatment with [RuCp*(CH3CN)3]+.We now
find that the presence of one or two substituents on the S-phenyl rings directs RuCp* coordination
selectively to the pincer arene ring, thus forming the 6,1-heterobimetallic architecture. On the
other hand, with a para-phenyl substituent on the pincer arene ring, 6-coordination occurs at
this para-phenyl substituent, and not at the arene ring of the pincer moiety. The electronic as well
as catalytic properties of these new complexes are being investigated. This methodology provides a
powerful tool to modify the structure as well reactivity of pincer complexes.
[1]. Bonnet, S.; Lutz, M.; Spek, A. L.; van Koten, G.; Klein Gebbink, R. J. M.; Organometallics 2008, 27, 159.
[2] Bonnet, S.; van Lenthe, J. H.; Siegler, M. A.; Spek, A. L.; van Koten, G.; Klein Gebbink, R. J. M.; Organometallics 2009, 28, 2325.
Supervisor:
Organometallic synthesis, NMR spectroscopy, Electrospray ionization (ESI) MS, High performance liquid
chromatography (HPLC)
Figure 1: Catalytic versatility of the developed semi-synthetic enzymes in function of the metallic center chosen, using
an NHC as the linking cofactor.
93
Supervisor:
In nature, mononuclear non-heme iron enzymes are found to play a central role in a broad array of
dioxygen activating reactions, metabolic transformations, and C-H activation reactions. In the past
decades, much research has been done on this type of enzymes and their synthetic analogues. It is
found that many of these enzymes share an active site in which two histidines and one carboxylato
group occupy one face of the iron coordination sphere leaving the other sites open for reactions.
This is the so called 2-His-1-carboxylate facial triad, shown in the figure (left). [1] Furthermore,
several studies showed that the active catalytic species of these enzymes is the high-valent iron-oxo
state of the enzymes. [2]
94
The aim of this project is to design a homogeneous iron catalyst, selective in the cis-dihydroxylation
of olefins by mimicking the active site of non-heme iron enzymes. The first generation of
biomimetic compounds were complexes of the N,N,O-ligand series introduced earlier by our
group (Figure). [3] One of the pitfalls in the use of these ligands is their tendency to form inactive
coordinately saturated FeL2 complexes with two ligands coordinating to the iron metal center.
Designing N,N,O ligands that preclude the binding of another N,N,O ligand to the same Fe
center is one of the major challenges of this project. Accordingly, very bulky ligands are developed
that prevent the formation of FeL2 complexes. Indeed it is observed that the FeL2 complexes are
not as easily formed with the more bulky ligands compared to the smaller ligands. Furthermore,
the influence of different co-ligands (figure (right)) is being investigated.
Figure: Left: Enzyme containing 2-His-1-carboxylate facial triad. Middle: N,N,O-ligand series. Right: Complex with
N,N,O-ligand and co-ligands (L-L).
[1]
[2]
[3]
Bruijnincx, P. C. A.; van Koten, G.; Klein Gebbink, R. J. M. Chem. Soc. Rev. 2008, 37, 2716-2744.
Costas, M.; Mehn, M. P.; Jensen, M. P.; Que Jr, L. Chem. Rev. 2004, 104, 939-986.
Bruijnincx, P. C. A.; Lutz M.; Spek, A. L. van Faassen, A. A.; Weckhuysen, B. M.; van Koten, G.; Klein Gebbink, R. J. M. Eur. J.
Inorg. Chem. 2005, 779-787.
Supervisor:
Biaryl compounds are ubiquitous in pharmaceuticals and functional materials. Hence, they
have received much attention from the pharmaceutical industry [1] as well as in materials and
supramolecular science. [2] The most investigated way to construct biaryl compounds through
metal mediated strategies mainly involves Ar1M as nucleophile and Ar2X as electrophile (M= Mg,
B, Zn, etc.; X=Halides, etc.), e.g. in the Suzki-Miyaura cross-coupling reaction.
Recently, direct arylation by means of C-H bond activation has been reported [3], in these cases
the Ar1M coupling partner is replaced by Ar1H to react with Ar2X. This kind of strategy provides
a much cleaner way to do cross coupling chemistry, which efficiently avoids the stoichiometric
amount of metal waste from Ar2M. However, most reports on direct arylation use expensive
noble metals such as Pd. Using catalysts based on first row transition metals such as iron in direct
arylation reactions may provide improved options for sustainable synthetic chemistry, due to their
inexpensive as well as non-toxic and environmentally benign properties.
Based on the first successful application of air stable and preformed iron phenanthroline complexes
catalyzed direct arylation reactions under air in our lab, we are interested in the mechanism of this
reaction and in the development of more efficient iron catalysts in this kind of reaction.
[1]
[2]
[3]
Hassan, J. Sevignon, M. Gozzi, C. Schulz, E. and Lemaire, M. Chem. Rev. 102 (2002) 1359.
Lehn, J. M. Science 295 (2002) 2400.
Alberico, D. Scott, M. E. Lautens, M. Chem. Rev. 107 (2007) 174.
95
Supervisor: Prof. dr. Robertus J.M. Klein Gebbink and Dr. J.T.B.H. Jastrzebski
Renewable sources (biomass) are currently considered to be used as the feedstock towards the
sustainable production of chemicals for the industries. Because fossil feedstocks are depleting
rapidly and are steadily increasing in price, it is essential to find an alternative source to produce
energy, fuels and chemicals. In particular, sugars and sugar-derived polyols contain many hydroxyl
group functionalities and are, accordingly, have a high oxygen content. In order to arrive at some
of the main chemical building blocks, e.g. olefins, the challenge is to remove the hydroxyl groups.
96
Partial or complete dehydroxylations of sugars and polyols lead to the formation of olefins
[1,2]. The removal of hydroxyl groups can also be accomplished by means of dehydration [3],
deoxygenation [4] or even deoxydehydration methods to arrive at olefins. Because rhenium has
the tendency to attract and release oxygen atoms, oxorhenium complexes have been considered
for these types of reactions. The versatile oxorhenium catalyst, methyltrioxorhenium (MTO),
has been reported in recent years for the conversion of polyols into their corresponding olefins.
Amongst those oxorhenium catalytic systems, we are working on the Cp-based catalysts [5], which
can have the potential to improve further to obtain more active and selective catalytic systems [6].
[1]
[2]
[3]
[4]
[5]
[6]
Shiramizu M. and Toste F.D., Angew. Chem. Intl. Ed. 51 (2012) 8082.
Yi J., Liu S. and Abu-Omar M.M., ChemSusChem 5 (2012) 1401.
Korstanje T.J., de Waard E.F., Jastrzebski J.T.B.H. and Klein Gebbink R.J.M., ACS Catalysis 2 (2012) 2173.
Sousa S.C.A. and Fernandes A.C., Tett. Letters 52 (2011) 6960.
Cook G. K. and Andrews M. A., J. Am. Chem. Soc. 118 (1996) 9448.
Raju S., Jastrzebski J.T.B.H. and Klein Gebbink R.J.M., confidential.
Supervisor:
Over the last 50 years, photography has gained increasing importance as a medium for artistic
expression. This includes not only photographs themselves, but also so-called photo-works:
composite artworks consisting of photography combined with one or more other techniques. The
latter may include a variety of materials, including paints, glues, cardboard, metals, wood, glass and
a range of polymers. Photo-works thus form an integral part of our cultural heritage, and they
represent an important part in the collections of several major Dutch museums including the
Stedelijk Museum in Amsterdam. Aside from this cultural aspect, there is also a financial side: many
of these artworks are worth tens of thousands or even hundreds of thousands of Euros.
However, because of the complex chemical nature of photographic material as well as the wide
variety of applications and environmental conditions, a myriad of problems has been encountered
in different artworks. These problems are not restricted to conservation issues such as aging as
degradation, but include transportation and exhibition issues as well. [1]
In constant close coordination with art historians, curators and restorers, the project focuses on
determining the nature of the interactions between photographic material and any applications,
whether they be physical or chemical in nature. The principal partners of the project include the
Stedelijk Museum in Amsterdam, the Kroller-Moller Museum in Otterlo, the Van Abbe Museum
in Eindhoven and Leiden University. In concert with these partners, it strives to develop strategies
to either retard or preferably stop these interactions, thereby slowing down the degradation
processes and preserving the artworks for the future. To this end, model systems as well as samples
of genuine artworks will be analyzed with a variety of techniques, including IR and Raman
spectroscopy, NMR and GC-MS. When necessary, model samples will be prepared and studied for
reference purposes.
[1]
Hummelen, Y.; Sill, D., Eds.; In Modern Art: Who Cares?; Amsterdam; 2006
97
Supervisor:
Prof. dr. R.J.M. Klein Gebbink, Prof. dr. B. M. Weckhuysen and Dr. P.C.A. Bruijnincx
98
Olefins can be found in nature as terpenes or unsaturated fatty acids, which are derived from
vegetable oils and animal fats. Such alkenes can be oxidatively cleaved into mono-or dicarbonyls,
i.e. aldehydes or carboxylic acids (Figure 1), which can be used in polymer, plasticizer, and stabilizer
production.These products are also useful as intermediate building blocks for subsequent reactions.
Expensive and often toxic transition-metal complexes derived from Ru, [1] W,[2] or Os[3] are
known to catalyze these specific oxidative cleavages, with the help of reactive and relatively
hazardous oxidants like NaIO4 or ozone.
We are investigating more benign processes for these oxidations. Fe-BPBP catalysts, can be used
with hydrogen peroxide in conjunction with sodium periodate to cleave aliphatic double bonds,
terpenes and unsaturated fatty acids to aldehydes. Furthermore, a combination of oxone and
periodate enables the transformation of similar alkenes into carboxylic acids without the use of
a transition-metal at all. Such procedures can be seen as green alternatives for the production of
chemical building blocks from renewable sources.
Figure 1: Reaction equation of the cleavage of unsaturated fatty acids into aldehydes using an Fe-catalyst (top), and into
carboxylic acids using sacrificial oxidants (bottom).
[1]
[2]
[3]
Rup, S., Zimmermann, F., Meux, E., Schneider, M., Sindt, M. and Oget, N., Ultras. Sonoch. 16 (2009) 266.
Turnwald, S.E., Lorier, M.A., Wright, L.J. and Mucalo, M.R, J. Mat. Sci. Lett. 17 (1998) 1305.
