TUM CRC BoA CRCGA Download Web PDF

Catalysis Research Center
Technical University of Munich

Graduate Academy 2016
focus topic: photocatalysis
June 5-8th 2016
TUM Science and Study Center Raitenhaslach
Book of Abstracts
crc.tum.de/graduateacademy
CRC Graduate Academy 2016 supported by
munich marseille
graduate school of
nanoscience
Faculty Graduate Centers CH and PH
Imprint
The CRC Graduate Academy 2016 is organized
in the framework of the DFH/UFA sponsored
PhD-Track PhD7-12.
dfh-ufa.org
Program Committee
Prof. Ueli Heiz, Prof. Conrad Becker,
Prof. Corinna Hess, Dr. Florian Schweinberger
Local Organization Committee
Prof. Corinna Hess, Dr. Florian Schweinberger,
Dr. Dimitrios Mihalios, Maximilian Krause,
Joachim Leibold, Irmgard Grtsch
Publisher
Prof. Ueli Heiz, Academic Director, TUM CRC
Layout and Editor
Dr. Florian Schweinberger, May 2016


Graduate Academy 2016
focus topic: photocatalysis
June 5-8th 2016
TUM Science and Study Center Raitenhaslach
Book of Abstracts
crc.tum.de/graduateacademy
Information
Venues
Wi-Fi-Access via mwn-events
TUM Science & Study Center Raitenhaslach

Raitenhaslach 3-9, 84489 Burghausen, Germany
raitenhaslach.tum.de
Wi-Fi name (SSID):

Username:
Password:
Hotel Glcklhofer
Ludwigsberg 4, 84489 Burghausen, Germany
hotel-gloecklhofer.de
Configuration profiles for wireless network

access are available via this URL:
https://www.lrz.de/wlan
(follow the link mwn-events). Access to this site
is available via the open Wi-Fi (the SSID) lrz.
mwn-events
TUMCatalysis
7RbjVrzW
Hotel Burgblick
Ach 31, 5122 Ach, Austria
altstadthotels.net
Information for speakers

Talk durations:
20 min = 15 min Presentation + 5 min Discussions,
30 min = 20 min Presentation + 10 min Discussion.
We kindly ask all speakers to provide the presentations (.pdf or .ppt format) prior to the start
of the session.
Information for poster presentations

Free choice of poster wall; please hang up your
poster during the first coffee break and keep
them available through the event.
4
Schedule
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
Posters
Johannes Bartl
Christoph Brenninger
Carla Courtois
Konstantin Epp
Stefan Ewald
Steffen Garbe
Prof. Suzanne Giorgio
Dr. Oliver Gutirrez
Han Li
Alena Hlzl
Benjamin Hofmann
Julius Hornung
Takaaki Ikuno
Dennis Knogler
Sebastian Kollmannsberger
Maximilian Krause
Paul Leidinger
Dr. Tony Lelaidier
Li Jiang
Pankaj Madkikar
Iman Marhaba
Amina Merabet
Vincent Mesquita
Elmar Mitterreiter
Daniel Rutz
Christian Schler
Jan Schwmmlein
Paul Stockmann
Moritz Wolf
Ioannis Zachos
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
Participants
66
Content
Lectures
Prof. Hermenegildo Garcia
Dr. Francesco Allegretti
Constantin Walenta
Mamouna Diouf
Prof. Richard Fischer
Dr. Oliver Thomys
Felix Kirchberger
Sebastian Standl
Marian Rtzer
Prof. Ib Chorkendorff
Prof. Conrad Becker
Jacob Ducke
Dr. Daniel Ferry
Dr. Sanyal Udishnu
Prof. Hans Niemantsverdriet
Dr. Thomas Cornelius
Jrgen Kraus
Martin Schwarz
Dr. Martin Strassburg
Kai Sanwald
Dr. Anthoula Papageorgiou
Manuel Kaspar
Ruth Haas
Prof. Miquel Costas
Schedule
Sunday June 5th
Monday June 6th
15:00 Bus shuttle from Munich to

Burghausen
08:00 Breakfast at Hotel

09:00 Bus shuttle to Raitenhaslach
16:00 Pick-Up: Airport MUC

09:30 Welcome note
10:00 Keynote Hermenegildo Garcia
16:00 Hotel Check-In
Registration
19:00 Welcome Dinner
Hotel Glcklhofer
11:00 Coffee break

11:30 Tour of the Raithenhaslach Monastery
12:30 Lunch break
14:00 Talk Francesco Allegretti
14:30 Talk Constantin Walenta
14:50 Talk Mamouna Diouf
15:10 Coffee break
16:00
16:20
16:50
17:10
17:30
MuniCat session
Introduction Richard Fischer
Talk Oliver Thomys
Talk Felix Kirchberger
Talk Sebastian Standl
Talk Marian Rtzer
18:15 BBQ
20:00 Poster Session & Informal Discussions
22:30 Bus shuttle to Hotel
Wednesday June 8th

Check-out
09:30 Keynote lecture Ib Chorkendorff
09:30
09:50
10:20
10:40
10:30 Coffee break

11:00
11:30
11:50
12:10
Talk Conrad Becker

Talk Jacob Ducke
Talk Daniel Ferry
Talk Sanyal Udishnu
Schedule
Tuesday June 7th
Talk Kai Sanwald

Talk Anthoula Papageorgiou
Talk Manuel Kaspar
Talk Ruth Haas
11:00 Coffee break

11:30 Keynote lecture Miquel Costas
12:30 Lunch break
12:30 Closing remarks
14:00 Workshop Hans Niemandsverdriet
13:00 Lunch
16:00 Coffee break

16:30 Talk Thomas Cornelius
17:00 Talk Jrgen Kraus
17:20 Talk Martin Schwarz
14:00 Bus shuttle from

Raitenhaslach to Munich
16:00 Drop-Off: Airport MUC
17:45 Looking Beyond Your Own

Backyard-Keynote Martin Strassburg
19:00 Conference Dinner
Conferment of MuniCat Poster Awards
21:30 Bus shuttle to Hotel
Lectures
Prof. Hermenegildo Garcia

Keynote
Photocatalysis for the production of solar fuels
After a short introduction in the concept of solar fuels and the use
of solar photocatalysis for their production, the presentation will
focus on the materials developed as photocatalysts by our group
including plasmonic photocatalysts, metal organic frameworks
and modified graphenes.
Technical University of Valencia, Av.
de los Naranjos s/n, Spain
hgarcia@qim.upv.es
[1]
[2]
[3]
[4]
[5]
10
Gomes Silva, C., Juarez, R., Marino, T., Molinari, R.,

Garcia, H., J. Am. Chem. Soc, 133 (3), 595-602 (2011).
Latorre-Sanchez, M., Primo, A., Garcia, H., Angew.
Chem. Int. Ed. 52 (45), 11813-11816 (2013)
Neatu, S., Antonio Macia-Agullo, J., Concepcion, P.,
Garcia, H., J. Am. Chem. Soc 136 (45), 15969 (2014).
Sastre, F., Puga, A.V., Liu, L., Corma, A., & Garcia, H.,
J. Am. Chem. Soc 136 (19), 6798 (2014).
Silva, C.G., Luz, I., Llabres i Xamena, F.X., Corma, A.,
Garcia, H., Chemistry-a European Journal 16 (36),
11133 (2010).
Dr. Francesco Allegretti
TiO2 is a promising candidate to convert sunlight into chemical

energy via photocatalytic splitting of water, however, a major drawback is that the efficiency is generally limited by the high band gap
of TiO2 and an energetically favourable backward reaction [1]. In
2012, theoretical work by A. L. Sobolewski and W. Domcke predicted that the metal-organic complex oxo-titanium porphyrin (TiOP)
can both photocatalytically split water and quench the backwards
reaction [2]. Motivated by investigations of O. Morawski et al. that
experimentally confirmed the proposed process by detection of
OH radicals generated upon irradiation to light of 445 and 570
nm wavelength [3], we aim to study the photocatalytic properties
of TiOP single layers under model conditions in ultra high vacuum
(UHV).
In this vein, we report here on the creation and characterization in UHV of a layer of oxo-titanium tetraphenyl porphyrin (TiOTPP), adsorbed on a well-defined single-crystal surface (Ag(111)),
upon metallation with Ti and subsequent exposure to molecular
oxygen of a free-base porphyrin species (2H-TPP) [4]. Through
state-of-the-art surface science methodology involving photoelectron spectroscopy, X-ray absorption spectroscopy, photoelectron
diffraction, scanning tunnelling microscopy and temperature programmed desorption techniques, we gain atomistic insight into
the structural and chemical changes leading to the formation of
an oxo-Ti group oriented perpendicular to the metal surface and
pointing outwards. The comparison with a related corrole molecule
is also presented.
Allegretti Francesco1, Deimel

Peter S.1, Duncan David A.1,2,
Casado-Aguilar Pablo1, Paszkiewicz
Mateusz1, Acres Robert G.3,
Wiengarten Alissa1, Papageorgiou
Anthoula C.1, Klappenberger Florian1,
Auwrter Willi 1, Feulner Peter 1,
Barth Johannes V. 1
Technical University of Munich,

Catalysis Research Center and
Physics Department, Chair of Molecular Nanoscience and Chemical
Physics of Interfaces, James-FranckStr. 1 and Ernst-Otto-Fischer-Str. 1,
85748 Garching, Germany
Diamond Light Source, Harwell

Science and Innovation Campus,
Didcot, OX11 0QX, UK
Sincrotrone Trieste, Strada Statale

14, km 163.5, 34149 Basovizza,
Trieste, Italy
francesco.allegretti@ph.tum.de
The prepared single layer of TiO-TPP represents an intriguing

model system for future atomic-level investigations of the photochemistry of adsorbed metal-organic complexes.
[1]
[2]
[3]
[4]
M. Ni et al., Renew. Sustainable Energy Rev. 11, 401

(2007).
A. L. Sobolewski, W. Domcke, PCCP 14, 12807 (2012).
O. Morawski et al., PCCP 16, 15256 (2014).
D. A. Duncan et al., Chem. Commun. 51, 9483 (2015).
11
Talk
Atomic-scale investigation of an in-situ prepared single

layer of oxo-titanium porphyrins on Ag(111) for model photocatalytic studies
Constantin Walenta
Talk
Ethanol photocatalysis on TiO2(110): a mechanistic study
Metal cluster-semiconductor systems are promising new hybrid

materials for combined light harvesting and conversion of photon
energy into chemical energy. As promising materials Au/TiO2 systems attracted considerable attention over the last years [1,2]. The
most explored model reaction is photochemical water splitting, but
the H2-production is still limited. Another renewable feedstock of
interest is ethanol, because alcohols are the main product from
biofermentation and as such are ideal precursors for biomass in
general [3].
In order to design ideal metal cluster-semiconductor hybrid systems and to maximize the hydrogen production yield, the understanding of the semiconductors surface photochemistry is of
paramount importance. To ensure very well defined conditions,
rutile TiO2(110) is studied under UHV conditions. Exemplified on
titania, we demonstrate how the mechanisms of photochemical
reactions can be elucidated via the judicious choice of different
experiments. It is shown, that ethanol is photooxidized to acetaldehyde. Although formally two hydrogen atoms remain from the
stoichiometric reaction equation, no molecular hydrogen production is observed [4]. The hydrogen forms water on the surface
which poisons the photocatalyst by site-blocking on a defect-rich
surface. This mechanism enables even the interpretation of ambient photocatalytic systems.
[1]
[2]
[3]
[4]
12
Murdoch et al., Nat Chem, 2011, 3, 6.

Yoshida et al., J. Am. Chem. Soc., 2009, 131, 37.
Navarro et al., Energy Environ. Sci., 2009, 2, 1.
Walenta et al., Phys. Chem. Chem. Phys., 2015, 17, 35.
Constantin Walenta1 ,2, Sebastian

Kollmannsberger1, Martin Tschurl1,
Ueli Heiz1,2
1
Chemistry Department, Chair of
Physical Chemistry, Lichtenbergstrae
4 and Ernst-Otto-Fischer-Str. 1,
Nanosystems Initiative Munich

(NIM), Schellingstr. 5, 80799 Munich,
Germany
c.walenta@tum.de
Mamouna Diouf
Producing solar fuel by water photoelectrolysis is a promising

solution for energy generation and storage. That has attracted lot
of interest towards development of photoelectrochemical cells
(PECs) that produce H2 and O2 from water splitting using solar
light [1]. PECs are generally based on semiconductor surfaces,
immersed in an aqueous electrolyte, that can use light energy
to drive electrochemical reactions such as water oxidation and
reduction. Silicon is largely used as a photoelectrode in these
PECs because of its high abundance and convenient bandgap
energy [2]. However, it is reflective and corrodes under operating
conditions in aqueous media. Micro-structuration can be used to
decrease reflectivity while increasing surface area without losing
any bulk properties of Si [3]. It has been reported that TiO2 thin film
provide protection against corrosion for silicon photoelectrodes
when they are appropriately coated [4].
Talk
Atomic layer deposition of TiO2 onto anodic black Si for

water photosplitting
Allegretti Francesco1, Mamouna

Diouf1, Lionel Santinacci1, Massa
Barr1, Bruno Fabre2, Loc Joanny2,
Francis Gouttefangeas2, Gabriel
Loget2
CINaM UMR 7325, Aix Marseille

Universit, CNRS, 13288, Marseille,
France.
Institut des Sciences Chimiques de

Rennes, UMR 6226 CNRS, Universit
de Rennes 1, Campus de Beaulieu,
35042 Rennes Cedex, France.
diouf@cinam.univ-mrs.fr
Therefore, photon absorption is increased leading to better PECs

efficiency. In this presentation , we report a rapid and cheap method to structure n-type Si with micro-pores. Antireflective silicon,
also named black silicon is has been produced by photoelectrochemical etching and subsequent alkaline etching of flat silicon.
Atomic layer deposition (ALD) is a unique method to conformably
coat high aspect-ratio substrates. ALD have been used to coat
the black silicon with anatase TiO2. These protected black silicon
photoanodes exhibit greater photocurrents under simulated sunlight than their planar counterparts.
[1]
[2]
[3]
[4]
K. Sivula and R. van de Krol, Nat. Rev. Mater., 1, 2,

15010, (2016).
K. Sun, S. Shen, Y. Liang, P. E. Burrows, S. S. Mao, and
D. Wang, Chem. Rev., 114, 17, 8662, (2014).
X. Liu, P. R. Coxon, M. Peters, B. Hoex, J. M. Cole, and D.
J. Fray, Energy Environ. Sci., 7, 10, 3223, (2014).
S. Hu, M. R. Shaner, J. A. Beardslee, M. Lichterman, B. S.
Brunschwig, and N. S. Lewis, Science, 344, 6187, 1005,
(2014).
13
Prof. Richard Fischer

Talk
Munich Catalysis The strategic alliance of TUM and Clariant
MuniCat comprises the strategic research alliance between

