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NANO

LETTERS

Synthesis of Platinum Multipods: An xxxx


Vol. 0, No. 0
Induced Anisotropic Growth A-G

Xiaowei Teng† and Hong Yang*,†,‡

Department of Chemical Engineering and Laboratory for Laser Energetics, UniVersity


of Rochester, Rochester, New York 14627

Received February 17, 2005; Revised Manuscript Received March 25, 2005

ABSTRACT
This paper reports a highly effective synthesis of platinum multipods from platinum 2,4-pentanedionate in organic solvents. A trace amount
of silver acetylacetonate is used to trigger the nucleation and the anisotropic growth of Pt nanocrystals. The morphologies of Pt multipods
made include I- and V-shaped bipods, various types of tripods, and planar and three-dimensional (3D) tetrapods. The 3D Pt tetrapods can be
well-defined, resembling those observed for II−VI semiconducting materials, such as CdS and CdSe. Control of morphology and the multipod-
to-sphere transitions under various conditions have been systematically studied. A mode of formation based on the induced kinetically controlled
growth has been discussed.

Introduction. Development of nanometer scale branched crystals. Although the formation mechanism is not com-
nanocrystals of metal,1-4 metal oxide,5-8 and semiconducting pletely clear, it appears that use of proper capping reagents
materials9-14 is an important research subject that has such as cetyltrimethylammonium bromide (CTAB) and poly-
attracted a great deal of attention in recent years. In addition (vinylpyrrolidone) (PVP) is very important, but it is only
to their intrinsic electronic, magnetic, photonic, and catalytic one of the prerequisites. The kinetic control of growth process
properties, these branched nanomaterials have been proposed is also critically important. The tested strategies for promot-
to be used as building blocks for making complex nano- ing the formation of metal multipods include homogeneous
structures through self-assembly processes.15 Such structures seeded growth4 and heterogeneous growth on metal
are directly relevant to the fabrication of multiple-terminal plates.3 Xia and co-workers have also demonstrated that the
nanodevices and as active components in new photovoltaic addition of NaNO3 could promote the formation of Pt
devices.16,17 Multipods such as 3D tetrapod nanocrystals can octapods and tetrapods in a polyol process.1 We noted that
also have advantages in the generation of hierarchical the length of the branches was rather short in these cases.
nanostructured network over their counterparts of nanorods, The branches were either not well defined or in a cone shape
nanowires, nanocubes, and nanoprisms. rather than straight rods, which could be related to the growth
Although well-defined tetrapods of CdSe and CdS have direction.
been developed for several years,18,19 the metal multipod and In this report, we present a synthetic method for making
hyper-branched nanostructures have only recently been Pt multipods through an induced anisotropic growth process
explored intensively.1-4 So far the level of control in the at temperatures below that for the homogeneous nucleation
anisotropic growth of branched metal nanocrystals cannot
and growth of Pt nanoparticles from platinum 2,4-pentanedi-
match that for the growth of well-defined tetrapods of
onate (Pt(acac)2). A small amount of silver acetylacetonate
cadmium chalcogenides (Se and S).10,11 This phenomenon
(Ag(acac)) was used to trigger the formation of branched Pt
may be due to the fact that most metals typically do not
nanocrystal, as this silver precursor could readily decompose
have polymorphism. The condition for branched growth
and be reduced to form colloidal metal clusters at < 200
based on the lattice match at the surfaces of two crystal types
°C.
(such as zinc blende and wurtzite) in nanocrystals of
cadmium chalcogenides can be hard to create for metal Experimental Section. In a typical synthesis, a mixture
nanocrystals through a homogeneous nucleation and growth of 1, 2-hexadecanediol (Aldrich, 90%, 800 mg), Pt(acac)2
process, though it is possible. Only gold, platinum, and (Gelest Inc., 200 mg), diphenyl ether (Aldrich, 99%, 2 mL),
rhodium have been shown to form branched metal nano- hexadecylamine (HDA, Aldrich, 90%, 4 g), and 1,2-
adamantanecarboxylic acid (ACA, Aldrich, 99%, 180 mg)
* Corresponding author: E-mail: hongyang@che.rochester.edu, Tele- was added into a 25 mL, three-neck, round-bottom flask
phone: (585) 275-2110; Fax: (585) 273-1348.
† Department of Chemical Engineering. under argon protection. The reaction mixture was heated and
‡ Laboratory for Laser Energetics. held at the designed temperature using a glycerol bath. The
10.1021/nl0503072 CCC: $30.25 © xxxx American Chemical Society PAGE EST: 6.2
Published on Web 00/00/0000
temperature of this oil bath was monitored by Chemglass used in this work because of its good solubility in organic
ETC temperature controller. A small amount of Ag(acac) solvents, such as diphenyl ether. The evolution of Pt
(Aldrich, 99%, 3 mg) was then quickly added into the flask, multipods and nanoparticles was followed by TEM.
which resulted in a rapid formation of gray suspension, Figure 1 shows a series of TEM images of Pt nanoparticles
indicating the formation of nanoparticles or multipods. The obtained at 180 °C for reaction times ranging from 4.5 to
color of the reaction mixture quickly turned into black. The 60 min after a tiny amount of Ag(acac) was added into the
temperature could be maintained within ( 1 °C for the entire flask. At the initial stage, largely faceted rather than spherical
reaction time period of 60 min. Aliquots of samples (∼200 nanocrystals began to appear at 4.5 min after adding the silver