Ley, S.V., Ramarao, C., Lee, A.L., Oostergaard, N., Smith, S.C., Shirley, I.M., Org. Lett. 5 (2003) 185
Supervisor:
Figure 1: POSS-decorated homogeneous catalysts for hydrocarbon oxidation (1-3). The epoxides and alcohols obtained
with these catalysts.
[1]
[2]
[3]
[4]
F.G. Gelalcha, B. Bitterlich, G. Anilkumar, M.K. Tse, and M. Beller, Angew. Chem. Int. Ed. 2007, 46, 7293 7296.
M.S. Chen and C.M. White, Science 2007, 318, 783-787.
V.A. Yazerski, R.J.M. Klein Gebbink, Heterogenization of Homogeneous Catalysts on Dendrimers in Catal. Met.
Complexes 2010, 33, 171201.
A. Berger, R.J.M. Klein Gebbink, and G. van Koten, Top. Organomet. Chem. 2006, 20, 1-38.
99
100
101
Supervisor:
We develop a magnetic separation setup to separate magnetic (nano)particles from solution, using
a magnetizable porous medium made of thin magnetizable fibers. We aim to understand the
separation process on different length scales by experiment and simulation; interesting properties
are e.g. the fluid dynamics in the porous medium and behavior (capture/release) of magnetic
particles in the medium.
102
As experimental model particles for separation we make use of magnetic particles based on
thermodynamically stable Pickering emulsions [1]. We will form functional composite particles by
coating emulsion droplets with a thin layer of silica and functionalize the silica surface. This opens
a wide range of possibilities for binding solutes to magnetic particles and subsequent separation
of solute and particle together. Particles based on these kind of emulsions have the advantage of
requiring only little energy input to form.
In order to understand the fluid dynamics of the porous medium, we must first generate packing
geometries. To this end, we perform mechanical contraction simulations of spherocylinders [2] for
different aspect ratios.We are interested in the relation between aspect ratio and liquid permeability.
Additionally, we modify existing methods to include fixed, cylindrical boundaries to account for
possible boundary effects in our experimental system.
Figure 1: Schematic drawing of the separation apparatus. In the lower left corner a typical magnetic emulsion is shown.
In the lower right corner a typical random porous medium of rods is shown.
[1]
[2]
S. Sacanna et al., Thermodynamically Stable Pickering Emulsions. Phys. Rev. Lett. 2007, 98, 13-16
S.R. Williams and A.P. Philipse, Random packings of spheres and spherocylinders simulated by mechanical contraction. Phys.
Rev. E, 2003, 67(5), 19
Supervisor:
Magnetic hydrogels that swell or shrink due to changes in their chemical environment are being
developed to realize a new type of biosensor that detects chemical changes magnetically. Hydrogels
are highly cross-linked networks of polymer strands that can absorb large amounts of water while
still maintaining their shape and structure. The volume of a hydrogel depends on the aqueous
environment, and for instance, upon increase of the pH, the gels swells, while upon decrease of the
pH, the volume of the hydrogel decreases. By incorporating magnetic nanoparticles and placing
the hydrogel on a magnetic sensor, pH changes can then be detected indirectly via the magnetic
field of the swelling or shrinking gel.
The first part of the project consists of the preparation of iron oxide nanoparticles with the desired
magnetic properties and sizes. To prevent magnetic nanoparticles from leaking from the hydrogel,
surface modification of the nanoparticles is performed to chemically bind them to the hydrogel
network.To confirm that they are chemically bound, frequency-dependent magnetic susceptibility
measurements are performed.
The second part of the project is the preparation of thin hydrogel layers and the investigation of
their swelling and shrinking kinetics by optical microscopy.
The third part of the project is the realization and characterization of a prototype sensor.
103
Cubicle membranes
Sonja Castillo, S.I.R.Castillo@uu.nl, phone: 030 - 253 25 40
Sponsor:
Supervisor:
104
Water treatment and water desalination require membranes that are highly selective, allow for a
high flux with a sufficient chemical and physical resistance. We aim to develop novel inorganic
separation membranes by the assembly of porous, hollow cubic colloids into a densely packed
array on a substrate to form `cubicle membranes (figure 1).The hollow cubic colloids are prepared
from template cubic iron oxide colloids coated with porous silica and their size and shape can be
controlled accurately [1]. The properties of these building blocks can be tailored by e.g., surfaceprotected silica etching for increased porosity [2]. Additionally, the incorporation of catalytically
active iron oxide enables these building blocks to catalyze the decomposition of organic molecules
in the presence of hydrogen peroxide. Presently, we focus on the ability of densely packed cubes
to function as a separation membrane by investigating the permeability and retention properties.
Figure 1: Cubicle membrane formed by densely packed hollow silica cubic colloids
[1]
[2]
L. Rossi et al. Cubic crystals from cubic colloids. Soft Matter, 7(9):4139-4142, 2011
Y. Hu et al. Control over the permeation of silica nanoshells by surface-protected etching with water. PCCP, 12(38):1183611842, 2010
Supervisor:
The total volume of water in the Earth is 1.4 billion km3. The volume of fresh water resources
is around 2.5% of the total volume. Of this fresh water, the 70% is in the form of ice at the high
mountains and poles [1]. Besides, available fresh water is not equally distributed.Thus, there is need
of desalination processes that allow the use of sea water for drinking, agriculture and technological
and industrial development.
There are many instances in nature of osmosis taking place as spontaneous water migration
without any external assistance, e.g. water transport in plants. We aim to mimic nature using
forward osmosis and to develop draw solutions to which water spontaneously migrates without
external pressures. The forward osmosis has several advantages over other desalination methods as
the reverse osmosis, for instance, the low energy cost or the low tendency to foul the filters.
However, the forward osmosis process requires draw solutions that can compete with the large
osmotic pressure of sea water. Besides, it is equally important to be able to modify the draw
solution such that it also can release water to a clean-water sink. This modification should be
reversible such that the draw system is able to switch between drawing water in from the sea, and
releasing it to the sink.
To this purpose, we synthesize draw solutions based on magnetic colloids or nanoparticles that
allow magnetic separation, ideally with complete recovery of the osmotic drawers. Besides, these
magnetic colloids should generate very high osmotic pressures so the migration of water from the
feed reservoir to the draw solution will be fast.
For this purpose, magnetic particles coated with different polyelectrolytes are studied to determine
the osmotic pressure that they are able to generate and their potential application as draw solutions
for forward osmosis.
Figure 1: Schematic representation of the desalination of sea water by forward osmosis employing draw solutions based
on magnetic nanoparticles.
[1]
105
Supervisor:
106
Recently a method was developed in our lab to produce colloidal particles with adjustable number
of patches and angles between them. [1,2] We explore these new particles as a model system for
self-organization by making theses patches sticky.
The idea is to be able to tune the valence of the colloids, where valence is defined broadly as
the potential number of bonds formed with other colloids. Ultimately, site-specific interactions
between individual particles are expected to give rise to materials with new optical or mechanical
properties. Furthermore, they can be used as a model system to more fundamentally understand
the influence of valence on stability and formation dynamics of for example virus capsid assembly.
The colloidal molecules synthesis route is modified to make one side of the dumbbells sticky, see
figure 1. We copolymerized styrene with a functionalized monomer, resulting in spherical seed
particles with functionalized surfaces. After formation of a protrusion on these seeds, mutually
attractive molecules can be specifically linked to one side of the dumbbell.
The self-assembly of the obtained patchy colloids is studied with optical microscopy and electron
microscopy. The colloids assembly into a variety of well-defined structures, and a preference for
2D orientation was observed.
Figure 1: Synthesis route for patchy colloids. First, cross-linked polystyrene spheres with functional surface groups are
swollen with monomer. Upon increasing the temperature to 80 degrees, the polymer network relaxes, and the
monomer phase separates. The formed protrusion is polymerized, and mutually attractive groups are linked to
the seed parts.
[1]
[2]
D.J. Kraft, W.S. Vlug, C.M. van Kats, A. van Blaaderen, A. Imhof and W.K. Kegel, Self-assembly of colloids with liquid
protrusions, J. Am. Chem. Soc. 131 (2009), 1182
D.J. Kraft, J. Groenewold, W.K. Kegel, Colloidal molecules with well-controlled bond angles, Soft Matter, 5 (2009), 3823
Supervisor:
We have investigated the effect of particle shape in Pickering emulsions by employing, for the
first time, cubic, rounded-ended ellipsoidal and peanut-shaped particles (Figure A). These uniform
anisotropic hematite microparticles adsorb irreversibly at the oil-water interface in monolayers
and form solid-stabilized o/w emulsions via the process of limited coalescence. Emulsions were
stable against further coalescence for at least one year. In addition to macroscopic examination of
the emulsions, direct microscopic observations allowed for studying the interfacial packing and
orientation of anisotropic microparticles at the single particle level.
In collaboration with Lingxiang Jiang and Andrei Petukhov, we introduce the thermo-reversible coassembly of colloids into a variety of ordered structures within surfactant-cyclodextrin molecular
microtubes (Figure B). We have demonstrated that colloid-in-tube assembly is generic for colloids
with different materials and shapes and is tunable via the tube-colloid size ratio. Unique features
of our co-assembly include the in-situ observation of colloid-in-tube structures including their
thermal assembly and disassembly, the presence of colloidal structures throughout the sample
volume and its facile upscaling to tens of grams. We envision that our molecular-colloidal coassembly approach may find application in the alignment, transportation, and controlled release
of particles.
107
Supervisors:
108
Semiconductor nanocrystals are also called quantum dots, because of the quantum-size effects
in their optical and electronic properties. They are of great interest for applications in, for instance,
fluorescent labels for biomedical imaging: they can be tagged to target molecules and have the
advantage of a good resistance against photobleaching. The properties of a quantum dot are greatly
affected by its electrical dipole moment and net electric charge. An electric dipole moment implies
the presence of a strong internal electric field, which affects the electronic states and the allowed
optical transitions through the Stark effect. Moreover, a net electric charge causes the optical
and electronic properties to be drastically different than for a neutral quantum dot, resulting in a
significantly lower photoluminescence quantum efficiency. The electrical properties of quantum
dots also affect their colloidal interactions, for instance enabling controlled assembly of particles
on a substrate using electric fields. Nevertheless, great uncertainty remains about the magnitude of
the dipole moment of quantum dots and how it is affected by a net charge.