TUM and the specialty chemicals company Clariant in the area
of catalyst development. Clariants Catalysts business unit is a
leading global developer and producer of catalysts for industrial
processes.
MuniCat follows an industry on campus approach: TUM scientists and Clariant researchers work together to resolve questions
of fundamental and applied research in chemical catalysis. Since
its inception in 2010, more than 50 PhD, master and bachelor students have worked on ten successful MuniCat research projects
Located in the newly build and recently opened TUM Catalysis
Research Center, MuniCat will continue the established research
projects and continue with vanguard, novel project ideas in the
future.
The presentation will give an overview of MuniCats organization,
its vision and mission. Selected examples will explain how MuniCat is working, to give the audience a basis for the following presentations of the Clariant Slot of the CRC Graduate Academy.
munich-catalysis.tum.de
14
Coordinator MuniCat,
Technical University of Munich;
Chemical Technology 1, Lichtenbergstrae 4, 85748 Garching,
Germany
richard.fischer@tum.de
Dr. Oliver Thomys
The methanation of carbon dioxide is referred to as a suitable

concept for energy storage connected to renewable energies
[1]. The aim of the COOMeth project was the development of
efficient catalysts for this so called Sabatier-process. Therefore,
several hundred catalysts were prepared by various impregnation
techniques and co-precipitation, employing DoE and Data Mining strategies. For the catalytic tests, a parallel testing unit was
applied. Promising catalysts were further characterized in their
physical and structural properties. Kinetic measurements were
conducted to explore the characteristics of the highly exothermic
reaction as well as the long-term activity of the catalysts. Furthermore, a kinetic model was developed, enabling the prediction of
the intrinsic kinetic of state-of-the-art catalysts under real process
conditions [2].
Highly active catalysts with increased stability towards the demanding process conditions have been developed in this project
supported by BMBF within a cooperation of two TUM-groups
(K.-O. Hinrichsen, K. Khler) and five industry partners (Clariant
AG/MuniCat, Wacker Chemie AG, MAN SE, Linde AG, E.ON SE).
In addition, screening experiments revealed promising opportunities to further decrease the metal loading. These positive results
were confirmed by test runs under real process conditions, using
a pilot reactor provided by MAN.
[1]
[2]
K. Khler1, K.-O. Hinrichsen2, O

Thomys1, F. Koschany2, D. Schlereth2

Chemistry Department, Associate
Professorship of Inorganic Chemistry,
Lichtenbergstrae 4 and ErnstOtto-Fischer-Str. 1, 85748 Garching,
Germany

Chemical Technology 1, Lichtenbergstrae 4 and Ernst-Otto-FischerStr. 1, 85748 Garching, Germany
oliver.thomys@tum.de
M. Specht, M. Sterner, B. Strmer, V. Frick, B. Hahn,

Renewable Power Methane - Stromspeicherung durch
Kopplung von Strom- und Gasnetz - Wind/PV-to-SNG,
Registered by ZSW, on 09.04.2009. Patent No: 10 2009
018 126.1.
F. Koschany, D. Schlereth, O. Hinrichsen, Applied
Catalysis B: Environmental, Juli 2015.
15
Talk
New catalysts for the hydrogenation of carbon dioxide to

methane for energy-storage
Felix Kirchberger
Talk
Methanol to olefins: tackling the problem of catalyst

deactivation
Catalytic conversion of methanol to hydrocarbons on solid acids,

especially on H-ZSM-5 and SAPO-34, has attracted great attention and effort in the past decades in respect of methane and
syn-gas transformation as well as gasoline (MTG) and olefin (MTO)
production. One of the main problems arising in these processes
is the fast deactivation of the zeolite catalyst due to accumulation of coke. Understanding the processes which lead to carbon
deposition and the associated catalyst deactivation is challenging,
because along conventional plug-flow reactors (PFR) the complex reaction network and the decreasing methanol concentration
generates different reaction zones where carbonaceous deposits
vary drastically. While the different reaction zones for MTO have
been discussed, the concentration and nature of carbon deposits
associated to each zone and the specific impact of such coke in
the overall deactivation is not well known yet.
In this work, the kinetics of carbon formation under MTO was
studied in a back-mixed reactor (CSTR) in order to generate
homogenously coked samples with different extent of deactivation. In addition, the different zones of a PFR were simulated by
connecting several reactors in line. The study was conducted at
short times on stream and partial conversions, with the aim of
monitoring the first chemical reactions conducting to formation
of carbonaceous deposits in each zone.
[1]
16
S. Mller, Y. Liu, M. Vishnuvarthan, X. Sun, A. C. van

Veen, G. L. Haller, M. Sanchez-Sanchez, J. A. Lercher,
Journal of Catalysis, Volume, 325, 48-59, 2015.
F. Kirchberger1, S. Mller1, Y. Liu1,

M. Sanchez-Sanchez1, J. A. Lercher1

felix.kirchberger@tum.de
Sebastian Standl
Lower olefins are widely used in the polymer industry. The ever
increasing demand for propene favors catalytic cracking since
it offers possibilities of influencing the product spectrum [1]. To
obtain a fundamental kinetic model which is independent of reaction conditions or feed, the single-event concept can be used to
describe the complex reactivity of olefins on the catalytic surface
[2]. This procedure allows extrapolation out of the experimentally covered range so that both process optimization and reactor
design are possible [3]. In this work, kinetic parameters for cracking of 1-pentene on ZSM-5 are used to maximize propene yields
combined with low ethene production and high conversion. This
is done by implementing two different reactor solutions using fundamental kinetic parameters which have been determined in an
earlier work with kinetic data from 165 experiments [2].
The first reactor concept is a two-zone reactor [4]. The influence
of temperature is used here to decouple propene and ethene
yields. An initial low temperature zone which favors dimerization
is followed by a high temperature zone which shows pronounced
cracking of higher olefins. This setup shows high flexibility in adjusting the product spectrum. The second solution is a recycle
reactor where all olefins higher than propene are separated from
the product stream and led back to the reactor inlet. The kinetic
model shows that the optimum operating point is a compromise
between desired product yields and process efficiency: low temperatures lead to high propene to ethene ratios, but also cause
high recycle ratios.
[1]
[2]
[3]
[4]
Talk
Boosting the yield: how single-event kinetics can help out of

the selectivity trap
Sebastian Standl1, Tassilo

von Aretin1, Markus Tonigold2,
Kai-Olaf Hinrichsen1

Clariant Produkte (Deutschland)

GmbH, D-83052 Bruckmhl,
Germany
sebastian.standl@ch.tum.de
Mokrani, T., Scurrel, M., Cat. Rev. Sci. Eng. 51 (2009) 1.

von Aretin, T., Schallmoser, S., Standl, S., Tonigold, M.,
Lercher, J.A., Hinrichsen, O., Ind. Eng. Chem. Res. 54
(2015) 11792.
Thybaut, J.W. and Marin, G.B., J. Catal. 308 (2013)
352.
von Aretin, T., Standl, S., Tonigold, M., Hinrichsen, O.,
Chem. Eng. J., in press, doi: 10.1016/j.cej.2016.04.089
17
Marian Rtzer
Talk
Acetylene hydrogenation on Pd nanoparticles

new insights into a classical system
The selective hydrogenation of acetylene in the presence of ethene

is of major industrial importance in order to produce high quality
ethene as a feedstock for polymerization, oxidation and halogenation. Because of its intrinsic high selectivity to form ethylene, palladium is the metal of choice for this reaction with the
Lindlar-type catalyst being a famous example. Although this type
of catalyst has been successfully operated for almost 50 years,
recent developments on both, theoretical and experimental level
have shown that the surface chemistry on these palladium metal
particles is enriched by the interplay of several parameters, e.g.
subsurface hydrogen and carbon deposits, which all influence the
catalytic performance.
Marian D. Rtzer1, Maximilian Krause1,

Andrew S. Crampton1, Florian F.
Schweinberger1, Heiz U.1
1
marian.roetzer@mytum.de
To this end, we investigated the selective hydrogenation of acetylene on supported palladium nanoparticles in the sub-nm regime
consisting of 20-35 atoms under ultra-high vacuum conditions
(UHV). The reactivity of these nanoparticles is tested by using a
pulsed molecular beam technique and it is shown that already
these small particles exhibit properties of larger nanoparticles like
the formation of subsurface hydrogen species. The properties of
these species can be effectively tuned by the appropriate choice
of support and effect the intrinsic selectivity of the supported metal
particles. Furthermore the surface of these particles is characterized by IRRAS in order to determine the formation of carbonaceous species under the applied reaction conditions. The results
of the selective hydrogenation of acetylene are compared to those
of the hydrogenation of ethylene, and important differences are
highlighted.
18
Prof. Ib Chorkendorff
Keynote
Photo-electro-chemical water splitting and the making of

renewable chemicals.
Hydrogen is the simplest solar fuel to produce and in this presentation we shall give a short overview of the pros and cons of
various tandem devices [1,2]. The large band gap semiconductor
needs to be in front, but apart from that we can chose to have
either the anode in front or back using either acid or alkaline conditions. Since most relevant semiconductors are very prone to corrosion the advantage of using buried junctions and using protection
layers offering shall be discussed [3-5].In particular we shall show
how doped TiO2 is a very generic protection layer for both the
anode and the cathode [6]. Next we shall discuss the availability
of various catalysts for being coupled to these protections layers
and how their stability and amount needed may be evaluated [79]. Examples of half-cell reaction using protection layers for both
cathode and anode will be discussed though some of recent examples both under both alkaline and acidic conditions. Notably
NiOx promoted by iron is a material that is transparent, providing
protection, and is a good catalyst for O2 evolution [10]. Si is a good
low band gap semiconductor and the optimal thickness of this in
a tandem device will be discussed [11]. Finally if time allows we
shall also discuss the possibility of making high energy density
fuels by hydrogenation of CO2 instead of hydrogen evolution [12].
We shall here show how we can investigate the recent ethanol
synthesis on oxygen derived Cu found by Kanan et al. and show
how acetaldehyde seems to be an important intermediate [13].
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
CINF, Department of Physics,

Department of Physics,
The Technical University of Denmark.,
Denmark
ibchork@fysik.dtu.dk
A. B. Laursen et al, Energy Environ. Sci. 5 5577 (2012).

B. Seger et al., Energy Environ. Sci. 7 2397 (2014).
B. Seger, et al., Angew. Chem. Int. Ed., 51 9128 (2012).
B. Seger, et al., J. Am. Chem. Soc 135 1057 (2013).
B. Seger, et al., J. Mater. Chem. A, 1 (47) 15089 (2013).
B. Mai et al., J. Phys. Chem. C 119 15019 (2015).
R. Frydendal et al., Chem.Elec.Chem 1 2075 (2014).
E. A. Paoli, et al., Chemical Science, 6, 190 (2015).
E. Kemppainen et al., Energy Environ. Sci., 8 2991 (2015).
B. Mei et al., J. Phys. Chem. Lett. 5 1948 (2014).
B. Dowon et al., Energy Environ. Sci.. 8 650 (2015).
A. Verdaguer-Casadevall et al., J. Am. Chem. Soc. 137
9808 (2015).
E. Bertheussen et al., Angew. Chem., 55 1450, (2016).
19
Prof. Conrad Becker

Talk
Single molecule chemistry by STM
Scanning tunnelling microscopy is today one of the standard techniques for the analysis of solid surfaces. It allows to elucidate
the geometric and electronic structure of surfaces with atomic
resolution. Recent research has shown that electron tunnelling
can also be used to chemically modify surfaces and adsorbates
either by manipulation or by inelastic electron transfer processes.
In this presentation we will review the possibilities of chemically
modifying adsorbed molecules using the STM under UHV conditions. The focus will be on dehydrogenation processes, which
have been observed for isolated molecules but also in compact
molecular layers.
We will use recent results obtained for dihydrotetraazapentacene
(DHTAP) on Au(111) to illustrate the power of the method for synthesizing molecules, which cannot be produced by conventional
organic synthesis. In one particular case the STM can be used to
produce tetraazapentacene (TAP) by dehydrogenation of the NHgroups of DHTAP and this with molecular resolution in compact
layers. TAP can be thus produced in the first and the second
monolayer. The decoupling of the DHTAP molecules in the second
molecular layer further allows for the creation of radicals by either
single hydrogenation or dehydrogenation.
We will discuss the potential applications of this method for the
production of entire molecular layers of TAP. This could lead to
semiconducting molecular layers, which should possess similar
properties as pentacence layers.
20
Conrad Becker1, Thomas Loni1,

Tony Lelaidier1, Anthony Thomas1,
Olivier Siri1
Aix-Marseille Universit, CNRS,

CINaM - UMR 7325, Marseille,
France
conrad.becker@univ-amu.fr
Jacob Ducke
Surface-assisted covalent linking of precursor molecules enables

the fabrication of low-dimensional nanostructures. Here, we
present a temperature-induced covalent dehydrogenative coupling mechanism of free-base porphine (2H-P) units. The oligomers
resulting from a homocoupling reaction have been characterized
by a multitechnique approach and theoretical modelling, however an atomically resolved study of the resulting nanostructures
was lacking [1]. With nc-AFM we are able to identify the resulting
bonding motifs and can confirm the proposed structural models.
Furthermore, we used a similar coupling mechanism to functionalize the edges of epitaxial grown graphene on Ag(111) with
2H-P [2]. Distinct configurations are identified and resolved at the
graphene edges with submolecular precision. Functionalization
reactions like metallation of the 2H-P and subsequent axial ligation
of adducts are conserved for porphines coupled to graphene.
Thus, our findings bear promise for functionalized graphene nanostructures and for the formation of tailored oligomeres on surfaces.
[1]
[2]
Jacob Ducke1, Yuanqin He1, Alissa

Wiengarten1, Felix Bischoff1, Manuela
Garnica1, Willi Auwrter1

Physics Department, Assistant
Professorship of Molecular Engineering at Functional Interfaces,
James-Franck-Str. 1 and
Ernst-Otto-Fischer-Str. 1,
jacob.ducke@tum.de
Wiengarten, A., et al., J. Am. Chem. Soc. 136 (2014): 9346.

He, Y., et al. Fusing tetrapyrroles to graphene edges by
surface-assisted covalent coupling. submitted.
21
Talk
Surface-assisted reactions of porphyrins investigated by

nc-AFM
Dr. Daniel Ferry

Talk
Structure, chemistry and optical properties of aircraft soot

nanoparticles
Aerosols affect the climate system through various physical processes as they can scatter and absorb solar radiation, emit thermal radiation, or act as cloud condensation nuclei that modify the
cloudiness coverage, changing its albedo. Carbonaceous solid
aerosols resulting from anthropogenic processes or biomass burning are one of the most significant contributors to global climate
change with respect to their impact on radiative forcing [1]. But, it
is not clear to date how their structural and chemical characteristics affect their reactivity with atmospheric gases and their optical
properties in the UV-visible spectrum.
In this context, a multi-scale examination of the morphology and
structure of aircraft soot particles is performed by High-Resolution
Transmission Electron Microscopy. The chemical speciation of
carbon and oxygen is determined from X-ray Photoelectron Spectroscopy and Near-Edge X-ray Absorption Fine Structure measurements, providing important informations on the nature of structural
and chemical defects [2]. Ultraviolet Photoemission Spectroscopy
and specific extinction measurements in the UV-visible spectrum
[3] enable determining interband electronic transitions and their
relation to structural defects and chemistry of nanoparticles. On
the basis of these interband electronic transitions, optical properties of soot nanoparticles can therefore be understood in term
of structural and chemical characteristics at the molecular level.
The next step consists in studying interactions between soot particles and atmospheric radicals/molecules (especially water) as
well as UV-visible radiations interaction with soot. This part of
the work aims at understanding the nucleation and ice growth
processes during contrails/clouds formation, and soot ageing
processes in the atmosphere.
[1]
[2]
[3]
22
Lohmann, U. and Feichter, J. (2005) Atmos. Chem. Phys.

5, 715.
Parent, Ph., Laffon, C., Marhaba, I., Ferry, D., Regier,
T.Z., Ortega, I.K., Chazallon, B., Carpentier, Y., Focsa, C.
(2016) Carbon 101, 86-100.
Bescond, A., Yon, J., Ouf, F.-X., Roz, C., Coppalle, A.,
Parent, P., Ferry, D., Laffon, C. (2016) subm. to Journal of
Aerosol Science.
Daniel Ferry1, Iman Marhaba1,

Philippe Parent1, Tom Z. Regier2
Aix-Marseille Universit, CINaM,

campus de Luminy case 913,
F-13009 Marseille - France
Canadian Light Source, Saskatoon,

SK, S7N 2V3, Canada
daniel.ferry@univ-amu.fr
Dr. Sanyal Udishnu

Sanyal Udishnu1, Song Yang1, Oliver
Y. Gutirrez1, Johannes A. Lercher1
The realization of zero-carbon-footprint energy carriers will depend

on the availability of H2 synthesized without CO2 emission and its
suitable storage in chemical bonds. The electric energy thus obtained from renewable sources such as wind, solar, and hydropower may be potentially stored as hydrocarbon energy carriers, e.g.,
as transportation fuels [1]. Electrocatalytic hydrogenation (ECH) is
one of the conceptually most promising routes to a decentralized
production of energy carriers. Overall, the aim of the ECH is to use
protons reduced at the cathode to hydrogenate organic reactants,
while oxidization equivalents produced at the anode could be used
to mineralize by-products [2-3].
Various carbon-supported metal catalysts such as Pt/C, Pd/C

and Rh/C are found to be effective towards the ECH of phenol at
ambient condition, wherein Rh/C is the most active [4]. The ECH
rates were manipulated by tuning the negative potential which
resulted in varying concentration of adsorbed hydrogen on the
metal surface. By increasing the negative potential from 0.4 to
0.9 V (vs Ag/AgCl) ECH rates were enhanced by 40 times. ECH
is always associated with the hydrogen evolution reaction (HER),
a side process that reduces the faradic efficiency. We showed
that controlling the particle size has tremendous influence on the
faradic efficiency of the ECH process. By varying the size of metal
particles, it is found that small particles favour the HER whereas
large particles favour hydrogenation of aromatic hydrocarbons.
Thus, ECH rates and selectivity can be controlled by judicious
selection of potential and size of the metal particles at the cathode.
[1]
[2]
[3]
[4]

udishnu.sanyal@tum.de
Xin, L.; Zhang, Z.; Qi, J.; Chadderdon, D. J.; Qiu, Y.;
Warsko, K. M.; Li, W. ChemSusChem 2013, 6, 674.
Li, Z.; Garedew, M.; Lam, C. H.; Jackson, J. E.; Miller, D.
J.; Saffron, C. M. Green Chem. 2012, 14, 2540.
Li, Z.; Kelkar, S.; Raycraft, L.; Garedew, M.; Jackson, J. E.;
Miller, D. J.; Saffron, C. M. Green Chem.
Song, Y.; Gutirrez, O. Y.; Herranz, J.; Lercher, J. A. Appl.
Catal., B 2016, 182, 236.
23
Talk
Manipulation of reaction pathways in the electrocatalytic

hydrogenation of phenol
Prof. Hans Niemantsverdriet

Workshop
Presenting science
Presenting your scientific work in talks, posters and articles largely

follows the same principle: Focus on a Crystal Clear Message
intended for a Specific Audience. This workshop emphasizes how
to present science in publications, based on a course developed
for prospective authors in the Journal of Catalysis.
A free video version of a similar course on article writing by Prof.
Roel Prins can be watched on www.catalysiscourse.com, while
a summary handout for the entire course Presenting Science is
available on www.scientificleaders.com.
Syngaschem BV, DIFFER,

De Zaale 20, 5612 AJ Eindhoven
PO Box 6336, 5600 HH Eindhoven,
The Netherlands
j.w.niemantsverdriet@tue.nl
catalysiscourse.com
scientificleaders.com
24
Dr. Thomas Cornelius
In recent years, synchrotron X-ray techniques progressed tremendously thanks to the increase of the brilliance of 3rd generation
synchrotron sources as well as the achieved improvements regarding focusing optics rendering possible to focus hard X-ray
beams down to the 100 nm scale. These highly brilliant and
highly focused hard X-ray beams allow for following in situ the
evolution of nanostructures for studying their properties. Together with the brilliance the coherence of the incident X-ray beams
was increased as well triggering the development of a new lensless imaging method Bragg coherent diffraction imaging. This
new technique facilitates the measurement of strain in individual
nanostructures with unprecedented precision [1-2]. While most
measurements concentrated on weakly deformed objects under
static conditions, recent developments aim on imaging defects
as well as the strain field in nanostructures in operando [3] and
during nano-indentation. The recent achievements on in situ X-ray
studies will be illustrated by nano-mechanical and local piezoelectric measurements employing dedicated instruments recently
developed in our group at IM2NP in Marseille [4-5].
[1]
[2]
[3]
[4]
[5]
Cornelius Thomas1, Ren Zhe1,

Robach Odile2, Micha Jean-Sbastien2, Mocuta Cristian3, Borges Araujo
Eudes3, Thomas Olivier1
1
Aix Marseille Universit, CNRS,
Universit de Toulon, IM2NP UMR
7334, 13397 Marseille, France
CRG-IF BM32 Beamline at the European Synchrotron (ESRF), CS40220,

38043 Grenoble Cedex 9, France
SOLEIL Synchrotron, DiffAbs beamline, LOrme des Merisiers, Saint-Aubin - BP 48, 91192 Gif-sur-Yvette
Cedex, France
thomas.cornelius@im2np.fr
S. Labat, M.-I. Richard, M. Dupraz, M. Gailhanou, G.

Beutier, M. Verdier, F. Mastropietro, T.W. Cornelius, T.U.
Schlli, J. Eymery, O. Thomas, ACS Nano 9 (2015) 9210.
M.C. Newton, S.J. Leake, R. Harder, I.K. Robinson,
Nature Materials 9 (2010) 120.
A. Ulvestad, J.N. Clark, A. Singer, D. Vine, H.M. Cho, R.
Harder, Y.S. Meng, O.G. Shpyrko, Phys. Chem. Chem.
Phys. 17 (2015) 10551.
C. Leclere, T.W. Cornelius, Z. Ren, A. Davydok, J.-S.
Micha, O. Robach, G. Richter, L. Belliard, O. Thomas, J.
Appl. Cryst. 48 (2015) 291.
A. Davydok, T.W. Cornelius, C. Mocuta, E.C. Lima, E.B.
Arajo, O. Thomas, Thin Solid Films 603 (2016) 29 33
25
Talk
In situ synchrotron X-ray diffraction techniques
Jrgen Kraus
Talk
Graphene membranes as electron transparent windows for

photoelectron spectroscopy
Ultrathin membranes are of great interest for applications where

gases or liquids should be enclosed in a small volume to introduce
them into UHV systems and investigate them by means of electron
spectroscopy. Monolayer graphene (MLG) combines a minimum
thickness with high mechanical stability which makes it the ideal
material for the fabrication of such ultrathin membranes.
Therefore, MLG films were grown by chemical vapor deposition
on copper foils. By locally etching the Cu-substrate underneath
the as-grown graphene, free standing graphene membranes could
be fabricated. We measured the transparency of the CVD-grown
graphene for low kinetic energy photoelectrons in the energy range
of 200-1400 eV showing a high transmission between 50 % and
80 %. In order to determine the sensitivity of this technique, gold
was deposited on one side of the graphene membranes and the
Au 4f photoelectron signal was collected through the graphene
membrane which proved that < 1% of a monolayer Au can be detected. This opens up many applications of suspended graphene
membranes for the surface characterization by photoelectron
spectroscopy under ambient conditions.
26
Jrgen Kraus 1, Robert Reichelt1,

Sebastian Gnther1, Luca Gregoratti2,
Matteo Amati2, Maya Kiskinova2,
Alexander Yulaev3, Andrei Kolmakov3

Professorship of Physical Chemistry
with Focus on Catalysis, Lichtenbergstrae 4 and Ernst-Otto-FischerStr. 1, 85748 Garching, Germany
Sincrotrone Trieste, Area Science

Park, 34149 Trieste - Basovizza, Italy
Center for Nanoscale Science and

Technology, NIST, Gaithersburg, MD
20899, USA
juergen.kraus@mytum.de
Martin Schwarz
Ultrathin films of hexagonal boron nitride (h-BN) have attracted

considerable interest in recent years due to their integration in
graphene-based nano-electronic devices and their use as spacer
layers to electronically decouple and order functional adsorbates.
The successful growth of single BN layers by chemical vapor
deposition (CVD) or subsequent chemical reactions has been reported on various transition metals.
Here, we introduce an h-BN monolayer grown on a copper single
crystal, representing a model system for an electronically patterned but topographically smooth substrate [1]. Furthermore we
explored different synthesis methods of boron nitride layers on
silver substrates. Beside the direct growth of h-BN on Ag(111),
silver intercalation on the h-BN/Cu(111) system was investigated.
The quality of the resulting layers has been examined by high-resolution scanning tunneling microscopy while the electronic structure
of the metal surfaces upon 2D layer growth has been studied by
scanning tunneling spectroscopy and complementary first-principle calculations. We demonstrate that the adsorption of the 2D
layer preserves the insulating character of bulk hexagonal boron
nitride but alters the substrates surface potential and has an impact on the binding energy of the Shockley-state. It is shown that
the catalytic metal substrates play a crucial role in the decomposition of the borazine precursor gas. The h-BN sheets are used to
create metal-organic networks featuring structural, electronic and
magnetic properties unachievable on metallic supports [2].
[1]
[2]
Schwarz Martin1, Garnica Manuela2,

Stradi Daniele3, Barth Johannes V.2,
and Auwrter Willi1


Department of Micro- and Nanotechnology, Center for Nanostructured Graphene, Technical University of
Denmark, Denmark
martin.schwarz@tum.de
Joshi, S. et. al., Nano Lett., 2012, 12, 5821-5828.

Urgel, J. I., et. al., J. Am. Chem. Soc., 2015, 137 (7), 2420.
27
Talk
Catalytic role of metal substrates for the growth of

hexagonal boron nitride
Dr. Martin Strassburg

Keynote
LEDs and laser diodes: Todays and future trends in lighting
Semiconductor based light emitting diodes (LEDs) and laser diodes (LDs) paved the way for novel developments in the general
illumination sector in the recent years, similar to the semiconductor triggered electronic revolution some decades ago. They
are compact in size and can be made very robust to be used in
various application fields supported by their long lifetimes. They
have demonstrated superior efficiency for almost every field of
application compared to incandescent and conventional lighting
technologies, from low-power (e.g., signaging) to high power
applications (e.g. projection). Today, lighting is by far more than
brightness and efficiency. Other properties of light have gained
increasing importance strongly triggered by the human perception
of light, such as correlated color temperatures, brilliance and color
rendering index. In addition, the convergence of photonics and
electronics yields technological integration and miniaturization of
LEDs enabling novel functionalities, steering routines and individual configurations.
An introduction to OSRAM Opto Semiconductors numerous
activities in research and development of next generation LEDs/
Lasers and future trends for lighting applications will be given.
Examples such as high power LEDs and pixelized LEDs will illustrate the close interplay of material development, thorough understanding of scientific background and of technological solutions
yielding to products keeping the leadership in many application
fields.
osram-os.com
28
OSRAM Opto Semicondutors GmbH,

Leibnizstr. 4,
93055 Regensburg, Germany
martin.strassburg@osram-os.com
Kai Sanwald
Photocatalytic reforming of biomass-derived oxygenates is as a

promising route to carbon-neutral H2. The technology may provide simpler pathways compared to overall water splitting, as the
recombination of H2 and O2 is avoided and separation is greatly
facilitated. The wide abundance of oxygenate contaminants in
water would make this even a preferred route, coupling water
cleaning with storing photon energy in H2.
We probed photoreforming of polyols and sugars over a benchmark Rh/TiO2 photocatalyst to identify the nature and kinetics of
transformations of reactants, intermediates, and elementary steps.
Anodic oxidation of oxygenates proceeds via direct and indirect
hole transfer mainly resulting in (i) oxidative rupture of C-C bonds,
and (ii) oxidation to aldoses or ketoses while evolving H2 at the
cathode. We establish that the molecular reactant structure has
a periodic impact on the contribution of those oxidation mechanisms, and photocatalytic rates. Increasing conversion of polyols via
direct C-C-cleavage in the first step with increasing chain length
result from the increasing number of anchoring OH-functionalities
favoring conversion through a direct hole transfer mechanism.
Photocatalytic rates of linear C1-C3 oxygenates are primarily dependent on the substrate specific apparent adsorption constants
and follow a Langmuir adsorption model. On the other hand,
declines in H2-evolution rates over time beyond this model are
encountered in the presence of cyclic hemiacetals and formates
derived therefrom, which is a consequence of blocking of anodic
sites by formate species while the cathodic half-reaction does not
limit to the overall photocatalytic rates under these conditions.
This contribution highlights the importance of the understanding
of the surface chemistry in photocatalytic transformations of structurally complex feeds.
[1]
[2]
[3]
Talk
Catalytic routes and oxidation mechanisms in photoreforming of oxygenates
Kai E. Sanwald1, Tobias F. Berto1,

Wolfgang Eisenreich1, Oliver Y.
Gutirrez1, Johannes A. Lercher1

kai.sanwald@tum.de
K. Shimura, H. Yoshida, Energ. Environ. Sci. 4 (2011)

2467-2481.
.T.F. Berto, K.E. Sanwald, W. Eisenreich, O.Y. Gutirrez,
J.A. Lercher, J. Catal. 2016, 338, 68-81.
R. Chong, J. Li, Y. Ma, B. Zhang, H. Han, C. Li, J. Catal.
2014, 314, 101-108.
29
Dr. Anthoula Papageorgiou

Talk
Metallo-porphyrin chemistry on surfaces
Metal-organic species and nanoarchitectures at well-defined interfaces provide high potential for key technological applications,
spanning over the design of single-site heterogeneous catalysts,
novel materials for light harvesting, the fabrication of molecular
rotors and nanomachines and the advent of molecular spintronics.
The advancement is underpinned by the continuous development
of materials with tailored properties controllable at the molecular
scale. Thus it is of central importance to explore new strategies
for synthesis and processing, which should ideally minimize costs
and effort and be clean, reproducible and highly controlled.
Tetrapyrrole molecules and in particular porphyrins are stable, naturally occurring compounds which can coordinate a vast array of
metal centres [1]. Here we visit the chemical transformations that
prototypical porphyrin species, such as tetra phenyl porphyrin
[2] and porphine [3], undergo upon thermal tr eatment on a silver
surface. In particular, we exemplify stereo and chemo-selectivity in
both intramolecular and intermolecular dehydrogenative reactions
which result in an extension of the conjugated molecular system.
We further investigate the on-surface functionalization of such
species with various metals, including Ru [4] and Os [5].
Our methodology encompasses a battery of cutting-edge experimental techniques developed for ultrahigh vacuum surface
science: scanning probe microscopies address single molecule
behaviour, while temperature programmed reaction spectroscopy,
photoelectron spectroscopy and near edge X-ray absorption fine
structure allow to scrutinize molecular ensembles. The integration of all these analysis techniques combined with theoretical
considerations generates a high degree of precision in the understanding of interfacial reactions at the atomic level. Henceforth the
structure function relationships of the reactions may be deciphered
enabling inno vative pathways for the bottom-up fabrication of
advanced, functional nanoarchitectures.
[1]
[2].
[3]
[4]
[5]
30
Diller, K., et al. Chem. Soc. Rev. 2016, 45, 1629-1656.