µL) were taken every minute during the first 10 min to precursor, Figure 1a. Although some morphologies resembled
monitor the growth kinetics. The concentrations of reagents those that were previously observed for Pt nanoparticles,23
were fixed for all the synthesis, while the reaction temper- the embryonic forms of various multipods began to develop.
atures were varied from 160 °C to 210 °C; unless indicated The population of multipods nevertheless was rather low at
otherwise. For those secondary injection experiments, a total this stage. These nanocrystals grew rapidly into multipods
amount of 2.5 mL of reactant mixture (100 mg of HDA, within the next minute, which was indicated by the rapid
100 mg of Pt(acac)2, 100 mg of ACA, and 100 mg of 1,2- change of color from brown to black. A large area of
hexadecanediol in 1 mL of diphenyl ether) was preheated multipods with several different shapes was observed, Figure
to 170 °C. Three equal aliquots (∼0.83 mL) of this mixture 1b. The various morphologies included triangular nano-
were injected into the reaction flask at 7, 9, and 12 min after prisms; I- and V-shaped bipods; regular, T- and Y-shaped
the addition of Ag(acac). tripods; and planar and 3D tetrapods. As the reaction
After the reaction, the nanoparticles were washed and continued, the growth along the branch directions became
separated using chloroform and ethanol. In a typical proce- obvious, Figure 1c and 1d. The overall length-to-width aspect
dure, a designed amount of the product (200 µL) was ratio of the branches in Figure 1c and 1d was visibly higher
dispersed in 800 µL chloroform in a small vial (2 mL), than those in Figure 1b, while the diameter of branches was
followed by the addition of 1 mL ethanol to induce the relatively constant. There were no obvious spherical Pt
precipitation of nanoparticles. The precipitates were separated nanoparticles. This observation was very different from the
from the solvent mixtures by centrifuge at 5000 rpm for 5 Au multipods formed on Ag plates, which contained ∼40%
min. Yellow-brownish supernatant was decanted and the spherical nanoparticles.2 The rod-like shape of the branches
black products were recovered by dispersing in 1 mL of was also different from those Pt tetrapods and octapods made
chloroform. This process was followed by a second wash in the polyol process through the addition of NaNO3 in that
and separation using 1 mL of ethanol. The final products these tetrapods were fully developed.1 After reaction for ∼10
were stored in chloroform. min, no distinct growth along the branch direction was
Transmission electron microscopy (TEM) specimens were observed; while the width of each branch began to increase,
prepared by dispersing the samples of nanocrystal in Figure 1e, followed by a continuous disappearance of
chloroform (∼1 mg/mL) and drop-cast onto carbon-coated multipods. The multipods turned into rice-shaped particles
copper grids. An ultrahigh vacuum scanning transmission with the dissolution and growth process, Figure 1f and 1g.
electron microscope (UHV-STEM, Cornell VG HB501) and Upon 40 min after adding the silver precursor, multipods
a regular TEM (JEOL 2000 EX) were used to examine the evolved into spherical nanoparticles, Figure 1h. The size
size and shape of the nanoparticles. The UHV-STEM was distribution of nanoparticles became relatively monodisperse
also used to conduct the energy-dispersive X-ray (EDX) at the reaction time of 60 min and no further morphology
analysis and nanoelectron diffraction (ED) of individual change was observed, Figure 1i. This shape evolution
nanoparticles. The electronic gun of this STEM system could suggested that the formation of multipods should be a
be focused into a spot with a diameter of less than 1 nm. kinetically controlled growth and the thermodynamically
The lattice fringes of Pt multipods were examined on a stable shape of nanocrystals should be spherical.
Hitachi HD-2000 STEM operating in ultra-high resolution Figure 2 showed PXRD and EDX spectra of Pt multipods.
mode at 200 kV and 30 mA. Powder X-ray diffraction All the X-ray diffraction peaks could be assigned to face-
(PXRD) spectra were recorded on a Philips MPD diffrac- centered cubic (fcc) platinum (space group: Fm3m). No
tometer with a Cu KR X-ray source (λ ) 1.5405 Å) at a diffraction signal from silver could be observed. EDX was
scan rate of 0.015 2θ/s. Details of the characterization used to analyze the chemical composition of individual
methods could be found elsewhere.20, 21 multipods. The observed EDX peaks at 2.1, 9.4, and 11.1
Results and Discussion. The temperature for the forma- keV could be assigned to Pt M, LR, and Lβ lines, respectively.
tion of Pt nanoparticles from Pt(acac)2 via a homogeneous The peaks at 8.0 and 8.9 keV could be assigned to the copper
nucleation and growth process was g ∼210 °C using the KR and Kβ lines, respectively, which were from the substrate.
reaction mixture described above. This reaction temperature No silver signal could be detected. These data indicated that
was similar to those reported for such systems.22 It is known the multipods were made of metallic platinum.
that various silver salts can be reduced to silver metal readily The structure details of multipods were analyzed by
through different pathways. We chose silver salt as the nanoelectron diffraction using the UHV-STEM. Figure 3
reagent to induce nucleation and growth of Pt nanocrystals shows the dark and bright field TEM images of a V-shaped
from Pt(acac)2 at temperatures below 210 °C. Ag(acac) was bipod, a regular 120° tripod, and a 3D tetrapod. As discussed
B Nano Lett.
Figure 1. TEM images of Pt particles synthesized at 180 °C for (a) 4.5, (b) 5.5, (c) 7.5, (d) 9.0, (e) 12, (f) 15, (g) 20, (h) 40, and (i) 60
min after Ag(acac) was added. All scale bars are 20 nm.