The permanent electric dipole moment and net charge of quantum dots can be determined by
measuring the complex permittivity spectrum (dielectric spectroscopy) of nanoparticles dispersed
in a liquid. Since the relative contribution of the nanoparticle dipole moments to the permittivity
spectrum is weak, we built a sensitive setup, which measures the differential signal in a bridge
circuit. Any background signal is removed using a computer controlled compensating voltage.
The complex permittivity can be measured sensitively in the range from 0.01 Hz to 10 MHz.
The dipole moment is observable as a Debye relaxation due to rotation of the nanoparticles in
the alternating electric field. At low frequencies, ions or charged nanoparticles migrate to the
electrodes, giving rise to a huge increase in permittivity, from which the diffusion coefficient and
concentration of charged species can be obtained. The complex permittivity spectrum due to
charge migration in apolar solvent, however, appears to be different from that for polar solvents.
Additionally we are exploring the use of electroacoustics. This technique employs ultrasound, as a
result of which the colloids move due to a density contrast between colloid and solvent, and the
dynamic mobility is measured from the resulting colloid vibration current (CVI). The dynamic
mobilities of TPM-coated silica particles in ethanol were measured at different ionic strengths. At
high ionic strengths the dynamic mobility (at 3.3 MHz) equals the electrophoretic mobility, which
was measured with laser-Doppler electrophoresis. At low ionic strength, however, the dynamic
mobility is significantly higher than the electrophoretic mobility, which can probably be attributed
to Maxwell-Wagner relaxation of the double layer.
Supervisor:
The objective of this project is to incorporate (mixed) dietary minerals into a colloidal, colorless,
inorganic matrix material suitable for food fortification, as food fortification is often problematic
due to the interaction of ionic minerals with the foodstuffs to which they are added. In search of
a stable colloidal dispersion of such a material, we have used various methods to prepare metal
pyrophosphate salts containing divalent mineral cations (MIIPPi), trivalent cations (MIIIPPi) or
mixtures thereof. We study the colloidal properties of the resulting systems and test the stable
dispersions for their reactivity with foodstuffs using a model system.
The systems seem to show anomalous behavior regarding DLVO theory, but we have shown that
the results can be explained by a combination of the slight solubility and the open structure of the
resulting clusters. Repeptization (redispersion) from an aggregated state is usually only possible in
charge-stabilized colloidal systems if the system is either coagulated in the secondary minimum
of the interaction potential or if the system cannot settle completely into the primary minimum.
We have analyzed the zeta potential, conductivity, and long-term stability of colloidal systems of
iron(III) pyrophosphate and surprisingly found that the system seems to defy conventional wisdom
as it can be repeptized from its coagulated state regardless of aging time and background ions.
Moreover, after having been stored for up to a month in 2 M NaCl, dialysis of iron pyrophosphate
will yield a colloidal dispersion that is actually stable for a longer period of time than a fresh system
with background electrolyte removed.
Figure 1: Anomalous redispersion explained by dissolution: clusters in dispersion (a) age over time and form large, open
aggregates (b). Dialysis of these large aggregates dissolves the linking particles, redispersing the clusters and
forming a stable dispersion.
109
Supervisor:
Prof. dr. H.N.W. Lekkerkerker, dr. A.V. Petukhov and dr. G.J. Vroege
110
Anisotropic colloids are known for their ability to form liquid crystalline phases.The main focus of
this research is on collodial gibbsite. In the bulk suspension these platelike particles can, depending
on the polydispersity and volume fraction, form a nematic and a (hexagonal) columnar phase. The
goal of this project is to investigate how structure formation is influenced by confinement.
Suspensions are therefore studied in wedge shaped cells. The role of confinement is increasing
towards the tip of the wedge. The liquid crystal structures are studied with SAXS but problems
arise because of the small cell thickness. Therefore large platelets (D600nm) are of interest
because they are optically accessible with optical microscopy. The colloidal system was adopted for
confocal fluorescence microscopy via two different methods: by covalently linking a fluorescent
dye to sterical stabilizers on the surface of the particles or by growing a fluorescent silica shell
around the particles. Preliminary microscopy results look promising.
These large gibbsite platelets have shown to form hexagonal columnar phases. Due to their size
they sediment faster, causing the columnar phase to be distorted. With SAXS this is observed as a
vertical deformation of the pattern; the pattern is elliptical in stead of circular. SAXS results show
that with an increasing effect of confinement, this elliptical distortion disappears; the distortion is
suppressed by confinement. SAXS results also indicate that confinement promotes better ordering.
Besides confinement it is also studied how other external fields (electric, magnetic) can be used
to manipulate the self-organization of anisotropic particles. In an electric field the platelets align
with their normals perpendicular to the field. SAXS and polarized light microscopy studies show
that in an isotropic suspension a paranematic phase with a negative order parameter is formed
within seconds when an electric field is applied. This paranematic ordering approaches perfect
anti-nematic order at high field strengths and strongly depends on the frequency of the field.
The second colloidal system that was studied is goethite. Suspensions of these boardlike particles
can form, again depending on polydispersity and volume fraction, (biaxial) nematic and smectic,
as well as columnar phases. Also here the influence of confinement and different external factors is
studied. We investigated the effects of an external magnetic field, as well as the effects of depletion.
It is predicted [1] that the addition of a depletant might induce the formation of biaxial nematic
and smectic phases, which is supported by preliminary results.
Supervisors:
Figure 1: LSCM pictures of assembly of hematite cubes (600nm in diameter) inside microtubes (dyed with Nile red) at
different magnifications.
[1]
[2]
[3]
[4]
111
Supervisor:
Colloidal synthesis, Confocal fluorescence microscopy, Static light scattering (SLS), Small angle X-ray
scattering (SAXS)
112
Colloids are ideal model systems for fundamental studies on the effect of building block shape and
inter-particle interactions on crystal lattice structures. Because colloids display Brownian motion,
they show phase transitions from a fluid to a crystal. Furthermore, colloids are larger and hence
slower than atoms, and thus can be studied with microscopy techniques. My project consists of
studying the crystal lattices and the defect structures, as well as their defect dynamics, for different
colloidal particles. These particles vary in shape from spheres to cubes, and their interaction
potential can be adjusted over a broad range from hard to soft and repulsive to attractive. This
allows us to systematically study the effects of different shapes and interactions on the order and
disorder in colloidal crystals.
One system we use are thermo sensitive poly-n-isopropyl acrylamide (PNIPAM) spheres that
change their size with temperature. By introducing PNIPAM particles in a non-termoresponsive
crystal, defect structures can be generated. In figure 1a,b confocal fluorescence microscopy images
are shown of the movement of a stacking faults induced by PNIPAM particles (red) in a crystal
(green). With IDL analysis tracking of the defect dynamics can be studied, as shown in the images
below where the stacking fault is highlighted.
A second system is that of hollow colloidal silica cubes. Their self-assembly into crystal structures
with convective assembly is studied. This occurs at the air-water interface in a colloidal sol under
the influence of capillary forces and solvent flux. In figure 1c-e scanning electron microscopy
images of a crystal of hollow colloidal silica cubes is shown, showing two preferred lattices. Current
investigations are focused on more cubic particles and their crystal growth and defect dynamics.
Figure 1: a,b) Top: Confocal images of a crystal doped with PNIPAM particles at different times after the start of cooling.
Bottom: 6 order of each particle, red is hexagonal order. Line defects are indicated with blue particles, which
disappear after a few seconds. c-e) SEM image of a single layer of assembled cubes. Different arrangements of
cubes occur, ranging from d) a square-like to e) hexagonal-like.
Supervisor:
Recently, a method to produce colloidal particles with adjustable number of patches and angles
between them was developed [1]. This synthesis is based on the fact that if crosslinked polymer
particles (seeds) are swollen with monomer (styrene (St) in this case), a liquid protrusion can be
formed on the surface of the seed if the swollen particles are heated. Subsequent polymerization
of the liquid monomer droplet leads to the formation of dumbbell shaped colloids.
However, this synthesis leads to the formation of chemically inert particles, since both the seed
and the protrusion consist of pure polystyrene (pSt). During this research we are investigating
the opportunities to introduce sticky character to these particles by starting off with a chemically
modified seed, for example a particle which is decorated with surface chlorine groups. This
functional seed can be used for dumbbell formation, leading to anisotropic particles which have a
chemical reactive group that is only present on the seed side of the particle (Fig. 1 top).
Subsequently the chlorine groups can be used to attach molecules which can cause stickiness
between the seed sides of multiple particles. Currently we are investigating the use of terpyridine
ligands to achieve this. Terpyridine ligands are able to coordinate a variety of metal cations [2].
Besides the mono-complex (Fig. 1 bottom), also bis-complexes, in which a cation is coordinated
to two ligands, can be formed. One can imagine that when terpyridine containing particles are
mixed with a linker which contains two metal binding ligands the particles can attach to each
other.
Figure 1: Schematic representation of synthesis chlorinated dumbbells (top) and sticky interaction via metal mediated
bonds (bottom).
The strength of the interaction between the particles can be regulated by the amount of ligands,
the amount of metal ions and by adding free competitive ligands to the system.
[1] D.J. Kraft, W.S. Vlug, C.M. van Kats, A. van Blaaderen, A. Imhof and W.K. Kegel, J. Am. Chem. Soc. 2009 131, 1182
[2] R. Shunmugam, G.J. Gabriel, K.A. Aamer, G.N. Tew, Macromol. Rapid Commun. 2010, 31, 784
113
114
The main goal of this project is to understand the formation of binary superlattices of colloidal
nanocrystals. These superlattices are new materials that combine the properties of individual
nanocrystals, for instance the fluorescent properties of semiconductor quantum dots and the
magnetic properties of ferromagnetic nanoparticles.
In the formation of these superlattices many complex interactions are involved. We will measure
the strength of these interactions by direct observation of the equilibrium structures of the
nanoparticles in a liquid dispersion as visualized with cryo-TEM both in 2D (figure 1a) and 3D
(figure 1b). Not only information about the particle-particle interactions can be obtained but
various properties related with the structure of nanoparticle dispersions can be accessed. Additional
information about the nature of the interactions will be determined with other techniques, such
as magnetometry and laser Doppler electrophoresis.
Besides this we will also characterize the properties of these nanoparticle superlattices; for instance,
we plan to make superlattices of semiconductor quantum dots and ferromagnetic nanoparticles
and to study the resulting fluorescent and magnetic properties.
