DOI: 10.1002/cctc.

201600612

Communications

Enhancing the Activity of Platinum-Based Nanocrystal

Catalysts for Organic Synthesis through Electronic
Structure Modification
Minjune Kim+, Yena Kim+, Yeonjoon Kim+, Yongmin Kwon, Kyungrok Ham, Woo Youn Kim,*
and Sang Woo Han*[a]
We report a systematic study on the correlation of the modified electronic structure of nanocrystal catalysts with the adsorption properties of the substrate and the resultant catalytic
activity by using BaeyerVilliger oxidation catalyzed by composition-controlled Pt-based nanocubes (NCs) as a model heterogeneous catalysis reaction. The incorporation of 3d transition
metals into Pt to form PtM (M = Zn, Co, and Ni) alloy NCs allowed fine-tuning of the electronic structure of Pt. PtM NCs
with a higher-lying d band center exhibited higher catalytic
performance owing to the enhanced initial activation of the
carbonyl group of the substrate. This work emphasizes the importance of fine-tuning the electronic structure of heterogeneous catalysts to advance their catalytic function.

The selective adsorption and stabilization of chemical species

onto the surface of a heterogeneous catalyst is an important
step to drive a catalytic reaction along a desirable pathway.[1] It
can be elaborately controlled by modifying either the structural parameters of the catalysts or the structure of the chemical
species. Because the latter approach may limit the usability of
heterogeneous catalysts, the former approach appears to be
more plausible. Indeed, the morphology, composition, surface
passivation, and supporting materials of heterogeneous catalysts have profound influences on their performance levels.[2]
However, the difficulty of structural modification should be resolved for the development of efficient heterogeneous catalysts for intended reactions.[1] In this context, the use of metal
nanocrystals with well-defined structural characteristics as heterogeneous catalysts has received considerable research attention, because it promises enhanced catalytic performance and
provides new opportunities for the development of heterogeneous catalysts through precise control over the characteristics
of the nanocrystals.[3]

Among the various structural variables of metal nanocrystals,

control of the composition can be highly promising in attempting to develop desirable catalysts, as it can be used to
modify the surface electronic structure of the nanocrystals and
thus to manage the interaction between the nanocrystal surface and the chemical species involved in catalysis reactions.[4]
This approach has been widely employed in applications of
metal nanocrystals toward electrocatalysis reactions associated
with low-temperature fuel cells, such as oxygen reduction and
fuel oxidation.[5] It has been evidenced that modification of the
electronic structure indeed plays a crucial role in the manipulation of the binding energy of the reaction intermediates, such
as active oxygen species and CO, on the surfaces of nanocrystal-based electrocatalysts, and this leads to an improvement in
the catalytic activity.[57] Therefore, we envision that fine-tuning
the electronic structure of metal nanocrystals by controlling
the composition will pave a new way to designing advanced
heterogeneous catalysts for organic synthesis reactions.
To corroborate the above inference, we performed heterogeneous BaeyerVilliger oxidation (BVO) reactions with composition-controlled metal nanocrystals as a proof-of-concept experiment (Scheme 1). BVO converts a ketone compound into
its corresponding ester derivative, for which the selective activation of the carbonyl functional group is the key to achieve
high product selectivity and thus high efficiency.[8] For proper

[a] Dr. M. Kim,+ Y. Kim,+ Y. Kim,+ Y. Kwon, K. Ham, Prof. W. Y. Kim,

Prof. S. W. Han
Center for Nanotectonics
Department of Chemistry and KI for the NanoCentury
KAIST
Daejeon 34141 (Korea)
E-mail: sangwoohan@kaist.ac.kr
wooyoun@kaist.ac.kr

[+] These authors contributed equally to this work.

Supporting Information and the ORCID identification number(s) for the
author(s) of this article can be found under http://dx.doi.org/10.1002/
cctc.201600612.

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Scheme 1. An illustration of the heterogeneous BVO reaction catalyzed by

the well-defined Pt-based NCs.