above, there were variations of bipods, tripods, and tetrapods.


The two-branched structures could exist at different angles
and subsequently lead to diverse forms, ranging from
V-shaped bipods, Figure 2b, to almost straight I-shaped rods.
For the tripods, different branches tended to have similar
length but could also have a different aspect ratio for each
branch in the same tripod. The angles between neighboring
branches could also change from close to 180° in a T-shaped
tripod to 120° or less. The ED images taken at the tip region
of each branch of the tetrapod were shown as insets of Figure
3d. By calculating the length ratio from the center spots to
the adjacent spots, we obtained the zone axes of the
branches,24 which were [111] axes. The high-resolution TEM
image shows the V-shaped Pt bipod is single crystalline,
Figure 4. The measured d spacing corresponded to 2.2 Å
(or 2.2 nm for 10 consecutive lattice fringes), which could
be assigned to the (111) plane. These results indicated that
the growth of the branches was along 〈110〉 directions.
It has been reported that the formation of metallic
multipods and controlled platonic shapes could be associated
with the competitive growth between (111) and (100)
planes.1,2,25 In the case of formation of gold tripods and planar
tetrapods in aqueous solution using pre-synthesized silver Figure 2. PXRD (top) and EDX (bottom) spectra of Pt multipods.
plates as seeds,2 the growth was preferentially inhibited on The samples used were synthesized at 180 °C for 9 min after the
(111) planes, and the particles ended up with cube shapes addition of Ag(acac).
Nano Lett. C
Figure 3. (a) Dark and (b-d) bright field UHV-STEM images of Pt multipods synthesized at 180 °C. The insets show the nanodiffraction
patterns used to determine the crystallographic direction (zone axis) of each branch. The 10 nm scale bars apply to all images.

Pt nanocrystals triggered by the trace amount of silver could


play an important role in directing the preferential growth
along a particular crystallographic direction. Although no
silver could be detected in the Pt multipods, we noted no
multipod formation without using silver precursors. In
addition, the Ag seeds have been used in the synthesis of
different metal particles.2,28-30 Addition of Ag(acac) into hot
organic solvent led to the formation of silver clusters that
promoted the Pt precursors decomposition and growth of Pt
on the low-index planes. These Ag clusters could contain as
few as four atoms.30 This seeded growth process allowed
the Pt nanocrystal to form below the nucleation and growth
temperature in the absence of silver species, which was
experimentally determined to be about 210 °C in our reaction
Figure 4. High-resolution TEM image of a V-shaped Pt bipod system. The growth kinetics could differ among the various
showing the (111) lattice fringes. The labeled length is for 10
repeating fringes. low-index planes.
Reaction temperature was another important parameter for
showing the (100) planes. On the other hand, when growth the kinetically controlled process, thus one would expected
on (100) planes was inhibited, the resultant particles termi- it could affect the shape evolution of Pt nanocrystals. Figure
nated by the (111) faces. When growth on both (111) and 5 shows the typical TEM images of Pt nanoparticles obtained
(100) planes was inhibited, (110) planes were dominant, at various times between 3.5 and 20 min after Ag(acac) was
which led to the formation of tripods. Under our synthetic added for the reactions conducted at 190 and 200 °C,
conditions, the formation mechanism of Pt multipods ap- respectively. The TEM data showed that the shape evolution
peared to agree with those for Au multipods. from Pt multipods to spheres had a trend similar to those
In the presence of surfactants, differences in the adsorption reactions conducted at 180 °C. The optimal reaction times
of surfactants on the various crystal planes led to the for the formation of high population and well-defined
competitive growth. In our case, It seems that the branches multipods were different from those formed at 180 °C. Large
grew preferentially along 〈110〉 directions. This could not populations of multipods appeared as early as 3.5 min after
be explained entirely by the steric hindrance in the case for the silver precursor added at 190 °C. The multipods began
typical Au and Pt nanoparticles.1-3,23,26-28 The formation of to turn into spheres at ∼12 min. For those formed at 200

Figure 5. TEM images of Pt multipods and nanoparticles synthesized at (a-e) 190 and (f-j) 200 °C after the addition of Ag(acac) for
given periods of times: (a, f) 3.5, (b, g) 5.5, (c, h) 7.5, (d, i) 12, and (e, j) 20 min. All scale bars are 20 nm.
D Nano Lett.
°C.22 It was plausible that silver might work not only to
induce the formation of nucleation seeds2,28-30 but also to
function as catalysts to facilitate the formation of Pt particles
below the decomposition temperature of Pt(acac)2. Recently,
Song et al. reported the synthesis of platonic shapes of Pt
nanoparticles with the addition of Ag precursors.28 Silver
species such as Ag42+ could adsorb on (100) planes of Pt
particles and promote the reduction of Pt salts preferentially
on (100) planes that adsorbed these Ag species continuously.
Further experiments are needed to determine if this mode
of formation is reasonable in our system.
The transitions from multipods to spherical nanoparticles
could be interpreted by the Ostwald ripening.31 In these cases,
Figure 6. Effect of temperature on the shape of Pt nanoparticles there was a critical size at the equilibrium state.10,22,31 Particles
and multipods. No Ag(acac) was added for reaction conducted at that were smaller than the critical size dissolved while the
210 °C, as particles formed spontaneously at this temperature.
large ones continued to grow. At the early stages after
°C, Pt multipods began to change their shapes as early as nucleation, the kinetic growth governed the shapes of Pt
∼7.5 min after the silver precursor was added. These results particles, resulting in multipod structures. When the monomer
indicated that anisotropic growth disappeared at an earlier depleted, the ripening process became dominant. The branches
time with the increase of reaction temperature. of multipods began to dissolve, subsequently resulting in the
A wide range of reaction times and temperatures was formation of spherical particles at relatively large diameters.
examined, and the results are summarized in Figure 6. The A thermodynamically controlled process should be favored
classification of shapes for each data point shown in this when thermal energy is sufficiently high. Particles tend to
figure was based on a series of TEM studies. Three distinct minimize the surface energy through the transformation from
regimes were observed for these reaction systems at the the highly faceted multipods to spheres that possess lower
different temperatures, i.e., no particles, multipods, and specific surface area than multipods. The temperature-
spheres. No Pt particles formed for the entire reaction period dependent transitions observed in our results could be
up to 60 min, when the reaction temperatures were between interpreted by this formation mechanism.
160 and 175 °C. Multipods were formed at 2.5 to 4.5 min We further investigated if the addition of Pt(acac)2 at the
after the addition of Ag(acac) for the reactions conducted various stages of the reaction could prolong the growth of
between 180 and 200 °C. The multipods disappeared and multipods. A reaction mixture with total amount of 100 mg
turned into spheres after reacting for additional 10 to 15 min. of Pt(acac)2 was injected into the reaction flask in three equal
The higher the reaction temperatures were, the earlier the Pt aliquots at 7, 9, and 12 min, respectively, after the addition
multipods formed and the sooner they evolved into spheres. of Ag(acac). To minimize the formation of new nuclei during
We noted that the temperatures used to synthesize Pt particles the secondary injections, less than 40% of the existing
were lower than that for the decomposition of Pt(acac)2 in reaction precursor was suggested in each addition.32 In our
the presence of HDA and ACA, which began at 210-220 case, each aliquot was equal to ∼17% of the total amount

Figure 7. TEM images showing the shape evolution of Pt multipods and nanoparticles after multiple secondary injections of reaction
mixtures at 180 °C. The TEM images were taken at (a) 7.0, (b) 8.5, (c) 11, (d) 15, (e) 20, (f) 30, (g) 40, and (h) 60 min, respectively. A
mixture of HDA (100 mg), Pt(acac)2 (100 mg), ACA (100 mg), 1,2-hexadecanediol (100 mg), and diphenyl ether (1 mL) was preheated to
170 °C and injected into the reaction flask in three equal aliquots at 7, 9, and 12 min after the reaction, respectively. All scale bars are 20
nm.
Nano Lett. E
Figure 8. TEM images showing the effect of Pt(acac)2 amount on the formation of Pt multipods. The amounts of Pt(acac)2 used were (a)
50, (b) 100, and (c) 200 mg, respectively. All scale bars are 20 nm.

of Pt(acac)2 in the reaction flask prior to the secondary CTS-041722), the DOE through LLE (DE-FC03-92SF19460),
injection. Figure 7 shows the TEM images of Pt nanocrystals and the subcontract of a MURI Grant from DoD (FA9550-
synthesized at 180 °C for the reaction time periods of 7 (prior 04-1-0430). This work made use of the Shared Experimental
to the first time of secondary injection), 8.5, 11, 15, 20, 30, Facilities at the Cornell Center for Materials research
40, and 60 min, respectively. Our results indicated that the (CCMR) supported by NSF and the Hitachi HD-2000 STEM
growth process of multipods could be extended using the at the Centre for Nanostructure Imaging, University of
multiple injection approach, and the transition time from Toronto, funded by Canada Foundation of Innovation and
multipods to spherical particles changed to 30 min after the Ontario Innovation Trust. We are grateful to LLE for a
initial addition of Ag(acac). Some multipods could still be Horton Fellowship (X.T.). We thank Drs. Mick Thomas
observed, even when the reaction time reached 60 min. In (Cornell University) and Marc Mamak (University of Tor-
comparison, without the multiple injection, the multipod- onto) for running the high resolution TEM. The support of
to-sphere transition happened at ∼20 min after the initial DOE does not constitute an endorsement by DOE of the
addition of Ag(acac). views expressed in this article.
The effect of the amount of Pt(acac)2 used on the shape
evolution of particles was also investigated. Pt(acac)2 precur- Note Added after ASAP Publication. Text phrase II-IV
sor at 50-, 100-, and 200-mg levels was chosen in these was corrected to II-VI in the Abstract and Conclusions. This
experiments. Reactions were conducted at 190 °C for 5 min paper was published ASAP on 4/9/05. The corrected version
after the addition of Ag(acac). Our TEM study shows that was reposted on 4/13/05.
at the low precursor concentration, spherical Pt particles were
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