Figure 1: (Left) Schematic representation of the interaction strength from cryo-TEM of particles in a liquid medium. Analysis
of the images yields the positions of the particles from which the cluster size distribution is determined. From
this distribution the pair interaction free energy can be calculated. (Right) Impressions of a sample reconstructed
with cryo-tomography.
Supervisor:
dr. Ben Ern, dr. Hans Tromp, and prof. dr. Albert Philipse
Water-soluble polymers such as dextran and gelatin are, above a certain concentration, incompatible
with each other in solution. As can be seen in Figure 1, two phases are formed, one rich in
dextran (top) and one rich in gelatin (bottom). As both phases consist for over 90% of water, this
phenomenon can be called water/water phase separation.
Our research focuses on the characterization of the water/water interface. This interface is quite
peculiar, as it is fully permeable to water. The interfacial tension is also ultra-low, on the order of
0.04 4 N/m, depending on the polymer concentrations.
In addition, there is a potential difference of a few millivolts across the water/water interface.
This potential difference is called the Donnan potential and is caused by the confinement of the
charged gelatin polymers to one of the phases. We want to characterize this Donnan potential and
its dependence on parameters such as salt or pH.
We also want to study the possibility of preparing stable water/water emulsions. By vigorously
stirring an aqueous dextran/gelatin mixture, a short-lived emulsion can be prepared, but droplet
coalescence rapidly leads to the re-formation of two macroscopic phases. By adsorbing colloids at
the interface, we aim to prevent coalescence and create stable water/water Pickering emulsions.
Because of the ultra-low interfacial tension, the adsorption of colloids will also be influenced by
the interplay between the Donnan potential and the charge of the particles.
Figure 1: Aqueous mixtures of dextran and gelatin form a homogeneous mixture at low concentrations (3 wt-% of each
polymer), while at higher concentrations the mixture phase separates into dextran- and gelatin-rich phases.
115
Supervisor:
Colloids can be used as building blocks for larger structures. Simple colloids can only form basic
colloidal crystals, whilst colloids with more complex or anisotropic features can be designed to
self-assemble into more complex structures. Patchy particles are an example of such complex
colloids. The number, size and orientations of sticky patches on a colloid surface determine the
interparticle interactions and therefore the result of their self-assembly.
116
In this project, particles are made that are anisotropic in shape and have a surface consisting
of well-defined rough and smooth areas. Attraction is induced by depletion interaction. When
choosing the right depletant size, the overlap volume of two smooth surfaces is higher than that of
two rough ones, making the smooth parts of the particle sticky. Rough particles with one curved,
smooth patch have shown to self-assemble into finite-sized micelle-like structures (Figure 1a and c) [1].
The goal of this project is to apply this principle on particles with different morphologies and
number of rough and smooth patches, in order to form new self-assembled structures. For instance,
particles with one smooth and two rough lobes (Figure 1b) were found to self-assemble into
elongated structures, as particle geometry does no longer limit longitudinal cluster growth (Figure
1d). With increasing complexity of the building blocks, more complex structures are obtained that
might form the basis for new, complex materials.
Figure 1: SEM images of particles with (a) one smooth and rough lobe and (b) one smooth and two rough lobes. (c and
d): Optical micrographs of their corresponding self-assembled structure.
[1] D.J. Kraft et al., PNAS 109(10787), 470 (2012)
117
Supervisor:
118
The overall aim of this project is to make use of new functional colloids and self-assemble these
colloids in photonic crystals. For this, anisotropic particles are being used, which upon formation
of an ordered phase scatter light preferentially along one axis. In contrast to ordinary photonic
crystals made of spherical particles that scatter light more uniformly.
So far, the research has been focused on the preparation of an inverse photonic crystal [1] that is
made from a template of ordered silica rods. Fluorescent silica rods have been prepared [2] and
are dispersed in a mixture of dimethyl sulfoxide (DMSO) and a photo-curable liquid monomer.
At high volume fractions of rods a liquid crystalline phase forms. This phase can in principle be
locked by polymerization of the dispersed medium with UV-light. In order obtain a free standing
colloidal crystal of rods, the solvent will be allowed to evaporate. Subsequently, the sample will
be heated up in order to remove the polymer and increase the scattering content. Hence, using
chemical vapor deposition and wet-chemical etching, an inverse colloidal crystal made out of air
rods in silicon can be obtained. Colloidal crystals will be characterized by confocal scanning laser
microscopy, UV-VIS-NIR-spectroscopy and light scattering methods.
Figure 1: A) TEM image of monodisperse silica rods B) Fluorescent silica rods forming a smectic phase.
[1]
[2]
Thijssen, J. H. J. Characterization of photonic colloid crystals in real and reciprocal space. PhD thesis. Utrecht University
(2007)
Kuijk, A., van Blaaderen, A. & Imhof A. Synthesis of monodisperse, rodlike silica colloids with tunable aspect ratio. J. Am.
Chem. Soc. 133 2346-2349 (2012)
Supervisor:
Figure 1: (a) Pictorial representation of the bulk phase diagram of a binary mixture, highlighting the demixing region and
the state points where critical Casimir effect and wetting phenomena are expected. (b) Adsorption isotherms
of a simple fluid in contact with an attractive wall obtained by means of density functional theory. The graph
highlights the wetting (TW) and the prewetting (TPW) temperatures.
119
Supervisor:
Confocal Fluorescence Microscopy, Particle Tracking, High Precision Parallel Plate Oscillating Shear Cell
(HIPPOS), Stimulated Emission Depletion (STED)
120
Drying of a colloidal suspension is a common phenomenon in nature and can give rise to interesting
self-assembled patterns. During evaporation of the solvent pressure is exerted on the particles,
which can lead to large stresses and undesirable fracture of the material. We want to significantly
increase our understanding of this process both for colloidal crystalline as amorphous particle films
using a new approach (quantitative, time and position resolved 3D real-space confocal analysis)
together with model particle systems in which we can tune the size, shape, interactions (including
the elastic constants of the particles and films), viscosity, wetting angle (particle and surface) and
application method (shear, vertical and horizontal drying).
Recently, it was shown that the (in)famous coffee-ring-effect is almost completely suppressed
when a drying suspension consists of ellipsoids instead of spheres, due to a difference in deformation
of the fluid-air interface [1]. Inspired by this example, we want to investigate the correlation
between the drying behavior of non-spherical particles and structure formation, using a model
system of fluorescent rod-like silica particles [2] and external fields such as electric fields and
shear flow. With recently developed image analysis software we can determine the positions and
orientations of the particles and subsequently quantify the structure with 3D bond (orientational)
order parameters. We can also study the dynamics of the process in real-space and real-time by
tracking the rotational and translational motion of the particles with the use of fast confocal
microscopy.
Figure: A) A typical rod as observed in the lab-frame. Translational trajectory (B) and rotational trajectory (C) of a single
silica rod with length L = 3.3 m and diameter D = 550 nm, dispersed in a glycerol/water mixture.
[1]
[2]
Yunker, P. J., Still, T., Lohr, M. A, & Yodh, A. G. Nature 476(7360), 308-311 (2011)
Kuijk, A., van Blaaderen, A., & Imhof, A. JACS 133(8), 2346-2349 (2011)
Supervisor:
Au nanorods (NRs) with their size in the tens of nanometer range have attracted much attention
due to their unique optical and electronic properties, which depend on their aspect ratio, shape,
and size. Like spherical Au nanoparticles, Au NRs have the ability to strongly absorb light of a
particular wavelength range due to so-called surface plasmon resonances (SPR). These SPR are
highly shape and size dependent. Due to the anisotropic shape of Au NRs, the SPR split into
two separate bands known as the transverse (TSPR) and longitudinal plasmon bands (LSPR). The
TSPR is in the visible wavelength between 500 nm and 550 nm, while the LSPR varies from
visible (600 nm) to near IR (>1200 nm), depending on the NRs aspect ratio.
The aim of our research is to incorporate these Au NRs inside emulsion droplets with an
emulsification process, forming variety of architectures such as supraclusters or supraballs. We will
both study structures resulting after drying of the droplets, but also keep the droplets liquid as then
the orientation of a possible liquid crystal phase can be tuned by an electric field. The effect of
their long range order on the plasmonic properties will be studied, and electron tomography is
used for observing their 3D structures. Moreover, a thin shell of SiO2 is coated on Au NRs surface
to tune their plasmonic properties. The SiO2 shell also acts as a spacer, which is very helpful for the
electron tomography and to tune the collectiveness of the plasmonic response.
Experiments have been started with the synthesis of Au NRs with different aspect ratio via a seedmediated growth method [1,2]. The resulted Au NRs are surrounded a bi-layer of CTAB, which
is easy to coat a mesoporous shell of SiO2 on their surfaces. The LSPR bands have red-shifted after
SiO2 coating, due to the increase of the refractive index around the Au NRs. Further studies will
involve emulsion droplet formation from the Au NRs and the SiO2 coated Au NRs.
Figure 1: SiO2 coated Au NRs with a SiO2 shell ~10 nm and vis-NIR spectra of Au NRs and Au NRs with SiO2.
[1]
[2]
121
Supervisor:
Prof.dr.ir. M. Dijkstra
122
Chirality plays a paramount role in life, chemistry, and materials science. A chiral molecule lacks
an internal plane of symmetry and has a non-superimposable mirror image. In life, many of the
biologically active molecules are chiral, for example most amino acids are left-handed, whereas
sugars are right-handed. The homochirality of the monomeric building blocks leads subsequently
to homochirality in the self-assembled higher-ordered structures (e.g. helix protein structures,
DNA). Chirality is also important in the formation of ordered structures, e.g. the exoskeletons of
crabs and shrimps, and these biological composites have inspired the interest in colloidal liquid
crystals as self-supporting ordered templates for metallic or semiconducting nanoparticles in
biomimetic composites.
Chirality also plays a major role in cholesteric (chiral nematic) liquid crystals, which are frequently
used in optoelectronic applications, such as liquid crystal displays of laptop computers, cell phones,
and flat screen televisions. The cholesteric phase can either be achieved in a pure system of chiral
molecules or by adding a small concentration of chiral dopants to a normal nematic liquid crystal
phase. However, the relation between the macroscopic chirality of the liquid crystalline phase
and the microscopic chiral details of the constituent molecules is still not understood, despite the
relevance for optoelectronic applications and biomimetic composites. Surprisingly, even the most
basic question how pronounced the chiral shape or interactions should be in order to stabilize the
cholesteric phase is still unknown. In fact, molecular chirality is not even a guarantee for the selfassembly of a chiral structure.
The overall aim of this project is to obtain a better fundamental understanding of the microscopic
origin of the macroscopic chirality in colloidal liquid crystals using state-of-the-art computer
simulations. The first objective is to study whether colloidal hard particles with a chiral shape
can form a purely entropy-driven cholesteric phase. The second objective is to investigate if the
cholesteric phase can be stabilized by pure electrostatic interactions. We plan to study different
model systems using standard MC/MD simulations, free energy calculations and developing adhoc simulation techniques.
Figure 1: (A) Schematic picture of a cholesteric phase (B-C) Systems that exhibit chiral structure [1,2] (D-E) Possible models
for chiral molecules [3].
[1]
[2]
[3]
Supervisor:
The aim of this research is to develop permeable shells that can act as containers for certain
chemicals. By manipulating the absorption and desorption behaviour of these shells, preferentially
by a trigger, one could release the contents of the shells in a controlled and localized way. These
systems are for instance interesting for drug delivery purposes and for surfactant flooding, an
enhanced oil recovery (EOR) technique, in which surfactants are used to reduce the interfacial
tension between oil and water still remaining in the rocks. By combining the triggered release of
surfactants with, possibly, a strong adsorption of the shells to the oil-water interface, we hope to
reduce the surface tension to such a level that spontaneous emulsification becomes possible.
For a proof of principle, we start with the synthesis of monodisperse, micron-sized silica/siloxane
shells using a method that was developed in our group [1]. By labeling the shells with a fluorescent
dye, the system can be monitored with Confocal Laser Scanning Microscopy (CLSM). Empty
shells buckle in a dried state, but they remain spherical in presence of a fluorescently labeled liquid
surfactant phase as a result of shell filling (Figure 1). Moreover, optical microscopy, Static Light
Scattering (SLS) and conductivity measurements are used to monitor shell formation as well as the
size and monodispersity of the system. Also, we will be studying the behavior of these shells, and
other colloids, at oil-water interfaces.
Figure 1: Confocal microscopy images of silica\siloxane shells in absence (left) and in presence (right) of a fluorescently
labeled liquid surfactant phase.
[1] Carmen I. Zoldesi and Arnout Imhof, Adv. Mater. (2005), 17, 924-928
123
Supervisor:
124
Polyhedra have exerted a fascination on man since ancient times. Recently, there has been
a resurgence in the interest in these shapes, with the advent of synthesis schemes capable of
producing colloidal polyhedra, as well as computational techniques capable of predicting the phase
behavior of such particles. In this manuscript, we consider the thermodynamic phase behavior of
a family of truncated hard cubes, where the shape evolves from a cube via a cuboctahedron to
an octahedron, as a function of level of truncation. We used Monte Carlo simulations and freeenergy calculations to establish the full phase diagram for this system. This phase diagram shows
a remarkable diversity in mesophase crystal structures and distinct close-packed structures, which
is surprising considering the smooth change in shape from cubes to octahedra. Our results are
of significant interest to the recent experimental studies performed on systems of nanoscopic
truncated cubes.
Figure: Complete Phase diagram for the truncated hard cubes family. (a) Various members of the truncated cube family
along with their shape parameter s values. (b) Phase diagram for the family of truncated cubes in the packing
fraction versus the level of truncation s representation. For more details see Ref. [1]
[1]
Anjan P. Gantapara, Joost de Graaf, Ren van Roij and Marjolein Dijkstra under preparation.
Supervisor:
Prof. dr. Alfons van Blaaderen & Dr. Arnout Imhof (SCM) and Prof. dr. Ir. Krijn de Jong & Dr.
Petra de Jongh (ICC)
Colloidal silica made from alkoxysilanes through base catalysis in water/alcohol mixtures has the
unique property that its porosity can be tuned from ultramicroporous (< 0.3nm) to micro-, mesoand even macro-porous. This kind of silica can be grown onto many metal (oxides) particles as
closed layers of 2-20 nm (or much thicker) even on noble metals as gold [1,2]. These core-shell
systems have been developed such that colloidal stability remained over the course of the reactions,
thus retaining the small size and dispersity of the catalysts.
In this project forces are combined between the groups involved in nanostructured catalysts (De
Jong and De Jongh) and the physics and chemistry of colloidal particles (Van Blaaderen and Imhof).
The multifunctional particles can be used as building blocks for solid catalysts or as catalysts on
their own.
Gold is used as a model system and is a promising catalyst for environmental processes (e.g.
low temperature CO oxidation[3]) as well as biomass upgrading (selective hydrogenation of
unsaturated aldehydes/ketones)[4]. Key problem of gold catalysts is the very low resistance against
sintering. Silica coated particles could be a remedy. Gold nanorods (NRs) coated with mesoporous
silica are used as a model system to analyze the thermal stability between coated and uncoated
gold NRs[5]. See the figure on the right for the TEM images of freshly prepared gold NRs, heat
treated gold NRs, silica coated gold NRs and heat treated silica coated gold NRs. The pictures
show that a silica coating is able to prevent the particles from sintering at elevated temperatures.
In situ TEM studies revealed more about sinter mechanisms of the coated and uncoated gold
particles in vacuum and during catalytic reaction. Catalysis studies involve liquid phase selective
hydrogenation of unsaturated cinnamaldehyde and gas phase CO oxidation.
[1]
[2]
[3]
[4]
[5]
125
Supervisors:
126
Jamming is a key feature of many systems with slow relaxation dynamics such as granular matter,
glasses, and compressed emulsions. Force networks form the skeleton of all these jammed states
of matter and these are what we want to study. The system we used for our study comprises of
monodisperse, fluorescent, hollow deformable shells in an index matched solvent. These shells are
compressed by an external pressure through centrifugation in a capillary (0.1x1mm) and because
of the density difference between the shell and the solvent, a force network develops within the
system in response to the applied stress. The interesting fact about these hollow elastic shells is
that they undergo nonlinear buckling and form dimples upon contact. The dimple formation or
change in inner volume at contacts is due to the permeability of these shells to the solvent. We
use confocal microscopy to study the structure of these compressed hollow elastic shells in 3D.
By carefully extracting the position and radius of individual particles using image J algorithms,
we measure the depth of the dimple, which varies quadratically with the force and hence the
interparticle forces for all contacts.The probability distribution of contact forces is found to show a
similar trend like other soft jammed systems like compressed emulsions and foams[1,2]. Moreover,
the stress is anisotropically distributed in the system with large number of forces in the force
network oriented in the direction of gravity/applied stress.
(a)
(b)
Figure: (a) Plot of interparticle forces inside the packing of hollow elastic shells at packing fraction 0.78. The plot
shows only forces greater than 1.4 times average force (<F>). Each rod joining the centres of two shells in
contact represents a force. The color of the rod is proportional to the orientations of the force segment, with
respect to gravitational field, g. (b) Probability distribution of normalized contact forces in the same system of
compressed shells at a packing fraction 0.78.
(1)
(2)
Supervisors:
Patchy particles are colloids with anisotropic inter-particle interactions [1]. Patchy particles are
currently an active field of research in both experiments and simulations. This research is aimed
at the synthesis and study of patchy silica particles with amongst others thermally switchable
interactions.
The interactions will be based on the presence or absence of steric stabilization. Colloids can
exhibit a temperature-dependent gelation transition in a well-chosen apolar solvent [2], when
grafted with linear aliphatic alcohols or acids. The gelation is caused by the freezing of a single
layer of alkane molecules on the particle surface, which increases Van der Waals attractions enough
to cause particles to stick to each other (e.g. octadecanol coated silica in hexadecane).
We will attempt to combine this gelation transition with techniques for producing patchy particles.
An example of such a technique is grafting of a close-packed crystal.The TEM image below shows
a patchy particle created via such a method. Such particles were made by grafting silica spheres
while packed in a crystal. The contact areas of the particles in the crystals were not modified, and
therefore silica could be grown onto these patches, yielding anisotropic particles.
1
2
Doppelhauer, G. et al. Self-assembly scenarios of patchy colloidal particles in two dimensions. J Phys: Cond
Mat 22 (2010), 104105
Roke, S. et al. Surface molecular view of colloidal gelation, PNAS 103 (2006), 13310
127
Supervisor:
Professor Dr. Han A.B. Wsten and Professor Dr. Hans C. Gerritsen
128
Fungi are well known as food (e.g. mushrooms, cheeses), and are utilized to produce industrial
and pharmaceutical proteins. Both are multibillion industries requiring quality control of the
mycelium and the mushroom. With non-linear spectral imaging we want to establish a new and
fast method to determine freshness, the absence of pathogens, and the productivity. Furthermore,
one can target more fundamental questions, like differentiation within fungal mycelium.
In non-linear spectral imaging, the contrast in the specimen arises from the autofluorescence
signal, excited by the simultaneous absorption of two near-IR photons. Some specific molecules
within the fungi are endogenous fluorophores. For example, NADH autofluorescence contains
information on the metabolic state of the fungi and the melanin is responsible for the browning
of the mushroom. Since excitation is limited to focal volume, the benefits of nonlinear imaging
include intrinsic 3-dimensionality, no out-of-plane photobleaching, and diffraction-limited spatial
resolution of 0.3 um, making it an optimal technology to study microbial metabolism at a cell
level.
Figure 1: Non-linear spectral image of the white button mushroom (A. bisporus).
Supervisor:
Density functional theory (DFT), kinetic Monte Carlo (kMC), transmission electron microscopy (TEM), cation
exchange (CE)
Heterogeneous nanostructures are nanosized crystals which consist of multiple materials, and
display a plethora of novel and tunable physical properties (optical and opto-electronic). The
structures are created under wet chemical conditions, through a process called cation exchange
(CE) whereby, e.g., the Pb atoms in a PbSe nanocrystal are partly replaced with Cd atoms. This
results in PbSe/CdSe nanostructures with complex morphologies such as CdSe nanorods with
multiple PbSe cores within.
The aim of the project is to gain understanding of the atomic mechanism behind cation exchange.
Vacancies on the cation sublattice are expected to be essential in the process of cation exchange.
Therefore, it is necessary to calculate formation energies of vacancies and interstitial atoms by
means of density functional theory (DFT) quantum mechanical calculations.
Also, energies of different phases will be calculated to determine their relative stability, and to
predict alloying and/or phase-separation of certain semiconductor mixed compounds. These are
non-time-dependent calculations which give only the potential energies in thermal equilibrium.
The DFT calculations, however, cannot describe the system at large timescales (seconds to hours) at
which cation exchange takes place. The idea is to calculate formation energies, potential energies,
and migration energies by means of DFT, and use these in Kinetic Monte Carlo simulations to
determine the shape evolution of heterongeneous nanocrystals during cation exchange.
The results of the simulations will be compared with experimental high-resolution TEM results
of (partly) cation exchanged nanocrystals, such as the PbSe/CdSe dot-in-a-rod nanocrystal shown
in Figure 1.
Figure 1: Heterogeneous core-shell nanocrystal, having a nanorod-shaped CdSe shell and a PbSe core inside. Before the
Cd-for-Pb cation exchange took place, the entire rod was PbSe. The calculations will be used to predict such
composite morphologies beforehand.
129
Supervisor:
130
The effective interaction of nanoparticles is still a little-explored field. Models used for larger
colloids fail here, mainly due to finite-size effects and the anisotropic nature of nanoparticles,
and only rudimentary models exist for them. A promising method, the Coupled Dipole Method
(CDM), treats the nanoparticles as being built up out of atoms that are being modeled as an
electron bound to the nucleus by a harmonic force.These atoms thus act as induced dipoles and can
interact with each other and possibly an external electric field, where all many-atom interactions
are taken into account by the CDM. Using a Hamiltonian approach[1,2], we can calculate the
frequencies of the eigenmodes of the system, and we can subsequently gain the ground state
interaction energy by simply summing these mode frequencies. The same Hamiltonian approach
also yields the electrostatic potential energy of the particle in an external electric field as well as
the corresponding polarizability of the nanoparticle. The CDM requires manipulations of a matrix
that is typically large (to be precise, it is a 3Nx3N matrix, where N is the number of atoms) and
optimized algorithms have to be used to achieve reasonable numbers of atoms. However, the
number of atoms the CDM can (practically) handle is below ~105, which is unfortunately slightly
below typical experimental system sizes. A possible solution to this problem is provided by noting
that the atoms that the CDM models do not necessarily have to correspond to real, physical atoms,
but could instead correspond to simply chunks of polarizable matter. The atomic polarizability
assigned to these generalized atoms can be calculated using the permittivity (contrast) of the
substance being modeled. One of the current aims of our research is to investigate how accurate
this approach is.
Figure 1: Nanoparticles can be modeled as somewhat spherical clusters of atoms, for example on an fcc grid.
[1]
[2]
Plastic crystal behavior of gold and silica nanorods with long ranged
repulsive forces
Bing Liu, b.liu@uu.nl, phone: 030 - 253 23 63
Sponsor:
Supervisor:
Rod-like particles can form liquid crystal phases (nematic and smectic). With sufficiently longranged repulsive forces, they can form crystal phases and even plastic crystal phases. These phase
transitions can be manipulated with an external electric field and have quite a potential in optoeletronic devices. This phase behavior has already been demonstrated by us for silica rods, but
with metal or semiconductor nanorods as model particles with stronger anisotropic properties
these collective phases and their switching will be even more interesting for phtonic applications.
Therefore, as a following-up, we are extending the study on silica rods to a gold rod system. The
first synthesis and optical characterization of the individual golds rods are visible in Fig. 1 next to
a plastic crystal phase of a silica rod system.
Figure 1: a) Fluorescent silica rods form plastic crystal (L=2.3m, D=0.6 m); b) TEM image and c) UV-Vis-NIR spectrum
of gold nanorods (L=46.3 nm, D=11.3 nm)
131
Supervisor:
132
Self-assembly of nanoparticles within a spherical confinement results in a multi scale system which
combines Nanomaterial properties e.g. Quantum confinement and localized Plasmon resonance
with colloidal properties e.g. Bragg-reflection. By evaporating emulsion droplets of a low boiling
apolar solvent in water we get a shrinking spherical confinement for hydrophobic media present
in the droplet. When loaded with nanoparticles a shrinking spherical confinement will force the
nanoparticles to self-assemble. Due to this spherical confinement a spherical crystalline cluster of
nanoparticles is obtained, which is called a supra-particle. If we freeze dry these supra-particles
and look at them with electron tomography, we can determine their internal crystal structures as
is shown in Fig. 1. The goal of this research is to make these assemblies monodisperse and let them
self-assemble into larger superstructures, an example of this is shown in Fig 2.
Figure: 1a) Electron tomography slice of a supra-particle showing inwards pointing wedge shaped crystalline domains
(scalebar = 30 nm). 1b) Tracked dataset where each crystalline domain is assigned a different color (only
crystalline particles are shown). 1c) Schematic representation of an icosahedron with a tetrahedral domain
pointing inwards.
Supervisor:
In recent years, growing attention has been paid to the preparation and properties of colloidal
particles that combine an anisotropic shape with a composite structure, because they combine
the properties of different materials in one particle and allow anisotropy in materials properties.
Micrometer-sized bullet-shaped silica rods can be used to make composite rod-like particles with
an asymmetric composition with respect to the direction along the main particle axis (e.g., by
copolymerization with monomers methyl methacrylate and styrene) has been recently developed
by our group (see Figure 1a). Examples of the combination of silica rods and Poly (methyl
methacrylate) (PMMA) are shown in Figure 1. This polymer end-on structure was induced by the
combination of geometric factors and a surface chemical heterogeneity of the rod particles, which
was proved with a series of experiments and theoretical calculations. In progress is the study on the
phase behavior and advanced properties of this system in the presence or absence of the external
fields (e.g., electric field).
Figure 1: Examples of as-synthesized silica-PMMA composite particles. The scale bar in a) is 200 nm and 500 nm in the
inset. Scale bars in (b-d) are 2 m and 200 in the insets.
133
Supervisor:
134
Figure 1: (a) Quasi-2D; (b) Top views of Quasi-2D hard octapod model; (c) The phase diagram for hard octapods in quasi-2D
systems; (d) An example of hard octapod model; (e) A rhombic crystal (RC) for L/D=1; (f) A square crystal (SC) for
L/D=4, which is not interlocking; (g) A binary-lattice square crystal (BSC) for L/D=6; (h) Another SC, for which
the octapods are interlocking (L/D=7).
[1]
W. Qi, J. de Graaf, F. Qiao, S. Marras, L. Manna, and M. Dijkstra, Nano Lett. 12, 5299 (2012).
Supervisor:
Colloidal synthesis, Luminescence spectroscopy, Dynamic light Scattering (DLS), Transmission electron
microscopy (TEM)
Commonly used glass fibers exhibit the lowest attenuation around 1500 nm light and for this
reason, trivalent erbium (Er3+) is often incorporated in fiber glass optics to amplify signals, as
erbium displays phosphorescence at a wavelength of approximately 1540 nm. The point at which
information still travels by photons rather than electrons is moved increasingly closer to the
individual home. Therefore the need for qualitatively better, cheaper and more versatile waveguide
materials is increasing, which explains the growing interest in polymer waveguide technology. A
drawback of polymer technology is the relatively higher loss at telecommunication wavelengths.
The use of different wavelengths with lower losses would make polymer technology incompatible
with existing optical infrastructure, so efforts are made to create polymers with low losses at
telecommunication wavelengths. Unfortunately, when these organic materials are doped with
erbium, the erbium emission is quenched.
The goal of this project is to create erbium doped silica colloids, in which the emission of erbium
is unquenched because of the protective silica layer. They must be small enough to not cause
significant scattering of light and they should be compatible with the low-loss poly(dimethylsiloxane)
(PDMS)-like polymers that are currently being developed by other partners in the FIREFLY
project.
First attempts at reaching this goal were made using a water-in-oil microemulsion, to which
ammonia, tetraethoxysilane (TES), and an erbium complex were added. The emulsion droplets
acted as reaction chambers in which the TES, catalytically driven by ammonia, converted to
monodisperse silica spheres, 50 nm in diameter at a polydispersity of 3%. During this process,
the erbium complex ended up in the centers of the particles. A transmission electron microscope
(TEM) image is shown in Figure 1.
Subsequent steps will involve the annealing of these particles to increase the quantum efficiency of
erbium luminescence, redispersion of annealed particles in a suitable solvent, and surface treatment
of the particles in that solvent. The latter serves to make them compatible with the PDMS-like
polymers that are being developed.
Figure 1: TEM image of silica particles made in an oil-in-water
microemulsion. The particles have been doped with an erbium
complex, visible as a dark dot in the middle of each particle.
135
Supervisor:
136
Nicotinamide Adenine Dinucleotide (NADH) and Flavin Adenine Dinucleotide (FAD) are
important coenzymes that play important role in regulating metabolism. It has been described
by various groups that auto-fluorescence property of NADH and FAD can be exploited to study
cancer progression and cell death [1,2] via two-Photon Fluorescence Lifetime imaging (FLIM)
system. In the general direction, we developed a unique approach of imaging and measuring
NADH (free in cytoplasm and bound to enzyme) and FAD in 3D culture by combining twophoton microscopy with spectral phasor (spectral image analysis). Our goal is to exploit this
technique to characterize cancer and non-cancer cellular spheroids (cell aggregates) by un-mixing
and quantifying the intrinsic fluorphores based on their emission spectrum. Furthermore, we can
employ NADH/FAD as possible apoptosis biomarker for 3D culture drug screening and invivo
imaging of tumor model.This is more feasible approach than standard histopathological assessment
which require fixation which likely alter fluorescence lifetimes compared with unfixed tissue.
Figure 1: Optical sectioning of CHO cell spheroid with multiphoton excitation. Spheroid of ~500 um was excited with
740 nm in which NADH and FAD can be detected. Shift in the spectrum correlates with the changes in depth.
Furthermore, shift from blue color (NADH) to yellow color (FAD) is observed. (A) Outer layer of spheroid (B)
Inner layer of the spheroid (C) Core of the spheroid.
[1]
[2]
Colloids and nanoparticles with attractive patches on their surface can establish highly directional
bonds, which allows them to form structures that cannot always be so easily realized using isotropic
interactions. Both experimentally as well as in computer simulations, such structures are found
[1-3]. However, there is not yet a reliable method to a priori predict stable crystal structures
of interacting patchy particles. We employ a combination of variable box shape Monte Carlo
computer simulations [4] and free energy calculations using thermodynamic integration schemes
[5]. In the floppy box, the unit cells of possible crystal structure candidates are computed in a
box containing a small number of particles. For a given pressure, temperature and number of
particles, the particle positions, orientations and the shape and dimensions of the box are allowed
to fluctuate. From the candidate structures, we use free energy calculations to determine their
stability.