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Communications
activation of the carbonyl functional group, we chose Pt-based
nanocrystals as a Lewis-acid catalyst and prepared shape-controlled Pt-based nanocrystals with different compositions, that
is, Pt and PtM alloy (M = Zn, Co, and Ni) nanocubes (NCs), for
comparison. The incorporation of different 3d transition
metals, such as Zn, Co, and Ni, into Pt can modify the electronic structure of Pt to different extents through interplay between the ligand and the geometric effects, which arise, respectively, from charge transfer between Pt and the 3d transition metal and modification of the surface lattice.[9] Through
comparative studies of the catalysis with the prepared Ptbased NCs as well as commercially available Pt catalysts, we
could extract an accurate correlation of the modified electronic
structure of the nanocrystal catalyst imparted by the change in
its composition with the adsorption properties of ketone substrates and the resultant catalytic activity. We also developed
an ecofriendly process for the heterogeneous BVO reaction, in
which the catalysis reaction proceeds in water at room
temperature.
Pt-based NCs were prepared by using an oleylamine-mediated synthesis method [see the experimental details in the Supporting Information].[10] As show in Figure 1 ac and Figure S1 a
(Supporting Information), all of the prepared nanocrystals have
a distinct cubic shape. The average edge lengths of the Pt,
PtZn, PtCo, and PtNi NCs were (9.14 1.55), (7.62 1.42),
(13.02 3.01), and (16.69 3.39) nm, respectively (Figures S1 b
and S2). High-angle annular dark-field scanning transmission
electron microscopy energy-dispersive X-ray spectroscopy
(HAADF-STEM-EDS) elemental mapping images (Figure 1 df)
and cross-sectional compositional line profile analyses (Figure S3) of the PtM NCs demonstrate their homogeneous alloy
structure. The Pt/M atomic ratios of the prepared PtZn, PtCo,
and PtNi NCs determined by inductively coupled plasma
atomic emission spectroscopy (ICP-AES) were 87.3:12.7,
87.8:12.2, and 87.2:12.8, respectively. The d spacings for adjacent lattice fringes measured in the high-resolution TEM
(HRTEM) images of the Pt, PtZn, PtCo, and PtNi NCs are close

to that of the (2 0 0) planes of face-centered cubic (fcc) Pt (Figure S4), which indicates that the prepared NCs are enclosed by
{1 0 0} facets. The X-ray diffraction (XRD) patterns of the Ptbased NCs exhibit typical diffraction peaks corresponding to
the reflections from the fcc structure, which is further indicative of the crystalline nature of the synthesized NCs (Figure S5).
Given that the prepared PtM NCs have similar structural and
crystallographic characteristics together with similar Pt/M
atomic ratios apart from the identity of the secondary metal,
systematic studies on the influence of the compositions of the
NCs on the catalytic performance were possible in this work.
Considering the fact that the activity of nanocatalysts depends
on their size,[11] the difference in the average size of the prepared NCs may affect the intrinsic catalytic efficacy of the NCs,
which would thus impede precise investigation of the composition-dependent catalytic function. However, this possibility
was excluded, because we compared the catalytic activities of
the NCs after their normalization to the number of surface
atoms of the NCs used in the catalysis reaction (see below).
The catalytic activities of composition-controlled Pt-based
NCs toward the BVO reaction were explored and benchmarked
against commercially available Pt catalysts, that is, Pt black and
Pt/alumina (Figure S6). To develop an ecofriendly process for
the heterogeneous BVO reaction, we optimized the reaction
conditions in water medium. The details of this optimization
process are described in the Supporting Information. On the
basis of the results of the optimization, we conducted the catalysis reactions by using 2-phenylcyclohexanone (0.5 mmol), 3chloroperoxybenzoic acid (mCPBA, 2 equiv.), Cs2CO3 (10 mol %),
and the Pt-based catalysts (0.1 mol %) in water at room temperature. Table 1 summarizes the yields of the isolated product,
6-phenyl-e-caprolactone, and the turnover frequencies (TOFs)
obtained with the different Pt-based catalysts. The selectivity
of the product for each catalysis reaction was approximately
100 % under our synthesis conditions. The TOF of each catalyst,
the conversion of 2-phenylcyclohexanone per surface atom,
was evaluated on the basis of the number of surface atoms

Figure 1. ac) TEM images and df) HAADF-STEM images and corresponding EDS elemental mapping images of the PtM NCs: a, d) PtZn, b, e) PtCo, and
c, f) PtNi NCs. Scale bars: ac) 30, d) 3, and e, f) 5 nm.

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Table 1. TOFs for the BVO reaction of 2-phenylcyclohexanone catalyzed
by the Pt-based catalysts.