Wiengarten, A., et al. Chem. Eur. J. 2015, 21, 12285-12290.
Wiengarten, A., et al. J. Am. Chem. Soc. 2014, 136, 9346-9354.
Papageorgiou, A. C., et al. ACS Nano 2013, 7, 4520-4526.
Saglam, ., et al. Surf. Sci. 2016, 646, 26-30.
Anthoula C. Papageorgiou1, Alissa

Wiengarten1, Katharina Diller1, Sybille
Fischer1, Seung Cheol Oh1, zge
Saglam1, Julian A. Lloyd1, Knud
Seufert1, David A. Duncan1, Manuela
Garnica1, Joachim Reichert1,
Francesco Allegretti1, Florian
Klappenberger1, Willi Auwrter2,
Johannes V. Barth1


a.c.papageorgiou@tum.de
Manuel Kaspar
So far, the reduction of protons is sufficiently fast only on rare and

expensive noble metal electrodes. However, current research focuses on the development of catalysts using abundant and cheap
metals to replace noble metals [1]. Over the past years, macrocyclic cobalt complexes have arisen as encouraging systems for
water splitting and proton reduction [2]. For the design of new
catalytic systems, one has to consider that the reduction of water
is a two electron process and that biological systems often use
redox-active ligands for multi-electron processes [3].
Therefore, we were interested in the bioinspired redox-active
macrocyclic N4 ligand (Mabiq), which supports formal metal valences from 0 to +3. We have synthesized a series of Co(Mabiq)
complexes and succeeded in isolating the formally Co(III), Co(II),
Co(I) forms and another low-valent compound. The complexes
have been characterized by means of different spectroscopic
methods, as well as by magnetic susceptibility studies. Electrochemical and reactivity studies indicate activity of the Co(Mabiq)
system with respect to hydrogen evolution.
[1]
[2]
[3]
Talk
Synthesis, characterization and reactivity of a series of

Co(Mabiq) complexes
Kaspar Manuel1, Corinna Hess1

Chemistry Department, Assistant
Professorship of Bioinorganic
Chemistry, Lichtenbergstrae 4 and
Ernst-Otto-Fischer-Str. 1, 85748
Garching, Germany
manuel.kaspar@tum.de
Mahammed, A.; Mondal, B.; Rana, A.; Dey, A.; Gross, Z.,
Chem. Commun. 2014, 50, 2725.
Artero, V.; Chavarot-Kerlidou, M.; Fontecave, M., Angew.
Chem. Int. Ed. 2011, 50, 7238-7266.
Jurss, J. W.; Khnayzer, R. S.; Panetier, J. A.; El Roz, K. A.;
Nichols, E. M.; Head-Gordon, M.; Long, J. R.;Castellano,
F. N.; Chang, C. J., Chemical Science 2015, 6, 4954-4972.
31
Ruth Haas
Talk
Asymmetric bimetallic complexes for multi-electron

catalysis
Non-innocent ligands, such as diimine or PDI (pyridine diimine)

scaffolds, are generating a platform of catalytically active complexes for small molecule activation. These scaffolds can store
up to three electrons [1] and therefore support metal complexes
with varied charged states. Several examples of metal complexes
containing non-innocent ligands are already known and have been
used for oxidation, hydrogenation [2] and polymerisation reactions
[3].
We have incorporated redox-active ligands into the design of our
new asymmetric bimetallic complexes. The ligand scaffold contains two coordination sites, a PDI group adjacent to a cyclam
ring, bridged by an aliphatic chain. The idea behind our design
is that the synergistic interactions of the metal might facilitate
multi-electron reactions and mimic enzyme activities.
A goal of our studies will be now to catalyse small molecule chemistry including like hydrogen production and CO2 activation. The
complexation chemistry of the ligands was studied and suggests
the formation of bimetallic compounds, which were examined by
spectroscopic and electrochemical methods. Results of these
studies and preliminary reactivity studies will be presented.
[1]
[2]
[3]
32
S. C. Bart, K. Chopek, E. Bill, M. W. Bouwkamp, E.

Lobkovsky, F. Neese, K. Wieghardt, P. J. Chirik, J. Am.
Chem. Soc. 2006, 128, 1390113912.
P. J. Chirik Acc. Chem. Res. 2015, 48, 16871695.
M. W. Bouwkamp, E. Lobkovsky, P. J. Chirik J. Am.
Chem. Soc. 2005, 127, 9660-9661.
Ruth Haas1, Corinna Hess

Chemistry Department, Assistant
Professorship of Bioinorganic
Chemistry, Lichtenbergstrae 4 and
Garching, Germany
ruth.haas@mytum.de
Prof. Miquel Costas

Keynote
Selective oxidation reactions with bioinspired catalysts
Biologically inspired catalysts are explored in our research efforts

with the aim to produce selective oxidation reactions. The quest
for catalytic methodologies that provide novel reactivities and
selectivities that could complement those attained with traditional oxidants, or that could represent a more efficient alternative
constitute major reasons of interest for this approach [1].
Towards this end, iron coordination complexes ligated to amine
and oxygen containing functionalities, and that could be viewed as
a minimalistic model of iron coordination sites in nonheme iron dependent oxygenases, are employed as catalysts for the oxidation
of organic substrates. By control of their structure and electronic
properties, catalysts have been designed by our research team
that engage in controlled O-O lysis of H2O2 to form highly electrophilic high valent metal-oxo species that are finally responsible for
enzyme-like selective oxidation chemistry [2-4].
Institute of Computational Chemistry

and Catalysis (IQCC) and
Departament de Quimica,
Universitat de Girona, Spain
miquel.costas@udg.edu
Principles of catalyst design and use of these catalysts in selective

C-H and C=C oxidation reactions as well as efforts aiming at the
Identification of reaction intermediates [5] responsible for these
oxidations will be discussed.
[1]
[2]
[3]
[4]
[5]
L. Que, W. B. Tolman, Nature 2008, 455, 333

Z. Codola, J. Lloret-Fillol, M. Costas, in Progress in
Inorganic Chemistry: Volume 59, John Wiley & Sons,
Inc., 2014, pp. 447-532.
O. Cuss, X. Ribas, J. Lloret-Fillol, M. Costas, Angew.
Chem. Int. Ed. 2015, 54, 2729-2733.
O. Cuss, M. Cianfanelli, X. Ribas, B. Klein Gebbink, M.
Costas, J. Am. Chem. Soc. 2016, 138(8), 27322738.
J. Serrano-Plana, W Oloo, L. Acosta-Rueda, K. Meier, B.
Verdejo, E. Garcia-Espaa, M. Basallote, E. Mnck, L.
Que, A. Company, M. Costas, J. Am. Chem. Soc. 2015,
137(50), 1583315842.
33
Posters
35
Johannes Bartl
Poster
High-performance photocatalytic hydrogen evolution on

size-range selected Ni-cluster decorated CdS nanorods
Addressing the overall limitation of fossil energy carriers and

noble metals, a noble-metal-free photocatalytic system using Ni
clusters for highly efficient hydrogen evolution as a renewable
energy source has been developed. Well-established nucleation and growth processes of metal clusters on semiconductor
photocatalysis are based on either light-assisted deposition [1] or
chemical reduction [2] of oxidized precursors in solution, however
lack independent control of cluster size and coverage. To this end,
recently a new photocatalytic hybrid material based on CdS nanorods (NRs) decorated with metal clusters has been introduced.
By means of catalyst deposition from a laser ablation cluster
source under ultra-high vacuum conditions independent control
of coverage and size of the co-catalyst could be established [3,4].
In this work size-range selected Ni clusters deposited on CdS
nanorods (NRs) in a highly alkaline environment are presented as
high-performance photocatalysis. The three-component system
consists of CdS NRs as a photosensitizer, EtOH as a sacrificial
electron donor and Ni as a co-catalyst. This allows on one hand
for an atomic scale insight into a photocatalytic system, by utilizing
sub nanometer clusters as tailored catalyst materials. On the other
hand, by independently controlling the number of clusters per CdS
NRs unit area together with highly optimized reaction conditions
exploiting the redox shuttle mechanism [5] a potent new hybrid
photocatalytic system is created. Considering the lower costs of
earth-abundant metals this novel platform promotes an overall
efficiency of four orders of magnitude higher than comparable
noble-metal based photocatalytic systems [3,4].
[1]
[2]
[3]
[4]
[5]
36
Berr, M. J. et al., Small 8, 291297 (2012).

Habas, S. E. et al., J. Am. Chem. Soc. 130, 32945 (2008).
Schweinberger, F.F. et al., J. Am. Chem. Soc. 135, 13262
13265 (2013).
Berr, M. J. et al., Nano Lett. 12, 59035906 (2012).
Simon, T. et al., Nat. Mater. 13, 10131018 (2014).
Johannes D. Bartl1,2, Christian M.

Wolff3, Marian D. Rtzer1, Markus
Dblinger4, Florian F. Schweinberger1,
Jochen Feldmann3, Ueli Heiz1

munich marseille graduate school

of nanoscience (m2gsn), Master
Nanoscience and Catalysis
m2gsn.tum.de
Ludwig-Maximilians-Universitt
Mnchen, Photonics and Optoelectronics Group, Department of Physics
and Center for NanoScience (CeNS),
Amalienstrae 54, 80799 Mnchen,
Germany
Ludwig-Maximilians-Universitt
Mnchen, Department of Chemistry,
Butenandtstrae 5-13 (E), 81377
Mnchen, Germany
johannes.bartl@tum.de
Christoph Brenninger
The [2+2] photocycloaddition is one of the most important and

most frequently used photochemical transformations and had
also a large impact on natural product synthesis.[1] In this type
of reaction two -bonds are used to obtain two new -bonds
and up to four stereogenic centres are set up. Due to its large
number of stereogenic centres and fast access to cyclobutanes
and their consecutive reaction products enantioselective methods
are desirable [1,2]. Therefore different enantioselective methods
using auxiliary based approaches, PET (photoinduced electron
transfer) catalysis, excitation via sensitization and Lewis acid catalysis were investigated [2]. Enantioselective intramolecular [2+2]
photocycloaddition reactions of enones are difficult due to their
unselective background reactions via * excitation and therefore
high catalyst loadings are necessary [3,4].
Poster
Sulfonium ions in organic photochemistry
Christoph Brenninger1, Thorsten

Bach1

Organic Chemistry 1, Lichtenbergstrae 4 and Ernst-Otto-Fischer-Str. 1,
christoph.brenninger@mytum.de
In this project the effect of acetalization and thioacetalization of

enones on their photo physical properties were studied. Due to
this modifications * transitions are no longer observable and
* transitions are shifted to shorter wavelengths, comparable to
those of isolated double bonds. As expected from their UV/Vis
spectra dioxalanes, dithiols and dithianes undergo no unselective background reactions, since there is no absorption between
250 nm and 400 nm. Formation of oxonium and sulfonium ions
by Brnsted acids leads to absorptions at 280 nm and 356 nm,
which can be used for photochemical reactions at 300 nm and 405
nm respectively. Racemic intramolecular [2+2] photocycloaddition
reactions were carried out with 7.5 mol% of catalyst. Chiral Brnsted acids might allow an enantioselective reaction, which is also
under investigation [5].
[1]
[2]
[3]
[4]
[5]
T. Bach, J. P. Hehn, Angew. Chem. Int. Ed. 2011, 50,

1000-1045.
S. Poplata, A. Trster, Y.-Q. Zou, Thorsten Bach, Chem.
Rev. ASAP.
R. Brimioulle, T. Bach, Science 2013, 342, 840-843.
R. Brimioulle, T. Bach, Angew. Chem. Int. Ed. 2014, 53,
12921-12924.
R. J. Phipps, G. L. Hamilton, F. D. Toste, Nat. Chem.
2012, 4, 603-614.
37
Carla Courtois
Poster
Light scattering on electrophoretic inks of carbon and TiO2

particles
Electrophoretic ink displays are nowadays used in many paper-like

devices, nevertheless not many open-source research information
about electrophoretic displays are available since the commercialization of E-Readers. Based on the research of Werts et al.,
we constructed an e-ink display cell. An image is produced by
applying an external electric field between a copper plate and
indium-tin-oxide (ITO) glass in which charged particles can align.
These particles reside between those two plates in a dielectric
suspension. For the purpose of getting a high contrast, white TiO2
particles and black functionalized carbon particles were charged
with polyisobutylene succinimide (OLOA 1200) [1].
Building of an e-ink cell requires measurement of the scattered
light to determine the contrast and the switching time. The reflectivity of a HeNe-laser on a prepared e-ink cell was measured by
a Si photodiode. In order to reduce the noise, a resistance was
added to the photodiode and the data acquisition was optimized
in a self-made LabVIEW program. The sensitivity of the photodiode
turned out to be higher using a brighter suspension; thus a higher
ratio of white TiO2 to black carbon particles was applied so that
an appropriate switching was measured. Finally, the setup was
improved so that a difference between black and white particles
results in 120 mV and the characteristics of the e-inks such as the
switching time and contrast were investigated.
[1]
38
M. P. L. Werts et al., Chem. Mater. 20, 1292-1298 (2008).
Courtois Carla1,2, Lukas Niederegger1,

Michael Rpke1, Radka Kittova1,
Friedrich Esch1


m2gsn.tum.de
carla.courtois@tum.de
Konstantin Epp
Metal-Organic Frameworks (MOFs) are materials which are formed

by a self-assembly of inorganic secondary building units (SBU)
connected by multitopic organic linkers. Like zeolites MOFs promise catalysis-friendly features such as large internal surface areas,
extensive micro- and/or mesoporosity, and crystallographically
well-defined cavities and portals of molecular dimensions, which
makes them attractive as potential heterogeneous catalysts [1].
Nowadays catalysts need to satisfy requirements such as sustainability, recyclability and also face challenges like insufficient
selectivity.
Therefore, we report on multi-functional catalyst design, f.e. the
controlled encapsulation of atom-precise clusters (Co, Mo etc.)
and nanoparticles (NP) into MOFs, abbreviated as metal@MOFs
(Pd, Cu, Au etc.) and discuss the catalytic properties [2]. This concept could be extended to core/shell metal NP (f.e. Pd@Pt) in order
to introduce novel centers of reactivity and also take advantage
of the size-selective catalysis of substrates induced by the given
pore-diameter [3]. As another concept, we report defect engineering as a synthetic tool for node-functionalization at the metal-oxo
clusters of the SBU, generating structural defects (in particularly
coordinatively unsaturated sites) which trigger enhanced reactivity
and engender catalyst design on an atomistic level in the isomerization/ hydrogenation of olefins [4].
[1]
[2]
[3]
[4]
Konstantin Epp1, Mirza Cokoja1,

Christoph Rsler1, Stefano Dissegna1, Francesc X. Llabrs i Xamena2,
Roland A. Fischer1

Inorganic and Organometallic Chemistry, Lichtenbergstrae 4 and ErnstOtto-Fischer-Str. 1, 85748 Garching,
Germany
Instituto de Tecnologa Qumica,

Consejo Superior de Investigaciones
Cientficas, Universidad Politcnica
de Valencia, Spain
konstantin.epp@tum.de
H. Li, M. Eddaoudi, M. OKeeffe, O. M. Yaghi, Nature

1999, 402, 276-279.
S. Hermes, Roland A. Fischer et al. Angew. Chem. Int. Ed.
2005, 44, 6237 6241.
I. Luz, C. Rsler, K. Epp, F. X. Llabrs i Xamena, Roland A.
Fischer, Eur. J. Inorg. Chem. 2015, 39043912.
O. Kozachuk, I. Luz, F. X. Llabrs i Xamena, H. Noei, M.
Kauer, H. B. Albada, E. D. Bloch, B. Marler, Y. Wang, M.
Muhler, R. A. Fischer, Angew. Chem. Int. Ed. 2014, 53,
7058-7062.
39
Poster
Metals@MOFs and defect engineering as methods for

catalysts optimization
Stefan Ewald
Poster
On the surface determination of a coprecipitated Ni/Al2O3

catalyst by chemisorption of N2O and H2
For the characterization of Ni surfaces H2-TPD and static H2 chemisorption are widely used [1-2]. Recently Tada et al. established the
pulse titration of N2O to determine the Ni surface area of impregnated Ni/-Al2O3 catalysts [4]. In this contribution N2O chemisorption for Ni surface area determination of a coprecipitated Ni/Al2O3
catalyst is compared with static H2 chemisorption and H2 TPD.
The catalyst is prepared via coprecipitation of the corresponding
metal nitrate salts. The precipitate is calcined at 723 K and analyzed by static H2 chemisorption. N2O chemisorption and H2-TPD
are conducted in a flow setup. H2 adsorption prior to H2 TPD is
either conducted by injecting diluted H2 into a He stream flowing
over the catalyst or by feeding non diluted H2 gas into the reactor.
N2O chemisorption is either conducted as flow experiment or as
titration experiment using N2O pulses flowing over the catalyst.
The Ni surface area of 16.6 m2/gcat after adsorption of 40 H2 pulses agrees well with 17.1 m2/gcat from static H2 chemisorption. In
contrast, the Ni surface area is 24.6 m2/gcat when adsorbing H2
for 30 min. N2O chemisorption gives a Ni surface area of 65,1 m2/
gcat which is higher than results from static H2 chemisorption and
H2-TPD. N2O titration experiments still give a significantly higher
Ni surface area. N2O chemisorption seems to overestimate the Ni
surface area of the catalyst studied. It is currently under investigation to what extent the catalyst support and synthesis influence
N2O chemisorption results.
[1]
[2]
[3]
[4]
40
L. Znak, J. Zielinski, Appl. Catal. A, 334 (2008) 268-276.

S. Velu, S.K. Gangwal, Solid State Ionics, 177 (2006)
803-811.
R. Geyer, J. Hunold, M. Keck, P. Kraak, A. Pachulski,
R. Schdel, Chem. Ing. Tech. 84 (2012)
S. Tada, M. Yokoyama, R. Kikuchi, T. Haneda,
H. Kameyama, J. Phys. Chem. C, 117 (2013) 14652-14658.
Stefan Ewald1, Kai-Olaf Hinrichsen1

stefan.ewald@ch.tum.de
Steffen Garbe
Poster
Intensity and wavelength dependence of a dye-sensitized

solar cell
Steffen Garbe1,2, Marvin Lechner1,

Jakob Filser1, Friedrich Esch1
The control and improvement of electricity gaining solar devices is

of great importance in emerging renewable energy technologies.
Commonly established solar cells are built out of semiconducting
materials on the basis of silicon to convert sunlight into energy.
Nanocrystalline dye-sensitized solar cells represent a promising
different technology, orientated at the two-step photosynthetic process in plants, i.e. excitation of an organic dye by electromagnetic
radiation in the UV/Vis range and deexcitation by electron transfer
into the conduction band of the semiconductor. Dye-sensitized
solar cells can be produced using natural anthocyanin dyes extracted from berries, titanium dioxide as semiconductor and iodide
electrolyte solution. However, further improvements concerning
efficiency performance and fill factor are essential for commercialization. The efficiency performance is mainly dependent on
the integrated materials, whereas non-ideal conditions caused by
parasitic effects decrease the power maximum and therefore the
fill factor. Determination and reduction of these effects pave the
way towards high-power dye-sensitized solar cells.
1

m2gsn.tum.de
steffen.garbe@tum.de
We report the construction of the cell, the acquisition of data and

the specific properties of the cell. The results of the experiments
show increasing power at higher radiation intensities, wavelength
dependency and lead to further investigations concerning the efficiency improvement.
[1]
[2]
A. D. Dhass et al., 2012 International Conference on

ICETEEEM, pp. 382386 (2012).
Greg P. Smestad et al., Journal of Chemical Education 75
752 (1998).
41
Prof. Suzanne Giorgio

Poster
In situ study of Au-Rh Nanoalloys, growth in solution and

reactivity
Au-Rh nanoalloys prepared from colloidal solution [1], were in

situ studied in a graphene liquid cell [2-3] and in an environmental sample holder [4], by transmission electron microscopy. The
growth mechanism in liquid was initiated under the electron beam,
the size and density number of NPs was recorded in the same area
during the nucleation and growth process. The density number
indicates a maximum after 25 s, then a drop after 50 s in the electron beam, corresponding to a mechanism by direct adsorption of
the monomers followed by coalescence of the particles. The effect
of oxidation- reduction cycles on the structure and morphology of
Au-Rh nanoparticles supported on TiO2 nanorods powders, was
in situ followed by ETEM.
A. De Clercq1, L. Piccollo2, S. Giorgio1
CINAM, Aix Marseille Universit,

CNRS, CINaM UMR 7325 Marseille
France.
IRCELYON, CNRS, Villeurbanne,

France.
suzanne.giorgio@univ-amu.fr
In the largest NPs, core- shell formation was clearly observed

during hydrogen adsorption. On the other hand, the observation
of Au-Rh NPs annealed ex situ in H2 at 400 C, also shows the
core- shell contrast which was not visible before H2 treatment. The
strong interaction between hydrogen and Rh is certainly responsible for the surface segregation of Rh.
We thank the ANR DINAMIC11BS10-009 for financial support and

Rgion PACA for a grant given for the PhD thesis of A. De Clercq
(2012-2015).
[1]
[2]
[3]
[4]
42
Konuspayeva et al., PCCP 17 (2015) 28122.

J.M. Yuk et al., Science, 336 (2012) 61.
De Clercq, et al., J. Phys. Chem Lett., 5 (2014) 2126-2130.
S. Giorgio et al., Ultramicroscopy. 106 (2006) 503.
Dr. Oliver Gutirrez
Photocatalytic overall water splitting requires co-catalysts, which

efficiently promote the generation of H2 but do not catalyze its back
reaction with O2 to water. We demonstrate, that CO chemisorbed
on precious metal co-catalysts (Rh, Pt, Pd) suppresses the back
reaction while preserving the H2 evolution reaction (HER). Over Rh/
GaN:ZnO, maximum H2 production rates are obtained between 4
and 40 mbar of CO while the back reaction is suppressed below
7 mbar of O2. The O2 evolution reaction (OER) and HER compete
with CO oxidation and a light-driven back reaction, re-spectively.
The rates of all these reactions rise with increasing photon absorption. However, due to different dependences on the rate of charge
carrier generation, the selectivities to OER and HER increase over
CO oxidation and back reaction with increasing photon flux and/
or quantum efficiency. Under optimum conditions, the efficiency
of the CO molecular layer (manipulable by CO partial pressure,
photon flux, and quantum efficiency of the photocatalyst) for hindering the back reaction is identical to the effect of a Cr2O3 layer
covering the HER-active core.
Poster
Overall water splitting over photocatalysts with CO-covered

noble metals
Tobias F. Berto1, Kai E. Sanwald1,

Oliver Y. Gutirrez1, Johannes A.
Lercher1

oliver.gutierrez@mytum.de
43
Han Li
Poster
Synthesis of new Fe-NHC complexes and corresponding

exploration of their photo properties
More and more attention has been drawn on the chemical utilization of solar energy in recent years. A range of sensitizers emerged
over these years, while the Ru and Ir complexes remain to be the
most widely utilized photocatalysts. Meanwhile, great efforts have
been made to replace the rare elements complex with the earth
abundant elements such as Fe.
Unfortunately, little progress was achieved due to the extremely
short-lived metal-to-ligand charge transfer states of iron complexes. However, a big breakthrough has been made recently, which
demonstrated that some iron complex bearing NHCs was able
to converts light to electrons with 92% yield.This throws highlight
on further research of exploring Fe complexes as new visible light
catalysts.
On this occasion, we plan to synthesis iron complex with new
structure, and explore its photo properties, aiming at making some
progress towards the utilization of Fe complex in photocatalysis.
[1]
[2]
[3]
[4]
44
Eur. J. Inorg. Chem., 2015, 2469.

Inorg. Chem. 2015, 560.
Nat. Chem. 2015, 883.
NPG Asia Materials, 2016, e261.
Han Li1, Fritz E. Khn1

Professorship of Molecular Catalysis,
Lichtenbergstrae 4 and Ernst-Otto-Fischer-Str. 1, 85748 Garching,
Germany
han.li@ch.tum.de
Alena Hlzl
One of the major challenges in photochemistry is the utilization

of visible light for enantioselective transformations. Having suitable sensitizers in hand visible light can be used for excitation,
similar or even more effective than UV-light. In 2014 Bach et al.
presented a chiral thioxanthon catalyst [(-)-TX] for enantioselective
[2+2] photocycloaddition reactions induced by visible light [1].
To further utilize this highly promising catalyst the identification
of new substrate classes is required. A special binding motif for
the substrates is necessary promoting a chiral environment by
non-covalent interactions between the substrate and catalyst.
Diazocompounds are an interesting substance class due to their
ability to form triplet carbenes after photochemical excitation
using a sensitizer [2-3]. Preliminary work by A. V. Silva showed
the reactivity of different diazocompounds towards alkenes and
alkynes after photochemical excitation. Irradiation ( = 419 nm)
of the diazocompound 3-diazopiperidin-2-one and an alkyne in
presence of the (-)-TX catalyst promotes the formation of an allene.
The enantioselective reaction could be performed with excellent
ee`s from 96% to 99% with yields up to 41%. The formation of the
allene was proved by deuterium experiments. To further optimize
the yields different reaction conditions will be screened and the
substrate scope will be extended.
[1]
[2]
[3]
Poster
Enantioselective photoreactions of diazocompounds using

a chiral thioxanthone catalyst
Alena Hlzl1, Thorsten Bach1

Organic Chemistry 1, Lichtenbergstrae 4 and Ernst-Otto-Fischer-Str. 1,
alena.hoelzl@tum.de
R. Alonso, T. Bach, Angew. Chem. Int. Ed. 2014, 53,

4368-4371.
J. P. Toscano, M. S. Platz, V. Nikolaev, V. Popic, J. Am.
Chem. Soc. 1994, 116, 8146-8151.
H. D. Roth, M. L. Manion, J. Am. Chem. Soc. 1975, 97,
779-783.
45
Benjamin Hofmann
Poster
Lignin as renewable carbon feedstock - Studies on the

cleavage of a -O-4 model substrate by Re2O7
Lignin is a promising renewable carbon feedstock due to its high

abundance and highly aromatic structure. For an application, low
molecular weight compounds have to be obtained by the selective
degradation of the macromolecular structure. For this purpose,
redox active catalysts as well as acids or bases are mainly applied,
although photocatalytic systems are also known in the literature
[1-2].
In this work, the Lewis acid Re2O7 is applied in the cleavage of the
most abundant -O-4 binding motif. Using 2-(2-methoxyphenoxy)-1-phenylethanol as a model substrate, full conversion is obtained within 7 h (TOF 240 h1) using low catalyst concentrations
of 0.1 mol% (TON >800). Conveniently, a good selectivity towards
guaiacol and phenyl acetaldehyde is observed with 75 80 %.
Detailed kinetic studies reveal the formation of different by-products depending on the reaction progress. In contrast to MTO, a
reduction step is no prerequisite for the formation of the active
species.[3] UV/Vis experiments at low temperatures suggest the
participation of nanoparticles in the early stage of the reaction.
[1]
[2]
[3]
46
L. J. Mitchell, C. J. Moody, The Journal of Organic

Chemistry 2014, 79, 11091-11100.
J. D. Nguyen, B. S. Matsuura, C. R. J. Stephenson, J.
Am. Chem. Soc. 2014, 136, 1218-1221.
R. G. Harms, I. I. E. Markovits, M. Drees, W. A. Herrmann,
M. Cokoja, F. E. Khn, ChemSusChem 2014, 7, 429-434.
Benjamin J. Hofmann1, Jens W.

Kck1, Fritz E. Khn1

Professorship of Molecular Catalysis,
Lichtenbergstrae 4 and Ernst-Otto-Fischer-Str. 1, 85748 Garching,
Germany
ben.hofmann@tum.de
Julius Hornung
During the last years a lot of effort has been made to successfully
synthesize a huge variety of molecular intermetallic compounds.
This research is based on the coordination chemistry of ER
(E = Al,Ga,In, R=Cp*) and MR (M = Zn, Cd, R = Cp*, Me) and
led to the synthesis of [Mo(ZnCp*)3(ZnMe)9][1], [Ni(ZnCp*)a(ZnMe)a
(PMe3)4-a](a = 1, 2, 4) [2] and [(CuAlCp*)6H4] [3]. These compounds
are not only interesting in terms of their conceptual bond descriptions but also as molecular models for surface reactions at
intermetallic catalysts and precursors for nanoalloy synthesis.
Especially, the preparation of Ru/Ga [4], Cu/Zn [5], Ni/Ga [6],
and Fe/Al nanoalloys is under investigation for their potential
applications as catalysts for industrially relevant hydrogenation
reactions. A molecular model for surface reactions is the 1:1 insertion product [(CuAlCp*)6H3(N=CHPh)] that was isolated after
reaction of [(CuAlCp*)6H4] with benzonitrile [3]. In this context,
the compounds [Ni(ZnCp*)a(ZnMe)a(PMe3)4-a] are also examined
as molecular congeners of catalytically relevant NiZn alloys.
In general, our concept is to transfer our knowledge and use the
above described molecular chemistry of clusters, mimicking structural cut-outs of Hume-Rothery type intermetallics, for applications
in catalysis.
[1]
[2]
[3]
[4]
[5]
[6]
J. Hornung1, H. Banh1, J. Wessing1,

K. Dilchert1, K. Freitag1, M. Cokoja1,
C. Gemel1, R. A. Fischer1
1
Inorganic and Organometallic Chemistry, Lichtenbergstrae 4 and ErnstOtto-Fischer-Str. 1, 85748 Garching,
Germany
julius.hornung@tum.de
T. Cadenbach, T. Bollermann, C. Gemel, M. Tombul, I.

Fernandez, M. v. Hopffgarten, G. Frenking, R. A. Fischer,
J. Am. Chem. Soc. 2009, 131, 16063-16077.
M. Molon, Dissertation, RUB, 2013; Metallatomreiche
Koordinationsverbindungen
C. Ganesamoorthy, J. Wessing, C. Kroll, R. W. Seidel, C.
Gemel, R. A. Fischer, Angew. Chem. Int. Ed. 2014, 53,
7943-7947.
T. Cadenbach, C. Gemel, R. Schmid, M. Halbherr, K.
Yusenko, M. Cokoja, R. A. Fischer, Angew. Chem. Int. Ed.
2009, 48, 3872-3876.
M. Cokoja, H. Parala, M.-K. Schrter, A. Birkner, M. W. E.
van den Berg, W. Grnert, R. A. Fischer, Chem. Mater.
2006, 18, 1634-1642.
K. Schutte, A. Doddi, C. Kroll, H. Meyer, C. Wiktor, C.
Gemel, G. van Tendeloo, R. A. Fischer, C. Janiak,
Nanoscale 2014, 6, 5532-5544.
47
Poster
Intermetallic clusters and nanoalloys and their applications

for catalysis
Takaaki Ikuno
Poster
Selective oxidation of methane into methanol on Cu-oxo

clusters supported on microporous materials
Methane is the main component of the natural gas, which is in

great abundancy and dispersed globally. However, transportation
infrastructure or facile method to convert it into easily condensable
energy carriers at or near the site is lacking, leading to flaring of
large quantities of natural gas causing both environmental damage
and economical loss. Direct oxidation of methane to methanol
would help addressing this problem, but it still remains a great
challenge due to higher reactivity of methanol compared to methane. Cu zeolites have been found to be reactive to this reaction
[1], which involves three consecutive steps: catalyst activation at
high temperature (typically 450-500 C), methane loading, and
subsequent methanol desorption by steam treatment. In order to
further address the partial oxidation of methane into methanol, in
this study, metal-organic framework (MOF) supported Cu-based
catalyst is investigated and compared to the reported Cu-exchanged zeolite with MOR structure (Cu-MOR) [1].
NU1000 (Zr6(3-OH)8(OH)8(1,3,6,8-tetrakis(p-benzoate)pyrene)2)
[2], possessing well-defined Zr-based nodes for the deposition of
Cu-species and also significantly larger pores (~3 nm) compared
to zeolites, is used as catalyst support, and Cu-species is deposited on NU1000 by atomic layer deposition. Even though CuMOR is found to be more active and selective than Cu-NU1000,
the latter successfully activates methane after significantly low
activation temperature of 150 C, demonstrating the application
of MOF as catalysts for direct oxidation of methane into methanol
at low temperatures.
[1]
[2]
48
Grundner, S.; Markovits, M. A. C.; Li, G.; Tromp, M.;

Pidko, E. A.; Hensen, E. J. M.; Jentys, A.; Sanchez-Sanchez,
M.; Lercher, J. A., Nat. Commun. 2015, 6, 7546-7554.
Mondloch, J. E.; Bury, W.; Fairen-Jimenez, D.; Kwon, S.;
DeMarco, E. J.; Weston, M. H.; Sarjeant, A. A.; Nguyen, S.
T.; Stair, P. C.; Snurr, R. Q.; Farha, O. K.; Hupp, J. T., J.
Am. Chem. Soc. 2013, 135, 10294-10297.
Takaaki Ikuno1, Maricruz SanchezSanchez1, Johannes A. Lercher1

takaaki.ikuno@tum.de
Dennis Knogler
Atomic force microscopy is a useful technique to investigate and

depict the topology of surfaces in nearly atomic resolution. Due
to its simplicity and its manifoldness it is widely used in a variety
of facilities, ranging from small laboratories up to factories of the
semiconductor industry. In order to exhibit this technique to a
broad audience, an atomic force microscope built of LEGOs NXT
robotic parts was assembled previously [1].
The construction as well as the LabView program for controlling are based up on the works of the micro/nanoscale energy
transport and conversion laboratory of the University of Utah. In
order to resemble a real atomic force microscope even more, a
position sensitive detector has been implemented. The integration was possible by minor mechanical changes and usage of
LabViews NXT light sensor subVIs. In contrast to the previous
employed LEGO NXT light diodes a tremendous improvement
in height resolution could be achieved, due to the more detailed
and continuous acquirement of topographic differences. Insights
in the operation and the implementation of a position sensitive
detector have been gained. This will strongly promote the usage
of this detector. Furthermore an impression on postprocessing the
obtained data by MatLab will be presented.
[1]
Dennis Knogler1,2, Theresa Zach1,

Maximilian Krause1, Friedrich Esch1
1

m2gsn.tum.de
dennis.knogler@tum.de
Albersberger S. and Braun T., LEGO AFM, TUM course

Messen-Auswerten-und-Simulieren (2015)
49
Poster
Improvement of a LEGO atomic force microscope for

educational purposes with a position sensitive detector
Sebastian Kollmannsberger
Poster
Probing semiconductor properties of GaN:

Effects of doping and photon-stimulated processes
Understanding the effects of doping on semiconductors in photocatalysis is of major importance for metal-cluster semiconductor
hybrid materials [1]. One of the most stable systems is gallium
nitride decorated with metal nanoparticles as a co-catalyst [2].
GaN is a semiconductor (3.4 eV band gap), which can be p- and
n-doped and its band gap can be tuned by alloying.
Sebastian L. Kollmannsberger1,
Constantin A. Walenta1, Andrea
Winnerl2, Saskia Weiszer2, Rui
Pereira2, Martin Tschurl1, Martin
Stutzmann2, Ueli Heiz1

In this work we demonstrate the elucidation of reaction pathways

on clean extended GaN surfaces in the UHV with a chemical probe
molecule. For this purpose CO is the molecule of choice, as it
exhibits photon-stimulated desorption (PSD) upon UV irradiation
on the bare semiconductor surfaces. Further, it is shown, that
the CO adsorption properties are dependent on semiconductor
doping, while the PSD kinetics remain the same.
A thorough characterization of the surface is of paramount importance and prerequisite for studies with size-selected Pt metal
clusters, as we show that major change in reactivity of the clusters
with different electronic properties of this hybrid materials can be
expected [1, 3].
sebastian.kollmannsberger@tum.de
[1]
[2]
[3]
50
Kim et al., Nano Lett., 2013, 13, 1352-1358.

Ohno et al., J. Am. Chem. Soc., 2012, 134, 8254-8259.
Winnerl et al., J. Appl. Phys., 2015, 118, 15.

Chair of Experimental Semiconductor
Physics, Physics Department, Walter
Schottky Institute and Catalysis
Research Center, Am Coulombwall 4
and Ernst-Otto-Fischer-Str. 1, 85748
Garching, Germany
Maximilian Krause
Precisely controlled catalytic model systems are needed for

understanding fundamental aspects of heterogeneous catalysis.
In this respect, supported size-selected clusters on metal oxides
are an ideal choice, since their number of atoms can be tuned
precisely independent of the coverage. Though considerable insights could be gained with such systems in the UHV [1-3] in the
last decades, they can be hardly compared to applied catalytic
systems, because of the well-known problematic of the pressure
and complexity gaps [4].
To this end, we report results of cluster catalysis under classical
wet chemistry conditions. Clusters of different metals, sizes and
size-distributions, in particular Ta (1, 4, >1, >3, >11) and Pt (1, >1,
>35) were deposited onto Si-wafers under vacuum and transferred to ambient conditions. The catalysts were used for different
test reactions: the oxidation of cyclooctene (Ta, Schlenk-Tube,
60C) and the reduction of p-Chloronitrobenzene (Pt, autoclave,
100C, 5 bar H2). Reaction products were quantified by GC-MS
and LC measurements. Furthermore characterization by means
of XPS and HAADF-STEM before and after the reactions were
performed. Both metals showed promising results concerning reactivity, though their stability is limited; both parameters depend
on catalyst size and material. The results demonstrate the potential
of using cluster model catalyst materials for applied reaction conditions. It contributes towards the understanding of cluster stability
in solution and reactivity of catalyst in the size regime of supported
sub-nm clusters at more relevant catalytic conditions in general.
[1]
[2]
[3]
[4]
Maximilian Krause1, Gregor Zwaschka1, Manuel Rondelli1, Dalaver

Anjum2, Mohammed Nejib Hedhili2,
Manuel Hgerl3, Marian Rtzer1,
Andrew Crampton1, Jean-Marie
Basset3, Valerio DElia3, Florian F.
Schweinberger1, Ueli Heiz1

King Abdullah University

of Science and Technology,
Advanced Nanofab. Imaging and
Characterization Core Lab, Bldg. 3,
Thuwal 23955-6900, Kingdom of
Saudi Arabia.
King Abdullah University of Science

and Technology, Kaust Catalysis
Center (KCC), Bldg. 3, Thuwal
23955-6900, Kingdom of Saudi
Arabia.
maximilian.krause@tum.de
Sanchez, A.; Abbet, S.; Heiz, U.; Schneider, W. D.;

Hkkinen, H.; Barnett, R. N.; Landman, U. The Journal of
Physical Chemistry A 1999, 103 (48), 9573.
Heiz, U.; Sanchez, A.; Abbet, S.; Schneider, W. D. Journal
of the American Chemical Society 1999, 121 (13), 3214.
Abbet, S.; Sanchez, A.; Heiz, U.; Schneider, W. D.; Ferrari,
A. M.; Pacchioni, G.; Rsch, N. Journal of the American
Chemical Society 2000, 122 (14), 3453-3457.
Freund, H.-J.; Kuhlenbeck, H.; Libuda, J.; Rupprechter,
G.; Bumer, M.; Hamann, H. Topics in Catalysis 2001, 15
(2), 201.
51
Poster
Supported size-selected metal clusters as model systems

for wet chemical applications
Paul Leidinger
Poster
Supressing nucleation for chemical vapour deposition (CVD)

growth of graphene
Controlling the nucleation density of graphene grown by chemical

vapour deposition (CVD) on polycrystalline copper is the key for
the production of large, high quality graphene single crystals. We
present systematic studies that show a correlation between the
carbon content of the copper foils and the graphene nucleation
rate during CVD growth. The carbon content on the sample surface was determined by ex-situ x-ray photoelectron spectroscopy
(XPS) applying a special fast cooling procedure.
Particular attention was paid on the pretreatment of the copper
foils that removes carbon contaminations already present before
growing graphene. One established pretreatment method of the
foil is at 950C in a highly diluted oxygen atmosphere, which
oxidatively removes the carbon. Samples with minimum carbon
content show a nucleation density reduced by three orders of
magnitude, resulting in approximately one graphene flake per
mm2. Thus, graphene flakes with diameters of up to 1 mm can be
obtained in the subsequent CVD growth step.
52
Paul Leidinger1, Magdalene Bbel1,

Gregor Zwaschka1, Jrgen Kraus1,
Sebastian Gnther1

Professorship of Physical Chemistry
with Focus on Catalysis, Lichtenbergstrae 4 and Ernst-Otto-FischerStr. 1, 85748 Garching, Germany
paul.leidinger@tum.de
Dr. Tony Lelaidier
The optical and morphological properties of thin film of 1,4-din-octyloxy-2,5-bis(pyren-1-ylethenyl)benzene (bis-pyrene) have
been studied by the means of surface cavity ring-down (s-CRD)
spectroscopy and scanning tunnelling microscopy under ultra high
vacuum. The appearance followed by a saturation of a shoulder
at 505 nm in the optical spectra has been observed as a function
of the molecular density deposited on the surface.
Combining observations from these measurements of the optical properties obtained by s-CRDS with conventional UV-Vis
measurement and STM experiment performed on Au(111) allow
us to assign this modification to an interaction of the transition
dipole moments of molecules of the first and the second layer.
Furthermore, these experiments also reveal that the molecular
growth process on the BK7 glass substrate is a Volmer-Weber
growth mode, which is different from the growth mode observed
for bis-pyrene on Au(111). We also observe that the substrate
temperature has a strong influence on the molecular diffusion and
the formation of molecular structure: higher temperature enhances
the molecular diffusion, leading to the formation of multi-layers
islands at lower molecular density compared to the deposition
performed at lower temperature.
T. Lelaidier1,2, T. Lnskens2, A. von

Weber2, T. Leoni1, A. Ranguis1,
A. DAlo1, F. Fages1, A. Kartouzian2,
C. Becker1, U. Heiz2
Centre Interdisciplinaire de
Nanoscience de Marseille.
UMR 7325 Aix-Marseille Universit

4 and Ernst-Otto-Fischer-Str. 1.
munich marseille graduate school of

nanoscience (m2gsn), m2gsn.tum.de
tony.lelaidier@univ-amu.fr
53
Poster
Optical and morphological properties of thin films of

bis-pyrenyl -conjugated molecules.
Li Jiang
Poster
Toward on-surface synthesis of low dimensional conjugated

nanomaterials
Recently, graphene nanoribbons, especially doped with heteroatoms have spurred extensive attention and exploration [1] and
covalent organic frameworks (COF) have been successfully synthesized based on Schiff base formation [2].
Inspired by these findings, we systematically investigated the
coupling reaction of a tetraamine molecule with a tetraketone
molecule on the three coinage close packed metal surfaces Au,
Ag and Cu under ultrahigh vacuum conditions by scanning tunneling microscopy. On all three substrates the reactants readily
intermix at room temperature forming two-dimensional bi-component networks. We demonstrated the feasibility to form Schiff
base conjugated oligomers on the Ag(111) surface by thermal
treatment. Statistical analysis of the reaction products as a function of reactant stoichiometry and further investigations with the
X-ray photoelectron spectroscopy provide mechanistic insight in
the on-surface polymerization process. In contrast to the behavior
on Ag(111), the monomers desorb from the Au(111) surface before
they react, whereas on the Cu(111) surface undesired thermal
decomposition is observed after annealing at lower temperatures
than that of imine formation.
[1]
[2]
54
L. Zhao, R. He, K.T. Rim, T. Schiros, K.S. Kim, H. Zhou,

C. Gutierrez, S.P. Chockalingam, C.J. Arguello, L. Palova,
D. Nordlund, M.S. Hybertsen, D.R. Reichman, T.F. Heinz,
P. Kim, A. Pinczuk, G.W. Flynn, and A.N. Pasupathy,
Science, 2011, 333, 999.
L. Stegbauer, K. Schwinghammer, and B.V. Lotsch,
Chem. Sci. 2014, 5, 2789.
Li Jiang1, Anthoula C. Papageorgiou1,

Seung Cheol Oh1, zge Salam1,
Joachim Reichert1, David A. Duncan1,
Yi-Qi Zhang1, Florian Klappenberger1,
Yuanyuan Guo1, Francesco Allegretti1, Sandeep More2, Rajesh Bhosale2,
Aurelio Mateo-Alonso2,3, Johannes V.
Barth1

Universitt Freiburg, Institut fr

Organische Chemie und Biochemie,
Albertstrae 21, 79104 Freiburg,
Germany
Ikerbasque, Basque Foundation for

Science E-48011 Bilbao, Spain
li.jiang@tum.de
Pankaj Madkikar
High cost and limited availability of platinum based catalysts for

Oxygen Reduction Reaction (ORR) is a major hurdle towards the
commercialization of Proton Exchange Membrane Fuel Cell (PEMFC) systems. Until today, replacing Pt by Pt-free and finally by
noble-metal-free catalysts for ORR is still restricted to the labs.
High activity and durability are the main requirements for a new
catalyst. MNxCy system (M = Fe, Co) are favored due to their low
cost, reasonable activity and remarkable selectivity towards ORR
[1]. On the other hand, MNxCy catalysts have a disadvantage in
their poor stability in corrosive environment. Since more than a
decade, Ota et al. are studying valve metal oxides (from group IV
and V) [2], observing some ORR activity for those compounds. In
addition these metal oxides are stable in an acid solution.
Poster
ZrO2/C as noble metal-free oxygen reduction reaction

catalyst in PEMFC
Pankaj Madkikar1, Thomas Mittermeier1, Michele Piana1, Hubert

Gasteiger1
1
Technical Electrochemistry, Lichtenbergstrae 4 and Ernst-Otto-FischerStr. 1, 85748 Garching, Germany
pankaj.madkikar@tum.de
Based on their work, we started our research on the same systems,

starting with carbon supported zirconia (ZrO2) nanoparticles [3].
The samples were synthesized using two different organometallic
precursors, namely, zirconium oxy-phthalocyanine (ZrOPc) and
zirconium acetylacetonate (Zr(acac)4). The difference in atomic
constitution and solubility in dispersing medium of the two precursors made their use and the investigation of the obtained catalyst
interesting. From the X ray diffractograms of supported zirconia
nanoparticles from both the precursors, samples synthesized from
ZrOPc at 900 C and from Zr(acac)4 at 750 C a ZrO2 phase is
assignable. The ORR electrochemical activity of these samples
was tested by thin-film RDE technique at 20 C in 0.1 M HClO4
electrolyte [4].
[1]
[2]
[3]
[4]
J.-P. Dodelet in N4-Macrocyclic Metal Complexes (Eds.:

J. Zagal, F. Bedioui, J.-P. Dodelet), Springer New York,
2006.
K.-I. Ota, A. Ishihara in Electrocatalysis in Fuel Cells (Ed.:
M. Shao), Springer London, 2013.
S. Yin et al. ECS Transactions 2013, 50, 17851790.
U. Paulus et al. J. Electroanalytical Chemistry 2001, 495,
134.
55
Iman Marhaba
Poster
Structure and chemistry of aircraft soot nanoparticles
Air traffic has increased of about 5%/year in the last decades but
little is known about the aviations impact on the atmosphere [1].
Particulate emissions from jet aircrafts are the most significant
source of carbonaceous particles in the upper troposphere/lower
stratosphere; they also contribute to black carbon pollution in near
airport areas. In the troposphere, they affect the climate system
through various physical processes like scattering and absorption
of solar radiation, thermal emission, and cloud formation (through
ice nucleation) that modifies the Earths albedo. Determining their
physical structure, chemistry and optical properties is then of
importance to improve our knowledge about their reactivity and
impact on human health and climate.
Iman Marhaba1, Carine Lafon1,

Philippe Parent1, Daniel Ferry1,
Tom Z. Rergier2
Aix-Marseille Universit, CINaM,

campus de Luminy case 913,
F-13009 Marseille - France
Canadian Light Source, Saskatoon,

SK, S7N 2V3, Canada
marhaba@cinam.univ-mrs.fr
In this context, the MERMOSE project aims at determining

physical and chemical characteristics of soot particles emitted
from a modern turbofan engine (SaM146 1S17) fuelled with Jet-A1.
Particles have been collected behind the engine during a sampling
campaign carried out on a test bench facility. We present results
obtained by HRTEM, X-Ray Photoelectron Spectroscopy (XPS)
and Near-Edge X-ray Absorption Fine Structure (NEXAFS) on the
collected carbonaceous particles. The structure and elemental
chemical composition as well as the chemical speciation of carbon
and oxygen are presented for different thrust regimes (take-off,
climb out, cruise, and final approach) [2]. We show for the first time
structural and chemical differences between the outermost part
and the inner part of nanometric soot primary particles.
We propose a detailed atomic representation of aircraft emitted
soot particles, a key step for understanding their physical and
chemical properties.
[1]
[2]
56
M. Masiol, and R.M. Harrison, (2014) Atmos. Environ. 95,

409-455.
Ph. Parent, C. Laffon, I. Marhaba, D.Ferry, T.Z.Regier, I.K.
Ortega, B. Chazallon, Y. Carpentier, and C. Focsa, (2016)
Carbon 101, 86-100.
Amina Merabet
The mechanical behavior of micro- and nano-structures depend

on their size. While a very large number of research groups are
focusing on the plastic properties of metal nano-structures, much
less work has been devoted to semiconductor nano-objects. Silicon is a very important material in modern technology and its
mechanical behavior certainly deserves attention. In the bulk, Si
is brittle at room temperature and needs temperatures in excess
of 600C to show ductility. Surprisingly, when the sample size
decreases below few hundreds of nanometers, Si pillars may show
an unexpected ductile behavior at room temperature [1] which is
still not really understood. In this context, this research project
aims at investigating in more details the deformation behavior of
silicon nanopillars by combining experimental techniques (SEM,
FIB, HRTEM) and molecular dynamics simulations. In this work
various nanopillars, with different orientations and diameters, were
patterned by Reactive-Ion Etching and FIB micromachining. These
pillars were then compressed with a slow-strain-rate (104 s1) at
room temperature using a nanoindenter equipped with a flat punch
and operated in displacement-control mode. Post mortem observations of deformed nanopillars performed by SEM and TEM
reveal the activation of different slip systems. The comparison between experimental and simulated HRTEM images notably evidences the simultaneous propagation of partial and perfect dislocations in {111} planes. In addition, unexpected plastic events have
also been observed in {113} planes. Various possible deformation
mechanisms involved during the nano-compression of the pillars
will be described, based on the microscopic observations.
Amina Merabet1, Michal Texier1,

Christophe Tromas2, Anne Talneau3,
Olivier Olivier1, Julien Godet1

Universit de Toulon, IM2NP UMR
7334, F-13397 Marseille, France
Institut Pprime, UPR3346 CNRS

Universit de Poitiers, F-86962
Futurscope Chasseneuil du Poitou
Cedex, France
Laboratoire de Photonique et de
Nanostructures, CNRS, F-91460
Marcoussis, France
amina.merabet@im2np.fr
This work is performed within the framework of the ANR-funded

research project BrIttle-to-Ductile Transition in Silicon at Low dimensions (ANR-12-BS04-0003-01, SIMI4 program).
[1]
F. stlund et al., Brittle-to-Ductile Transition in Uniaxial

Compression of Silicon Pillars at Room Temperature,
Adv. Func. Mat., 19, p1(2009).
57
Poster
Plastic deformation of silicon nanostructures at room

temperature: an electron microscopy investigation
Vincent Mesquita
Poster
Catalysis spatially resolved on a surface
The main objective of this study is to show how the probe of an

atomic force microscopy (AFM) can locally and selectively initiate a
chemical reaction on a surface. Scanning probe lithography (SPL)
is a highly promising tool for the creation of specific nanosized
patterns on a surface with high spatial resolution [1]. We have
recently reported a novel approach to chemically selective lithography using an AFM probe with immobilized manganese complex
homogeneous catalyst, potentially opening access to a diversity
of nanoscale transformations of the surface-bound functional
groups [2]. This new concept was proven for local epoxidation
of alkene-terminated self-assembled monolayer (SAM) on silicon
using H2O2 as an oxidant and a catalytic silicon AFM tip charged
with manganese complexes with 1,3,7-triaza-cyclononane type
ligand in double heterogeneous conditions. The reaction was
revealed by selective grafting of N-octylpiperazine molecules or
other compounds like ferrocene, fullerene or porphyrin derivatives
onto the modified areas of the surface.
We have further studied the influence of the physicochemical parameters on the reaction yield of this chemical model reaction, like
the applied force, the reaction time or the catalyst configuration.
We could achieve a resolution limit of ~30nm. We found that the
catalytic system is very robust and could successfully be used for
grafting laterally an equivalent surface of at least 450m2, but also
vertically for sequential grafting of a 3D pyramidal edifice of up to
three molecular layers high.
[1]
[2]
58
S.A.M.Carnally, L. S. Wong, Nanoscale, 6, 4998 (2014)

D.A. Valyaev, et al., Chem. Sci. 4, 2815 (2013)
Vincent Mesquita1

IM2NP UMR 7334
mesquita.vincent@hotmail.fr
Elmar Mitterreiter
Poster
Photoelectron spectroscopy study of 3-hexyne on surfaces
Elmar Mitterreiter1,2, Marian D.

Rtzer1, Florian F. Schweinberger1,
Ueli Heiz1
Current research has lead to a profound understanding of interaction processes during the adsorption of simple molecules on
surfaces. However, with respect to more complex molecule structures there are still some scientifically challenges [1].
Thus, the presented study examined the adsorption properties of
3-hexyne on Pt(111) under UHV conditions using different spectroscopic techniques such as Ultraviolet Photoelectron Spectroscopy
(UPS), Metastable Impact Electron Spectroscopy (MIES) and Auger Electron Spectroscopy (AES) in combination with Temperature
Programmed Desorption (TPD) [4]. These techniques, which are
extremely surface sensitive, allow to investigate precisely the electronic properties of the adsorbed molecules [2-3].
With increasing concentration of 3-hexyne on the Pt(111) surface
an increasing shift of the peaks towards higher binding energies
was observed up to a saturation concentration for all molecular orbitals (MOs). Also, the value of the work function changed towards
larger values as a function of coverage. The relative peak positions
of the different MOs however remained unchanged. Comparing
the experimental results with DFT calculations of the molecular
structure of 3-hexyne, the interacting MOs were identified. Complementary TPD data showed for higher coverages an increased
amount of 3-hexyne and also additional reaction products, such as
hydrogen, hexane and benzene. These findings are interpreted in
the framework of a chemisorption process [2] of 3-hexyne on the
Pt(111) surface attended by self-hydrogenation/dehydrocyclization
reaction pathways. Additional experiments are proposed in order
to develop a better understanding of the reaction mechanism and
to allow for a refined interpretation of the data.
[1]
[2]
[3]
[4]
1
4 and Ernst-Otto-Fischer-Str. 1.

m2gsn.tum.de
elmar.mitterreiter@tum.de
Schth, F. Chemie in unserer Zeit, 2006, 40, 92-103.

Schweinberger, F.F. Catalysis with Supported Size-selected
Pt Clusters, 2014, Springer Internat. Publishing.
Kuno, M. Introductory Nanoscience, 2011.
Heinz,B., Morgner, H. Journal of Electron Spectroscopy
and Related Phenomena, 1998.
59
Daniel Rutz
Poster
Insight into electrochemical measurements of

platinum nanoparticles
The future of electromobility depends on the development of batteries and hydrogen fuel cells, based on hydrogen produced by
renewable energies [1]. It seems that this is the only opportunity
to meet the European future CO2-emission targets of <95 g CO2
per km [2]. The investigation of platinum nanoparticles as potential
catalysts is fundamental to fully understand the electrocatalytic hydrogen oxidation/evolution reaction (HOR/HER) and the potential
of hydrogen for energy storage in fuel cells [2, 3]. The RDE used
in a three electrode system is a powerful tool when investigating
reaction mechanisms related to redox reactions, such as the HER/
HOR [3]. With the aid of the Levich-Equations we can predict
the height of peak currents in a cyclic voltammogram (CV). The
catalytic electrode surface (and consequently the roughness factor) is found by integrating the reduction current in the hydrogen
adsorption area. Hence, we can determine the specific catalytic
activity of the nanoparticles.
We present an experimental setup, consisting of a classical three
electrode system, using glassy carbon as a support material for
nanoparticles (0.24 mmol Pt) in 0.1 M HClO4 (>99.99%) as electrolyte. Moreover, a gas switch enables the usage of various gases,
such like H2, Ar, O2, CO, independently. The cell is controlled by
a software. Our results showed a Gaussian-like decrement of the
roughness factor with increasing number of runs. This could be
explained by a surface degradation of the nanoparticles [4].
[1]
[2]
[3]
[4]
60
Grger, O.; Gasteiger, H . A.; J. Electrochem. Soc., 2015,

162, A2605-A2622.
Durst, J.; Siebel, A.; Gasteiger, H., Energy and Environ.
Science, 2014, 7, 2255 -2260.
K.J.J. Mayrhofer, M. Arenz, V. Stamenkovic, P. Ross, N.
Markovic, Electrochimica Acta, 50, 2005, 5144-5154.
J. Meier, C. Galeano, A. Topalov, C. Baldizzone, F. Schth,
K.J.J. Mayrhofer; Beilstein J. Nanotech. 2014, 5, 4467.
Daniel Rutz1,2, David Mayer1, Sarah

Wieghold1, Friedrich Esch1, Ueli Heiz1


m2gsn.tum.de
d.rutz@tum.de
Christian Schler
As part of the energy transition, the expansion of renewable

energy is focused on reducing CO2 emissions. Here, however, it
is challenging to store the excess energy effectively. A promising
approach to solve this problem is the power-to-gas concept [1].
In this case, hydrogen obtained by electrolysis is converted with
carbon dioxide into methane by means of the Sabatier process.
From literature is known that Rh-, Ru- or Ni-based catalysts show
promising catalytic results [2-4]. In this study, the performance
of CVD-prepared Ni/SiO2 should be enhanced via the addition of
further metals during the deposition process.
The advantage of CVD-prepared catalysts is that these catalysts
have high active metal surfaces and high dispersions at low nickel
loadings. The bimetallic deposition is investigated with focus on
its influence on dispersion and active metal surface by means of
N2 Physisorption (BET) and H2/CO2 chemisorption techniques. The
received data are compared with the pure nickel catalyst to see the
influence of the several doping metals. The effects on the reaction
of the doping metals are evaluated by means of kinetic studies.
These studies are performed in a single-pass tubular reactor where
the methanation performance is determined by measuring the CO2
conversion at different temperatures. After reduction and formation
of the catalyst, the kinetic performance of the catalyst is recorded
and the temperature-dependent performance is compared at a
conversion of 50%. The next step of this study is to combine the
most promising doping metals on the nickel catalyst and investigate the combined effects.
[1]
[2]
[3]
[4]
Poster
Preparation of bimetallic nickel catalysts for CO2

methanation via chemical vapor deposition
Christian Schler1, Kai-Olaf

Hinrichsen1

chris.schueler@ch.tum.de
M. Sterner, PhD Thesis, Kassel University, 2009.

M. Bowker, T.J. Cassidy, A.T. Ashcroft, A.K. Cheetham, J.
Catal. 143 (1993) 308313.
J.M. Rynkowski, T. Paryjczak, A. Lewicki, M. Szynkowska,
T.P. Maniecki, W.K. Jozwiak, React. Kinet. & Catal. Lett. 71
(2000) 5564.
G.M. Shashidhara, M. Ravindram, React. Kinet. & Catal.
Lett. 37 (1988) 451456.
61
Jan Schwmmlein
Poster
Origin of the superior activity of bimetallic Pt-Ru catalysts

towards hydrogen oxidation in alkaline media
Platinum shows an exceptionally high activity for the hydrogen

oxidation reaction (HOR) in acidic environment, enabling ultra-low
Pt-loadings on the anode side of proton exchange membrane fuel
cells (PEMFCs) [1]. Unlike in acid, this reaction is about two orders
of magnitude slower on platinum and other platinum metals in alkaline electrolyte [2]. Bimetallic Pt-Ru catalysts were demonstrated
to exhibit significantly higher HOR activities in acid [3] and base
[4] compared to Pt catalysts.
One hypothesis for the high HOR activity of Pt-Ru alloys in base
is a bi-functional mechanism, with hydrogen being adsorbed on
Pt and hydroxide being supplied by more oxophilic Ru, whereby
the presence of hydroxide in the vicinity of Pt-Hads would accelerate the rate of the hydrogen oxidation. The second hypothesis
considers a modification of the electronic structure of platinum
by ruthenium [4], leading to a lower Pt Hads binding energy and
ultimately to a higher activity of platinum towards the oxidation
of hydrogen. While the exposure of ruthenium on the surface of
the catalyst is absolutely mandatory for a bi-functional mechanism [5], this is not the case for an activity enhancement due to a
modification of the electronic structure of platinum. Based on this
fundamental difference, we have attempted to identify the actual
HOR mechanism on bimetallic Pt-Ru catalysts by evaluating Ru@
Pt core-shell nanoparticles with various Pt-coverages and shell
thicknesses.
[1]
[2]
[3]
[4]
[5]
62
H. A. Gasteiger; J. E. Panels and S. G. Yan, J. Power

Sources, 1-2, 162 (2004).
P. J. Rheinlnder; J. Herranz; J. Durst and H. A. Gasteiger,
J. Electrochem. Soc., 14, F1448F1457 (2014).
J. X. Wang; Y. Zhang; C. B. Capuano and K. E. Ayers,
Scientific reports, 12220 (2015).
K. Elbert; J. Hu; Z. Ma; Y. Zhang; G. Chen; W. An; P. Liu;
H. S. Isaacs; R. R. Adzic and J. X. Wang, ACS Catal., 11,
6764 (2015).
S. St. John; R. W. Atkinson; R. R. Unocic; T. A. Zawodzinski
A. B. Papandrew, J. Phys. Chem. C, 24, 13481 (2015).
Jan N. Schwmmlein1, Hany A.

El-Sayed1, Bjrn M. Sthmeier1,
Hubert A. Gasteiger1

Technical Electrochemistry, Lichtenbergstrae 4 and Ernst-Otto-FischerStr. 1, 85748 Garching, Germany
jan.schwaemmlein@mytum.de
Paul Stockmann
The epoxidation of terpenes is of great interest owing to the fact

that they are valuable chemicals in the fragrance, cosmetic and in
the near future polymer industries. The epoxides are intermediates
to the upcoming steps in the polymer synthesis. An enzymatic
epoxidation procedure was optimized using the Taguchi method of
parameter optimization and is presented here. Mild reaction conditions, easy work-up make this process a simple and an easy to
scale-up one. The monoterpenes limonene, 3-carene and -pinene
have been epoxidized and obtained with an isolated yield of 62.5,
88.8 and 72.3%. Moreover, the selective epoxidation of limonene
(a diene) was also developed which could be further extended
to all dienes in the future. The first step of the polymerization
procedure was the rearrangement to a ketone which was done
chemically using Lewis acids.
Sumanth Ranganathan1, Paul Stockmann1, Volker Sieber1
1
Straubing Center of Science, Chair
of Chemistry of Biogenic Resources,
Schulgasse 1, 94315 Straubing and
Garching, Germany
paul.stockmann@tum.de
With this new approach of olefin to ketone, the way toward green
monomers for polymerization could be achieved with relative ease.
63
Poster
Development of an enzyme mediated terpene epoxidation

process
Moritz Wolf
Poster
CO2 methanation: deactivation due to sulfur poisoning
Catalyst deactivation due to sulfur poisoning is a common problem

for a wide range of catalytic processes. In the current study, the
poisoning effect of sulfur on the methanation of CO2 over different
nickel and sulfur loadings was studied. Therefore, catalysts were
poisoned using the ex-situ method [1]. The activity of the as-prepared catalysts was tested in a plug flow reactor, characterization
was done via elemental analysis, XRD and XPS.
Supported nickel catalysts were prepared by incipient-wetness
impregnation or co-precipitation, dried and calcined. These reference samples were poisoned in a subsequent step via the ex-situ
method, using an aqueous solution of ammonium sulfate [1]. The
reference and poisoned samples were tested for activity in a single
pass plug flow reactor. Hereby, the performed activity measurements all followed the same routine procedure.
Characterization of the bulk material by XRD analysis confirmed,
that the bulk morphology of the catalysts was not significantly
affected upon the addition of small amounts of sulfur. In contrast
to that, a sulfate signal in the S 2p spectral region was observed
during XPS analysis [2]. The catalytic tests showed, that sulfur
addition has a significant effect on the CO2 methanation reaction.
A dramatic loss of activity was observed.
On the basis of this study, we are able to compare the performance of different catalytic systems in the presence of sulfur and to
develop different approaches to increase sulfur tolerance.
[1]
[2]
64
V. Curtis, C. P. Nicolaides, N. J. Coville, D. Hildebrandt, D.

Glasser, Catal. Today 49 (1999) 33-40.
J. F. Moulder, W. F. Stickle, P. E. Sobol, K. D. Bomben,
Phys. Electron. (1995) 60-61.
Moritz Wolf1, Elena Fritzler1, Yang

Wang1, Kai-Olaf Hinrichsen1

moritz.wolf@ch.tum.de
Ioannis Zachos
Photocatalytic water splitting is an artificial photosynthesis process with photocatalysis in a reaction cell used for the dissociation
of water into its constituent parts, hydrogen and oxygen, using
either artificial or natural light. Theoretically, only solar energy,
water, and a catalyst are needed. The successfull combination
of photocatalysis and biocatalysis is the aim of PHAROS (Photocatalytic activated reduction module for enzymatic processes).
Here we want to drive enzymatic redox reactions with the power of
light and thus create an efficient and green way to perform many
interesting reactions.
Ioannis Zachos1, Josef Sperl1, Volker

Sieber1

Straubing Center of Science, Chair
of Chemistry of Biogenic Resources,
Schulgasse 1, 94315 Straubing and
Garching, Germany
ioannis.zachos@tum.de
65
Poster
Photocatalytic activated reduction module for enzymatic

processes
Participants
Dr.
Prof.
Prof.
Prof.
Dr.
Prof.
Prof.
Dr.
Prof.
Prof.
Prof.
Prof.
Dr.
Prof.
Prof.
Prof.
Prof.
Prof.
Dr.
Prof.
66
Allegretti
Auwrter
Barth
Bartl
Becker
Brenninger
Carsten
Chorkendorff
Costas
Courtois
Diouf
Ducke
Epp
Ewald
Ferry
Fischer
Garbe
Garcia
Giorgio
Grtsch
Gnther
Gutierrez
Haas
Heiz
Hess
Hintermann
Hofmann
Hlzl
Hornung
Ikuno
Inoue
Kaspar
Kirchberger
Knogler
Khler
Kollmansberger
Kratky
Kraus
Krause
Leibold
Leidinger
Lelaidier
Lercher
Li
Li
Francesco
Willi
Johannes
Johannes
Conrad
Christoph
Jrg
Ib
Miquel
Carla
Mamouna
Jacob
Konstantin
Stefan
Daniel
Richard
Steffen
Hermenegildo
Suzanne
Irmgard
Sebastian
Olivier
Ruth
Ulrich
Corinna
Lukas
Benjamin
Alena
Julius
Takaaki
Shigeyoshi
Manuel
Felix
Dennis
Klaus
Sebastian
Tim
Jrgen
Maximilian
Joachim
Paul
Tony
Johannes
Jiang
Han
francesco.allegretti@ph.tum.de
wau@tum.de
jvb@tum.de
jjohannesbartl@gmail.com
conrad.becker@univ-amu.fr
christoph.brenninger@mytum.de
joerg.carsten@tum.de
ibchork@fysik.dtu.dk
miquel.costas@udg.edu
carla.courtois@tum.de
diouf@cinam.univ-mrs.fr
jacob.ducke@tum.de
konstantin.epp@tum.de
stefan.ewald@ch.tum.de
daniel.ferry@univ-amu.fr
richard.fischer@tum.de
steffen.garbe@tum.de
hgarcia@qim.upv.es
suzanne.giorgio@univ-amu.fr
irmgard.groetsch@ch.tum.de
sebastian.guenther@tum.de
oliver.gutierrez@mytum.de
ruth.haas@mytum.de
ulrich.heiz@mytum.de
corinna.hess@ch.tum.de
lukas.hintermann@tum.de
ben.hofmann@tum.de
alena.hlzl@tum.de
julius.hornung@tum.de
takaaki.ikuno@tum.de
s.inoue@tum.de
manuel.kaspar@tum.de
felix.kirchberger@tum.de
dennis.knogler@gmx.de
klaus.koehler@tum.de
sebastian.kollmansberger@tum.de
tim.kratky@tum.de
juergen.kraus@mytum.de
maximilian.krause@tum.de
joachimleibold@me.com
paul.leidinger@tum.de
tony.lelaidier@univ-amu.fr
johannes.lercher@ch.tum.de
li.jiang@tum.de
han.li@ch.tum.de
Prof.
Dr.
Dr.
Prof.
Dr.
Dr.
Dr.
Dr.
Pankaj
Nicole-Artemis
Iman
Amina
Vincent
Dimitrios
Elmar
Hans
Anthoula
Marian
Daniel
Kai
Debotra
Christian
Jan
Martin
Florian
Volker
Sebastian
Paul
Martin
Cornelius
Oliver
Sanyal
Constantin
Moritz
Ioannis
pankaj.madkikar@tum.de
artemis.marangos@tum.de
marhaba@cinam.univ-mrs.fr
amina.merabet@im2np.fr
mesquita.vincent@hotmail.fr
dimitrios.Mihalios@ch.tum.de
elmar.mitterreiter@ph.tum.de
J.W.Niemantsverdriet@tue.nl
a.c.papageorgiou@tum.de
marian.roetzer@tum.de
d.rutz@tum.de
kai.sanwald@tum.de
debotra.sarkar@tum.de
chris.schueler@ch.tum.de
jan.schwaemmlein@mytum.de
martin.schwarz@tum.de
florian.schweinberger@tum.de
sieber@tum.de
sebastian.standl@ch.tum.de
paul.stockmann@tum.de
martin.strassburg@osram-os.com
thomas.cornelius@im2np.fr
oliver.thomys@tum.de
udishnu.sanyal@tum.de
c.walenta@tum.de
moritz.wolf@ch.tum.de
ioannis.zachos@tum.de
Participants
Dr.
Madkikar
Marangos
Marhaba
Merabet
Mesquita
Mihalios
Mitterreiter
Niemantsverdriet
Papageorgiou
Rtzer
Rutz
Sanwald
Sarkar
Schler
Schwmmlein
Schwarz
Schweinberger
Sieber
Standl
Stockmann
Strassburg
Thomas
Thomys
Udishnu
Walenta
Wolf
Zachos
67

crc.tum.de

TUM CRC BoA CRCGA Download Web PDF

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

TUM CRC BoA CRCGA Download Web PDF

Hochgeladen von

Copyright:

Verfügbare Formate

Catalysis Research Center

Technical University of Munich

Catalysis Research Center

CRC Graduate Academy 2016 supported by

Faculty Graduate Centers CH and PH

Catalysis Research Center

Catalysis Research Center

Wi-Fi-Access via mwn-events

TUM Science & Study Center Raitenhaslach

Wi-Fi name (SSID):

Configuration profiles for wireless network

Information for speakers

Information for poster presentations

Sunday June 5th

Monday June 6th

15:00 Bus shuttle from Munich to

08:00 Breakfast at Hotel

16:00 Pick-Up: Airport MUC

11:00 Coffee break

Wednesday June 8th

08:00 Breakfast at Hotel

08:00 Breakfast at Hotel

09:00 Bus shuttle to Raitenhaslach

09:00 Bus shuttle to Raitenhaslach

09:30 Keynote lecture Ib Chorkendorff

10:30 Coffee break

Talk Conrad Becker

Tuesday June 7th

Talk Kai Sanwald

11:00 Coffee break

12:30 Lunch break

12:30 Closing remarks

14:00 Workshop Hans Niemandsverdriet

16:00 Coffee break

14:00 Bus shuttle from

17:45 Looking Beyond Your Own

Prof. Hermenegildo Garcia

Photocatalysis for the production of solar fuels

Gomes Silva, C., Juarez, R., Marino, T., Molinari, R.,

Dr. Francesco Allegretti

TiO2 is a promising candidate to convert sunlight into chemical

Allegretti Francesco1, Deimel

Technical University of Munich,

Diamond Light Source, Harwell

Sincrotrone Trieste, Strada Statale

The prepared single layer of TiO-TPP represents an intriguing

M. Ni et al., Renew. Sustainable Energy Rev. 11, 401

Atomic-scale investigation of an in-situ prepared single

Ethanol photocatalysis on TiO2(110): a mechanistic study

Metal cluster-semiconductor systems are promising new hybrid

Murdoch et al., Nat Chem, 2011, 3, 6.

Constantin Walenta1 ,2, Sebastian

Nanosystems Initiative Munich

Producing solar fuel by water photoelectrolysis is a promising

Atomic layer deposition of TiO2 onto anodic black Si for

Allegretti Francesco1, Mamouna

CINaM UMR 7325, Aix Marseille

Institut des Sciences Chimiques de

Therefore, photon absorption is increased leading to better PECs

K. Sivula and R. van de Krol, Nat. Rev. Mater., 1, 2,

Prof. Richard Fischer

Munich Catalysis The strategic alliance of TUM and Clariant

MuniCat comprises the strategic research alliance between