Figure 1: Two examples of crystal structures of Janus particles inside a floppy box with periodic boundary conditions.
Janus particles consist of two different hemispheres. The hemispheres depicted in orange attract each other
via square-well attractions. The hemispheres drawn in blue interact via hard-core repulsions only. To show the
crystal structure more clearly, the unit cell was copied a number of times in all three directions.
[1]
[2]
[3]
[4]
[5]
*In collaboration with Prof. Dr. Francesco Sciortino, Sapienza Universit di Roma.
137
Supervisor:
Colloidal synthesis, Confocal fluorescence microscopy, Transmission electron microscopy (TEM), CryoElectron
tomography (cryo-3D-TEM)
138
The overall aim of the FOM program, of which this is one project, is to obtain control over the
assembly and properties of colloidal semiconductor nanoparticles into functional nanostructured
materials with interesting optical and electrical properties. To realize this, nanoparticle solution
interaction potentials need to be measured.
The radial distribution function (RDF) shows the chance of finding a particle some distance,
r, away from another particle. RDFs for nanoparticles have so far only been obtained in 2D
systems. In combination with computer simulations, the particles pair potential can be extracted
from the RDF data, leading to insight into the interparticle interactions. The role of interparticle
interactions will be studied with the aim to quantitatively understand and thus manipulate (binary)
nanocolloid crystallization.
3D RDFs will be measured using confocal fluorescence microscopy and cryo-electron tomography.
Initial studies will focus on large spherical particles with long range repulsive interactions (11.5 m silica colloids). Once these are understood, particles of smaller size and different shapes
will be investigated. One step in this process is the fixation of particles in their medium by
polymerizing (part of) the solvent with UV light. Later, the same methods will be extended to
metallic nanoparticles.
Measuring the RDF in 3D for large spherical particles has been reported in literature [1]. Using
Stimulated Emission Depletion (STED) Confocal Microscopy with a fast resonant scanner, we will
extend this to smaller particles and distances. The interaction potential measurements currently
being performed on nanoparticles in 2D will be extended to 3D using cryo-electron tomography.
Figure 1: Schematic representation of project steps. A: colloidal particle synthesis, B: confocal microscopy imaging, C: 3D
imaging (z-stack)/tomography projections, D: particle tracking, E: determining g(r).
[1]
Royall, C. P., Leunissen, M. E. & van Blaaderen, A. A new colloidal model system to study long-range interactions quantitatively
in real space. J. Phys. Condens. Matter 15, S3581-S3596 (2003)
Supervisor:
The procedure of taking biopsies is relatively slow; it often takes a week before results are available.
For this project we develop an optical biopsy method where, since biopsy is performed optically,
you get results on the spot. For this goal we have designed and built a miniaturized microscope.
Two different nonlinear microscopy techniques are used that rely on contrast based on two photon
excitation of fluorescence and second harmonic generation respectively. These techniques provide
contrast in living tissue without applying stains. Signals are detected from, amongst others, autofluorescence of metabolic products (e.g. NADH and FAD), pigments (melanin), and second
harmonic generation of connective tissue (collagen). The microscope utilizes a miniaturized
scanner that drives a fiber tip with an objective lens attached to it (developed by Philips Research).
The scanner is fitted into a 3mm diameter tube and can be operated at a 1Hz frame rate. The focal
spot is usually scanned in a circular pattern or in a raster pattern in the xy-plane and z-scanning
is accomplished by a piezo drive. The scanner is fiber coupled to the rest of the microscope using
a special double clad photonic crystal fiber. This facilitates signal guiding of both single-mode
near-infrared excitation pulses and broadband multimode visible emission. Pulse broadening of
the excitation light due to chromatic dispersion in the fiber is pre-compensated by a custom built
grating compensator. Emission is detected using a custom built spectrograph with a sensitive EM
(electron multiplication) CCD for fast (10 kHz spectral rate) spectral detection. The optical setup
is built on a mobile platform which facilitates the employment in different rooms in the clinic. It
is being used at the moment in the Erasmus MC in Rotterdam to monitor skin tumor growth in
hairless mice.
139
Supervisor:
140
Manoharan and Pine reported that, when small numbers of polystyrene microspheres were
attached to the surface of liquid emulsion droplets, removing the fluid from the droplets led
to clusters of microspheres with regular configurations [1]. Self-assembly of nanoparticles in a
spherical confinement results in multi scale system which combines nano-scale properties, e.g.
localized plasmon resonances, with colloidal properties, e.g. Bragg-reflection. Up to now, emulsiontemplated regular clusters of nanoparticles have not been reported yet.
In this research, we synthesized several kinds of nanoparticles. The nanoparticles are suspended in
low boiling solvent. This suspension is then emulsified with water as a continuous phase. When
the low boiling solvent is carefully evaporated, the nanoparticles are forced to self-assemble
within a spherical confinement. We found that under a compressive force, small numbers (n) of
nanoparticles packed into distinct and identical polyhedra for each value of n. Each cluster comes
from a single droplet containing n spheres, but n is different from cluster to cluster because the
initial droplets are not uniform in size.
In a further stage, we aim to separate clusters with certain configuration by density gradient
centrifugation.
Figure 1: The TEM images of spherical FeCoOx nanoparticles (A), spherical Au nanoparticles (B), and clusters from spherical
FeCoOx (C).
[1]
Supervisor:
Microscopy has become increasingly more important in biological and biomedical work. This
is to a great extent due to the development of advanced imaging methods such as confocal
microscopy[1,2] and multi-photon excitation microscopy[3] that provide 3-D imaging in
(optically thick) specimens. At present, multi-photon excitation microscopy is the technique of
choice for high-resolution in-vivo imaging. Unfortunately, the use of these techniques is seriously
hampered by specimen-induced aberrations[4] that result in reduced depth penetration, loss of
spatial resolution, and increased phototoxicity (Fig. 1).
Current implementations of adaptive optics[5] (AO) provide evidence that AO can significantly
improve image quality, depth penetration, and spatial resolution while reducing phototoxicity in
scanning microscopy[6]. However, severe speed limitations render them impractical for real-life
applications.
In this project we focus on the development of fast, active compensation methods for specimeninduced wavefront aberrations. High compensation speeds will be realized by using adaptive optics
in combination with smart predictive algorithms that take into account all system properties
including the scanning nature of the acquisition, the dynamic properties of the deformable mirror
based AO and the nature of the optical optimization.
We are currently investigating which wavefront sensing methods are suitable for measuring sample
induced wavefront aberrations in a microscopy context.
Figure 1: Left: without sample, a plane wave can be focused into a diffraction limited spot. Middle: in the presence of a
perturbing sample, the focus breaks up leading to loss of signal and resolution. Right: using adaptive optics we
can correct these tissue-induced aberrations.
[1]
[2]
[3]
[4]
[5]
[6]
J. B. Pawley and B. R. Masters. Handbook of Biological Confocal Microscopy. Journal of Biomedical Optics, 13(2):029902+, 2008.
David M. Shotton. Confocal scanning optical microscopy and its applications for biological specimens. Journal of Cell
Science, 94(2):175206, October 1989.
W. Denk, J. H. Strickler, and W. W. Webb. Two-photon laser scanning fluorescence microscopy. Science, 248(4951):7376,
April 1990.
M. Schwertner, M. J. Booth, and T. Wilson. Specimen-induced distortions in light microscopy. Journal of Microscopy,
228(1):97102, October 2007.
Martin J. Booth, Adaptive optics in Microscopy, Philosophical transactions. Series A, 365(1861):28292843, December 2007.
Martin J. Booth. Wavefront sensorless adaptive optics for large aberrations. Optics letters, 32(1):57, January 2007.
141
Theoretical Chemistry
142
Theoretical Chemistry
143
Theoretical Chemistry
Supervisor:
144
In our group, we use quantum chemical calculations to determine the electronic structure of
molecules and molecular complexes, their heats of formation, geometries, potential energy surfaces
and various other properties. We do ab initio Quantum Chemistry with large programs, some of
them are partly written by our group and also massively parallelised. The Valence Bond SelfConsistent Field (VBSCF) method and its efficient implementation in TURTLE VB code is such
a program, which has been developed in the Theoretical Chemistry Group of Utrecht University
and is under continuous improvement for the past two decades. The ab initio Valence Bond
approaches are especially important to get an insight into the electronic structure and properties
of molecules, because the VB wave functions can be easily interpreted in a language, which is very
familiar to chemists. However, these approaches are also computationally very demanding because
of the fact that VB wave functions are much difficult to calculate due the non-orthogonality of the
orbitals. The most notorious part in these calculations is the optimisation of the non-orthogonal
orbitals to get consistent results, which are independent of the starting point.
The aim of this project is to explore new and innovative methods for the optimisation of VB
wave functions. Very recently we have developed a second-order converging VBSCF method,
which is quite efficient compared to the previously available schemes. To make the second-order
converging scheme even more robust, further possibilities will be explored. Also, the newly written
part of the code will be parallelised before releasing it in the final form.
TURTLE
Author Index
145
Author Index
146
Author Index
Author Index
Surname, Initials
Name
Page
c.angelici@uu.nl
24
Carlo
Anjam, S.
Sohail
s.anjam@uu.nl
92
Au,Y.
Yuen
y.s.au@uu.nl
25
Baars, R.J.
Roel
r.j.baars@uu.nl
102
Bakker, H.E.
Henriette
h.e.bakker1@uu.nl
118
Basauri Molina, M.
Manuel
m.basaurimolina@uu.nl
93
Belli, S.
Simone
s.belli@uu.nl
119
Roy
r.vandenberg1@uu.nl
26
Berkum, S. van
Susanne
s.vanberkum@uu.nl
103
Besseling, T.H.
Thijs
t.h.besseling@uu.nl
120
Hendrik
h.e.vanderbij@uu.nl
27
Boga, D.A.
Dilek
d.a.boga@uu.nl
28
Boneschanscher, M.P.
Mark
m.p.boneschanscher@uu.nl
10
Bons, P.C.
Pieter
p.c.bons@uu.nl
76
Borodina, E.
Elena
e.borodina@uu.nl
29
Bramwell, P.L.
Peter
p.l.bramwell@uu.nl
30
Brand, R.P.
Rogier
r.p.brand@uu.nl
31
Casavola, M.
Marianna
m.casavola@uu.nl
32
Castillo, S.I.R.
Sonja
s.i.r.castillo@uu.nl
104
Cats, K.H.
Korneel
k.h.cats@uu.nl
33
Cicmil, D.
Dimitrije
d.cicmil@uu.nl
34
Costo Camara, R.
Rocio
r.costocamara@uu.nl
105
Deng, T.
Tian-Song
t.deng@uu.nl
121
Dijk, L. van
Lourens
l.vandijk@uu.nl
77
Dussi, S.
Simone
s.dussi@uu.nl
122
Eilers, J.J.
Joren
j.j.eilers@uu.nl
11
Elbers, N.A.
Nina
n.a.elbers@uu.nl
123
Eschemann, T.O.
Thomas
t.o.eschemann@uu.nl
35
Evers, C.H.J.
Chris
c.h.j.evers@uu.nl
106
Folkertsma, E.
Emma
e.folkertsma@uu.nl
94
Folter, J.W.J. de
Julius
j.w.j.defolter@uu.nl
107
Frey, A.M.
Anne Mette
a.m.frey@uu.nl
36
Gantapara, A.P.
Anjan
a.p.gantapara@uu.nl
124
Gao, J.
Jinbao
j.gao@uu.nl
37
Gatz, H.A.
Henriette
h.a.gatz@uu.nl
78
Arjen
a.j.vandeglind@uu.nl
125
147
Author Index
148
Groot, A.
Alexander
a.groot@uu.nl
79
Haasterecht, T. van
Tomas
t.vanhaasterecht@uu.nl
38
Harvey, C.E.
Clare
c.e.harvey@uu.nl
39
Hendriks, F.C.
Frank
f.c.hendriks@uu.nl
40
Hofmann, J.P.
Jan
j.p.hofmann@uu.nl
41
Huang,Y.
Yuxing
y.huang@uu.nl
95
Jastrzebski, R.
Robin
j.jastrzebski@uu.nl
42
Jong, M.M. de
Minne
m.m.dejong@uu.nl
80
Jongerius, A.L.
Annelie
a.l.jongerius@uu.nl
43
Jose, J.
Jissy
j.jose@uu.nl
136
Kamp, M.
Marlous
m.kamp@uu.nl
127
Knaus, H.
Helene
h.knaus@uu.nl
128
Kortschot, R.J.
Rob
r.j.kortschot@uu.nl
108
Koster, R.S.
Rik
r.s.koster@uu.nl
129
Krumer, Z.
Zachar
z.krumer@uu.nl
12
Kuang,Y.
Yinghuan
y.kuang@uu.nl
81
Kurian, R.
Reshmi
r.kurian@uu.nl
44
Kwaadgras, B.W.
Bas
b.w.kwaadgras@uu.nl
130
Landheer, C.
Kees
c.landheer@uu.nl
82
Arjon
a.j.vanlange@uu.nl
84
Leeuwen,Y.M. van
Mikal
y.m.vanleeuwen@uu.nl
109
Anke
a.b.g.m.leferinkopreinink@uu.nl
110
Lezcano-Gonzalez, I.
Ines
i.lezcanogonzalez@uu.nl
45
Lima Oliveira, R.
Rafael
r.delimaoliveira@uu.nl
46
Joost
j.vanderlit@uu.nl
13
Liu, B.
Boyang
b.liu1@uu.nl
47
Liu, B.
Bing
b.liu@uu.nl
131
Liu, P
Ping
p.liu@uu.nl
111
Luo, W.
Wenhao
w.luo@uu.nl
48
Martin-Rodriguez, R.
Rosa
r.martinrodriguez@uu.nl
14
Meijer, J.
Janne-Mieke
j.meijer1@uu.nl
112
Mitoraj, D.
Dariusz
d.mitoraj@uu.nl
15
Moes, R.J.A.
Relinde
r.j.a.moes@uu.nl
16
Mohan, A.
Akshatha
a.mohan@uu.nl
85
Munnik, P.
Peter
p.munnik@uu.nl
50
Mumann, B.O.
Ole
b.o.mussmann@uu.nl
86
Nale, A.
Angeloclaudio
ac.nale@uu.nl
51
Nijs, B. de
Bart
b.denijs@uu.nl
132
Oord, R.
Ramon
r.oord@uu.nl
52
Arjan
j.h.denotter@uu.nl
53
Ozturk, Z.
Zafer
z.ozturk@uu.nl
54
Peng, B.
Bo
b.peng@uu.nl
133
Author Index
Pietra, F.
Francesca
f.pietra@uu.nl
17
Prastani, C.
Caterina
c.prastani@uu.nl
87
Pratama, S.
Sandy
s.pratama@uu.nl
Prieto, G.
Gonzalo
g.prietogonzalez@uu.nl
55
Qi, W.
Weikai
w.qi@uu.nl
134
Qian, Q.
Qingyun
q.qian@uu.nl
57
Rabouw, F.T.
Freddy
f.t.rabouw@uu.nl
18
Raju, S.
Suresh
s.raju@uu.nl
96
Rascn, L.F.
Fernando
l.f.rasconcruz@uu.nl
58
Rashid, Z.
Zahid
z.rashid@uu.nl
144
Bas
b.g.p.vanravensteijn@uu.nl
113
Reijers, E.B.
Bas
e.b.reijers@uu.nl
97
Rijssel, J. van
Jos
j.vanrijssel@uu.nl
114
Ristanovic, Z.
Zoran
z.ristanovic@uu.nl
59
Samarai, M. al
Mustafa
m.alsamarai@uu.nl
60
Sankar, M.
Meenakshisundaram
m.sankar@uu.nl
49
Sattler, J.J.H.B.
Jesper
j.j.h.b.sattler@uu.nl
61
Evelien
e.m.vanschrojensteinlantman@uu.nl
62
Shakeri, M.
Mozaffar
m.shakeri@uu.nl
63
Sliwa, M.M.
Michal
m.m.sliwa@uu.nl
64
Spannring, P.
Peter
p.spannring@uu.nl
98
Spee, D.A.
Diederick
d.a.spee@uu.nl
88
Sprung, C.
Christoph
c.sprung@uu.nl
65
Ward
w.vanderstam@uu.nl
19
Stellwagen, D.R.
Daniel
d.r.stellwagen@uu.nl
66
Stewart, J.A.
Joseph
j.a.stewart@uu.nl
67
Stiefelhagen, J.C.P.
Johan
j.c.p.stiefelhagen@uu.nl
135
Telalovi, S.
Selvedin
s.telalovic@uu.nl
68
Truong, H.H.
Hao
h.h.truong@uu.nl
136
Veldhuizen, L.W.
Pim
l.w.veldhuizen@uu.nl
89
Vis, M.
Mark
m.vis@uu.nl
115
Vissers, T.
Teun
t.vissers@uu.nl
137
Vlug, W.S.
Wessel
w.s.vlug@uu.nl
138
Johan
c.j.vanvoskuilen@uu.nl
139
Bert
l.k.vanvugt@uu.nl
20
Wang, D.
Da
d.wang@uu.nl
140
Werkhoven, T. van
Tim
werkhoven@strw.leidenuniv.nl
141
Whiting, G.T.
Gareth
g.t.whiting@uu.nl
69
Wiedemann, S.C.C.
Sophie
s.c.c.wiedemann@uu.nl
70
Wolters, J.R.
Joost
j.r.wolters@uu.nl
116
Xie, J.
Jingxiu
j.xie@uu.nl
71
Yazerski,V.A.
Vital
v.yazerski@uu.nl
99
149
Author Index
150
Yu, D.
Dechao
d.yu@uu.nl
21
Zandvoort, I. van
Ilona
i.vanzandvoort@uu.nl
72
Zeev, J.
Jovana
j.zecevic@uu.nl
73
Zhang, H.
Hao
h.zhang1@uu.nl
90
Zhao,Y.M.
Yiming
y.m.zhao@uu.nl
22
Techniques Index
Technique Index
Computer simulations
Ab-initio calculations
Reshmi Kurian
Reshmi Kurian
Einstein integration
Bas Kwaadgras
Roel Baars
Simone Dussi
Simone Belli
Zahid Rashid
Microscopy
Atomic force microscopy (AFM)
AFMRaman
Minne de Jong
CryoTEM
Yinghuan Kuang
Fluorescence microscopy
Caterina Prastani
Gareth Whiting
151
Techniques Index
Optical microscopy
Polarization microscopy
Mustafa al Samarai
Thijs Besseling
Zoran Ristanovi
Spectral imaging
X-Ray microscopy
Jesper J. H. B. Sattler
152
Scattering Techniques
Dynamic light scattering (DLS)
Johan Stiefelhagen
Mustafa al Samarai
Clare Harvey
Spectroscopy
Atomic absorption spectroscopy (AAS)
Techniques Index
Autofluorescence
Helene Knaus
Gareth Whiting
Dielectric spectroscopy
Rob Kortschot
(in-situ) FTIR
Pim Veldhuizen
IR spectroscopy
IR microspectroscopy
Luminescence spectroscopy
Luminescence microspectroscopy
Ines Lezcano-Gonzalez
NMR spectroscopy
Caterina Prastani
Raman spectroscopy
Reflection/transmission spectroscopy
Henriette Gatz
Freddy Rabouw
Two-photon excitation
Helene Knaus
UV-Vis-NIR spectroscopy
UV-Vis spectroscopy
153
Techniques Index
UV-Vis microspectroscopy
Sankar Meenakshisundaram
Synthesis methods
Catalyst Preparation
Cell culture
Hoa Truong
Yinghuan Kuang
Cluster Deposition
Colloidal synthesis
Akshatha Mohan
iCVD
Diederick Spee
Inorganic synthesis
Nanoimprint lithography
Nanoparticle synthesis
Organic synthesis
Organometallic synthesis
154
Techniques (general)
Adaptive Optics
Analytical centrifugation
Rocio Costo
Catalytic testing
H2-Chemisorption
Techniques Index
Conductivity measurements
Da Wang
Mark Vis
Electroacoustics
Rob Kortschot
Emulsification
Thijs Besseling
Homogeneous catalysis
Vital A.Yazerski
Laser cooling
Joseph Stewart
Magnetic traps
Microtomy
Peter Munnik
N2-physisorption
Optical tweezers
Pieter Bons
Particle Tracking
Thijs Besseling
Ultrafast pump-probe
Dariusz Mitoraj
Wavefront Sensing
X-ray crystallography
Sohail Anjam
X-ray nanotomography
Korneel Cats
155
Techniques Index
156