Entry

Catalyst

Yield [%]

TOF [h1]

1
2
3
4
5
6
7

Pt black (1 mol %)
Pt/alumina
Pt NCs
PtZn NCs
PtCo NCs
PtNi NCs

6
20
29
53
75
84
92

11.5
51.0
369
437
844
1183

used in the catalysis reaction (see the Supporting Information

for details). Noticeably, the catalytic activity of the Pt-based
NCs outperformed that of the commercial Pt catalysts. Because
all of the reactions were conducted at an identical stirring rate
of 750 rpm, and the catalytic activity of the supported catalyst,
Pt/alumina, was not significantly affected by the stirring rate
(Figure S7), the higher activity of the Pt-based NCs relative to
that of the commercial Pt catalysts is likely a result of their uniform shape and well-defined surface. Interestingly, the catalytic
performance of the prepared Pt-based NCs was distinctly dependent on their compositions. The PtM NCs exhibited higher
catalytic activity than the monometallic Pt NCs. Among the different PtM NCs, the PtNi NCs showed the highest activity for
the BVO reaction, followed by the PtCo and PtZn NCs. The

same activity trend across the different PtM NC catalysts was

also identified in the isothermal reaction profiles obtained by
monitoring the progress of the consumption of the reactant
and the consequent formation of the product by in situ
1
H NMR spectroscopy, for which chloroform was used as a solvent for convenience of the NMR spectroscopy experiments
and 1,1,2,2-tetrachloroethane was used as an internal standard
(Figure 2 a).
To examine the possibility that Pt leached from the NCs catalyzes the reaction, we measured the amount of leached Pt in
the reaction solution after the BVO reaction. Pt was not detected in the ICP-AES measurements, whereas less than 4 ppb of
Pt was detected by ICP-mass spectrometry. It can be inferred
that such an insignificant amount of leached Pt is not correlated with the high catalytic activity of the NCs. For further confirmation of the negligible effect of the leached Pt on the catalysis, an Hg-poisoning test was also performed.[12] Indeed, the
catalysis reaction did not proceed after Hg treatment of the reaction mixture. These results unequivocally indicate that the
catalysis reaction proceeds on the surface of the NCs. On the
other hand, the uncontrolled presence of residual stabilizing
agents on the surface of the NCs is not associated with the
trend in the activity of the Pt-based NCs (Figure S8).
As mentioned previously, the incorporation of different 3d
transition metals into Pt can modify the electronic structure of
Pt to different extents owing to different interplay between
the ligand and the geometric effects. As such, the interaction
between the nanocrystal surface and the chemical species involved in the catalysis reactions could be manipulated. It is
generally accepted that the adsorption energy of oxygen-con-

Figure 2. a) Reaction profiles of the PtM NC-catalyzed BVO reaction. The filled and hollow symbols represent, respectively, the amounts of the reactant and
the product at different reaction times for the PtZn (square), PtCo (triangle), and PtNi NCs (circle). b) Pt 4f7/2 binding energies (filled squares) and TOFs (filled
circles) of the various Pt-based catalysts. FTIR spectra for the n(C=O) mode of 2-phenylcyclohexanone on the c) PtZn, d) PtCo, and e) PtNi NCs. The gray and
green bands are attributed to weakly and strongly binding 2-phenylcyclohexanone on the NC surfaces, respectively.

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Communications
taining species on a metal surface increases as the position of
the metal d band center relative to that of the Fermi level is
shifted upward.[6, 7] This is because antibonding states, which
are formed from coupling between the metal d states and the
oxygen 2p states, are also shifted upward and are thus less
filled upon the upward shift of the d band center.[6] To determine the correlation of the modified electronic structures of
the Pt-based NCs with the catalytic activity, the electronic
structures of the prepared NCs were investigated by X-ray photoelectron spectroscopy (XPS) measurements of the Pt 4f core
level (Figure S9). Core-level XPS measurements are widely used
to examine d band shifts as a result of their high consistency
with those on the valence band.[13] As shown in Figure 2 b and
Figure S9, the Pt 4f binding energies of the Pt-based NCs were
redshifted relative to those of Pt/alumina, and the magnitude
of the shift follows the order Pt PtZn < PtCo < PtNi NCs,
which implies that the d band centers of the Pt-based NCs
were shifted upward by controlling the shape and composition. Apparently, the trend in the shift of the Pt 4f binding
energy and thus the shift in the d band center of the NCs is
highly correlated with that in the catalytic performance (Figure 2 b). As the d band center shifted upward, the catalytic activity increased. Given that selective activation of the carbonyl
group in the reactant molecule is the key to achieving high efficiency in the BVO reaction, this result indicates that the increase in the BVO activity in the order Pt < PtZn < PtCo < PtNi
NCs can be attributed to the increase in the extent of initial activation of the carbonyl group in the same order. Specifically,
as the d band center of the Pt-based NCs shifts upward, the
carbonyl group of the reactant molecule can be more effectively activated owing to its increased adsorption energy on
the metal surface. Accordingly, the accessibility of the peroxidant to the carbonyl group increases, which facilitates the formation of an acetal-like reaction intermediate, that is, a
Criegee adduct (Scheme 1 and Figure S10).[8]
To confirm the above inference, we performed FTIR spectroscopic studies on the adsorption properties of 2-phenylcyclohexanone on the Pt-based NCs (Figure S11). Given that the
bond strength of the carbonyl group weakens upon interaction with the metal surface,[14] a close inspection of the band
associated with the C=O stretching mode [n(C=O)] of 2-phenylcyclohexanone adsorbed on the Pt-based NCs would allow verification of the extent of the initial activation of the carbonyl
group. As shown in Figure 2 ce, the n(C=O) band for each PtM
NC has an asymmetric line shape, which is likely a result of the
presence of both weakly and strongly binding 2-phenylcyclohexanone on the NC surfaces. The corresponding band for the
Pt NCs has a symmetric line shape, which is similar to that of
pristine 2-phenylcyclohexanone. The observed asymmetric features are not attributed to residual stabilizing agents on the
NC surfaces, as the organic compounds used in the synthesis
of the NCs have no specific spectral features in this region.
Each n(C=O) band was deconvoluted and fitted with Lorentzian curves to resolve each component. The high-wavenumber
component, of which the position is similar to that of free 2phenylcyclohexanone, can be attributed to weakly binding 2phenylcyclohexanone on the NC surface, and the low-waveChemCatChem 2016, 8, 2450 2454

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number component corresponds to the weakened carbonyl

group of strongly binding 2-phenylcyclohexanone. Notably,
the relative portion of the low-wavenumber component increased in the order PtZn (33 %) < PtCo (53 %) < PtNi NCs
(66 %), which is consistent with the results of the catalysis experiments and XPS measurements.
With the optimized reaction conditions of BVO, we performed substrate tolerance tests with the PtNi NCs, the most
efficient catalyst under our experimental conditions, to check
their wide applicability for various substrates. Apparently, the
NC-catalyzed BVO of various cyclic ketones successfully yielded
the desired ester products (Table S3). Interestingly, (+
+)-trans-dihydrocarvone, which contains an alkene functional group,
gave the ester product in a high yield. The yield of an epoxideester counterpart formed from overoxidation was less than
5 %. This further revealed that the NC catalysts could indeed
selectively activate the carbonyl functional groups. Furthermore, the recyclability of the PtNi NCs was explored by reusing
the catalyst for the BVO reaction of 2-phenylcyclohexanone
(Table S4). The yields of the product were 91 and 87 % in the
second and third cycles, respectively, which implied that the
prepared NCs could be used as efficient recyclable catalysts in
heterogeneous catalysis reactions. Because the amount of
leached Pt after each catalysis cycle was negligible, the slight
decrease in the product yield during the recyclability test can
thus be ascribed to the loss of NCs during the re-collection
process. TEM measurements of the PtNi NCs after the reactions
revealed that most of the NCs maintained their original shape
(Figure S12).
In summary, we performed heterogeneous BaeyerVilliger
oxidation reactions with composition-controlled Pt-based
nanocubes. Through systematic studies on the catalysis of the
prepared Pt-based nanocubes, we established a correlation between the modified electronic structure of the nanocrystal catalyst imparted by the change in its composition and the adsorption properties of the substrate and the resultant catalytic
performance. The present work suggests the importance of
fine-tuning the electronic structure of heterogeneous catalysts
to advance their catalytic function. We foresee that such insight will aid in the rational design of advanced nanocrystal
catalysts that can be useful for important chemical reactions.

Acknowledgements
This work was supported by the Basic Science Research Program
(2015R1A3A2033469) through the National Research Foundation
of Korea (NRF) funded by the Ministry of Science, ICT & Future
Planning.
Keywords: alloys composition heterogeneous catalysis
nanostructures platinum

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Received: May 20, 2016

Published online on July 27, 2016

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2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim