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Nano Today xxx (2018) xxx–xxx

Contents lists available at ScienceDirect

Nano Today
journal homepage: www.elsevier.com/locate/nanotoday

Review

Heterogeneous catalysis by gold and gold-based bimetal nanoclusters

Jianbo Zhao a,b,∗ , Rongchao Jin b,∗
a
Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, No.136 of Science Road, Zhengzhou 450001,
China
b
Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, United States

a r t i c l e i n f o a b s t r a c t

Article history: Gold and gold-based bimetallic catalysts have shown great potential for many important chemical trans-
Received 8 September 2017 formation reactions owing to their good activity and high selectivity under relatively mild conditions.
Received in revised form 8 November 2017 However, elucidating their structure-property relationships remains a major challenge because of size
Accepted 23 December 2017
distributions and ill-defined structures (i.e. structural heterogeneity) of conventional nanoparticle cata-
Available online xxx
lysts. Recently, controlled synthesis of homogold and gold-based bimetal nanoclusters with precise atom
numbers have been accomplished, and more importantly their atomic structures have been elucidated,
Keywords:
which provide new model systems for understanding the catalytic behavior at the atomic level. Due
Catalysis
Homogold nanoclusters
to their ultra-small size, gold and bimetal nanoclusters exhibit unique properties, which contribute to
Gold-based bimetal nanoclusters novel catalysts or precatalysts for many chemical reactions. Herein, we review the recent progress in
Ligand the catalytic research of atomically precise gold and gold-based bimetal nanoclusters. Specifically, this
Structure-property relationship review covers the application of nanoclusters with or without ligands as catalysts for reactions such as
selective oxidation, selective hydrogenation, C–C coupling and photocatalysis. Finally, we provide some
future perspectives about metal nanocluster catalysis.
© 2017 Elsevier Ltd. All rights reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Synthetic breakthroughs of gold and bimetallic nanoclusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Homogold nanoclusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Size-focusing methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
LEIST methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Gold-based bimetal nanoclusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Catalytic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Homogold nanoclusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Carbon–Carbon coupling reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Gold-based bimetal nanoclusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Selective hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Carbon–Carbon coupling reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

∗ Corresponding authors at: Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, United States.
E-mail addresses: zhaojianbo@zzuli.edu.cn (J. Zhao), rongchao@andrew.cmu.edu (R. Jin).

https://doi.org/10.1016/j.nantod.2017.12.009
1748-0132/© 2017 Elsevier Ltd. All rights reserved.

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Introduction

Heterogeneous catalysis occupies a pivotal position in the man-

ufacture of essential products in the fields of chemical industry,
agriculture, pharmaceuticals and numerous materials [1]. One of
the core missions of heterogeneous catalysis is to design and
develop high-performance catalysts. As an important type of het-
erogeneous catalysts, metal catalysts have been extensively applied
in many important reactions such as partial oxidation and selec-
tive hydrogenation [2,3]. Particularly, with the rapid development
of nanoscience and nanotechnology, both academia and industry
communities have shown increasing interest in controlling metal
nanoparticles for enhancing the catalytic activity, tuning the selec-
tivity and even obtaining unique chemo- and stereo-selectivity for
important catalytic processes [4–7].
Gold was once considered to be catalytically inactive for a
long time. However, since the 1980s there has been increasing
interest in gold catalysis [8,9]. It was the first time for gold to
become a high-performance catalyst, in sharp contrast to the ear-
lier reports about no or poor activity of gold. Since then, much
work has further explored the highly dispersed Au catalysts for
a range of chemical transformations, such as selective oxidations,
selective hydrogenations, C–C coupling reactions, and the addi- Scheme 1. Schematic Diagram of the Size-Focusing Methodology. Reproduced with
tion of multiple C C bonds [10–14]. The Au nanocatalysts are permission from [18]. Copyright 2016 American Chemical Society.

usually obtained by conventional preparation methods, including

the deposition-precipitation, co-precipitation and sol precipitation
methods [8,10]. Such nanocatalysts are apparently more or less
polydispersed in size and have no uniform composition in the case
of bimetallic catalysts, not to mention the lack of well-defined
structures, which result in major difficulties in identifying the cat-
alytic sites and determining the structure-property relationships of
Au catalysts. Thus, designing novel Au nanocatalysts with precise
particle size and well-defined structure is highly desirable in order
to solve the above issues.
Controlled synthesis of nanoparticles with precise numbers of
atoms has long been a major dream of nanochemists. In recent
years major breakthroughs have been made in preparing atomically
precise nanoparticles with diameters from subnanometer to a few
nanometers, which are often called nanoclusters [15–19]. Among
them, controllable synthesis of atomically precise Au nanoclusters
was first attained [15–18]. These Au nanoclusters with excellent
size control provide new opportunities for investigating the precise
size-dependent catalytic properties and also obtaining structural
insights into catalytic mechanisms. Besides, due to the ultra-small
size (less than 2 nm), these Au nanoclusters exhibit unique and
even unexpected properties that are not observed in bulk gold and
conventional gold nanoparticles. Finally, the precise atomic struc-
tures of more nanoclusters of gold and bimetals have also been
determined by X-ray crystallography [17,18,20], which allows for
precise correlation of the structure with the catalytic property of
nanoclusters. Herein, we review the recent progress in the cataly-
sis by homogold and gold-based bimetal nanoclusters in the past
five years. We first introduce the synthetic strategies briefly, and
then focus on the catalytic properties of homogold and gold-based
bimetal nanoclusters reported in the last few years. Finally, we pro-
vide some perspectives of metal nanoclusters for future catalysis
research.
Synthetic breakthroughs of gold and bimetallic
nanoclusters
Homogold nanoclusters
Gold-thiol chemistry was traced back to the 1980s due to the
research on thiol self-assembled monolayers on bulk gold surfaces
[21]. Subsequently, thiol was employed in the preparation and
functionalization of gold nanoparticles [22,23]. However, it was not
until 2005 that ultra-small gold clusters (∼1 nm) of a series of sizes
protected by glutathione were for the first time isolated from a
mixture by the Tsukuda group [24]. The gel electrophoresis method,
however, did not offer large quantities of nanoclusters and the yield
of each size was low, thus bulk solution synthesis with size con-
trol remained to be developed. The Jin group made major progress
in 2007 [25] and established two systematic methodologies in the
following years, including the size-focusing methodology [26] and
the ligand exchange-induced size/structure transformation (LEIST)
methodology [27]. The rational synthesis of atomically precise Au
nanoclusters with molecular purity and high yield can be accom-
plished by these methodologies, which provides opportunities for
investigating the structure, properties and applications of Au nan-
oclusters.
Size-focusing methodology
An ideal synthesis is to achieve one-sized Au nanoclusters
in high yield. In 2007, Zhu et al. achieved for the first time
Au25 (SCH2 CH2 Ph)18 nanoclusters in molecular purity and high
yield through kinetic control [25]. Particularly, it was discovered
that the kinetic formation for the Au(I)-SR intermediate was crit-
ical for the high yield of Au25 (SCH2 CH2 Ph)18 . Subsequently, the
size-focusing method was extended to successful syntheses of
Au38 (SR)24 [28,29], Au64 (SR)32 [30], Au99 (SR)42 [31], Au144 (SR)60
[32], Au246 (SR)80 [17] and Au333 (SR)79 [33]. It has since become
a universal method for rational synthesis of atomically precise
Aun (SR)m nanoclusters in molecular purity, which are also effective
for preparing both the organic-soluble nanoclusters and aque-
ous nanoclusters [34,35]. In general, this methodology involves
two steps: the kinetic control and the thermodynamic selection
(Scheme 1) [18]. The key point lies in the effective control of the
size distribution of the initial Aux (SR)y product prior to the size-
focusing step. A too-broad size range would lead to more than one
stable size in the final product after the size-focusing and their iso-
lation would be difficult. Controlling the Aux (SR)y mixture largely
depends on the kinetic control. Some important factors are such as
the temperature, solvent and reactant ratio. For more details of the
methodology, the reader is referred to ref [26].

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Scheme 2. Reaction pathway for conversion of Au38 (PET)24 to Au36 (TBBT)24 . Stage I, ligand exchange; II, structure distortion; III, disproportionation; IV, size focusing.
Reproduced with permission from [37]. Copyright 2013 American Chemical Society.

Fig. 1. X-ray structure of Au25 (SCH2 CH2 Ph)18 (magenta, gold atoms of the core; cyan, gold atoms of the shell (or surface)). (A) ball stick view; (B) space-filling view. Adapted
with permission from ref [41]. Copyright 2008 American Chemical Society.

LEIST methodology
This methodology, which is based on the size-focusing one,
employed the Aun (SR)m nanoclusters as the starting material for
reaction with sufficiently different ligands than the surface lig-
ands on Aun (SR)m to create new sizes of Au nanoclusters [27].
A number of new Au nanoclusters have been prepared by this
methodology, which are otherwise difficult to synthesize through
the size-focusing methodology. Taking Au36 (TBBT)24 (where TBBT
represents 4-tert-butylbenzenethiolate) as an example (Scheme 2)
[36,37]. Starting with molecularly pure Au38 (SCH2 CH2 Ph)24 , ligand
exchange reaction with a large excess of TBBT under thermal condi-
tions (∼80 ◦ C) resulted in the formation of Au36 (TBBT)24 in greater
than 90% yield and molecular purity. Two key points affecting
the LEIST process were observed. First, the high ratio of incom-
ing TBBT to the original PET (where PET represents SCH2 CH2 Ph)
on the nanoclusters is required. Second, the thermal process is
required to overcome the energy barrier between different stable
sizes (i.e. Au38 vs Au36 ). On the basis of the method, the conversions
of Au25 (SR)18 to Au28 (SR )20 [38], Au25 (SR)18 to Au20 (SR )16 [39],
Au38 (SR)24 to Au36 (SR )24 [36,37], and Au144 (SR)60 to Au133 (SR )52
[40] were also accomplished.
Further, the aforementioned methodologies have led to suc-
cessful crystallization and structure determination of many Au
nanoclusters [18]. Due to the extensive application of Au25 (SR)18
in many fields, its structure and electronic properties are briefly
discussed herein [41]. The Au25 (SR)18 (where R = CH2 CH2 Ph) con-
tained a 13-atom Au13 icosahedral core (Fig. 1A, magenta portion)
and a Au12 (SR)18 shell (Fig. 1A, cyan and yellow) [41,42]. Due to
the unique structure, the shell Au atoms and even some of the
icosahedral core Au atoms are accessible to reactant molecules,
thereby providing potential catalytic sites (Fig. 1B). The electronic
structure of Au25 (SR)18 showed discrete energy levels caused by
the quantum-size effect [41]. The molecular orbitals can be divided
into the core orbitals (primarily contributed by Au13 ) and the shell
orbitals s (primarily contributed by Au12 (SR)18 ), thus exhibiting the
geometric and electronic core-shell structures [41,43]. It was also
proven that the ligand type has no effect on the geometric struc-
ture [44], evidenced by the same optical absorption spectrum of
Au25 (SR)18 regardless the −R groups of the thiolates [45,46]. The
crystal structures of other Au nanoclusters have been reviewed
elsewhere [18].
Gold-based bimetal nanoclusters
A common synthetic strategy for gold-based bimetal nan-
oclusters is similar to that of gold nanoclusters except the
use of combined gold and heterometal salts as the precursor
[18,20,47–53]. Generally, two kinds of heteroatom substitution
behavior have been found: (1) a specific number of foreign atoms
(e.g. Pd or Pt) can be incorporated into gold nanocluster irrespective

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Fig. 2. X-ray crystal structure of the Au25-x Agx (SR)18 . The X-ray crystallography averaged composition is Au5.6 Ag19.4 (SC6 H11 )18 . (a) The 13-atom icosahedral alloy core. (b)
Six [–SR–Au(Ag)–SR–Ag–SR–] dimeric staples with different occupancy of Au/Ag atoms. (c) Total structure of Au25-x Agx (SR)18 . Magenta: Au, gray: Ag/Au, yellow: S, grey: C.
Reproduced with permission from ref [54]. Copyright 2016 Royal Society of Chemistry.

Fig. 3. (A) Reaction temperature dependence of CO conversion over Au25 (SR)18 /MOx catalysts. Pretreatment condition: N2 at room temperature (rt) for 0.5 h. Reaction
conditions: GHSV = 7500 mL g−1 h−1 , catalyst = 0.1 g. (B) Reaction temperature dependence of CO conversion over Au25 (SR)18 /CeO2 catalyst after different pretreatments.
GHSV = 7500 mL g−1 h−1 . Adapted with permission from ref [65]. Copyright 2012 American Chemical Society.

of the salt precursor ratio; (2) a range of heteroatom substitution
(e.g. Ag or Cu) depending on the initial precursor ratio but the total
number of metal atoms in the parent cluster is preserved [20]. For
Pd or Pt doping, experimental and theoretical works show that
Pd or Pt is located in the center of Au25 (SR)18 clusters [20]. For
Ag or Cu substitution, here we illustrate the case of heteroatom
substitution in Au25 (SR)18 since such bimetallic clusters have been
investigated for catalysis recently. It is noted that Ag or Cu substi-
tution in Au25 (SR)18 clusters with a specific number has not been
obtained yet [20]. The similarities between Ag and Au readily lead
to alloy clusters with a distribution of Ag atoms rather than a spe-
cific number. As an example, the total structure of Agx Au25-x (SR)18
(where R = C6 H11 ) is shown in Fig. 2 [54], in which the central atom
remains to be gold, whereas the icosahedral shell is composed of Au
and Ag (Fig. 2a), and heavy doping can also lead to Ag distribution
into the external staple motifs (Fig. 2b).
Besides the common method of mixed metal salt precursors for
bimetallic nanocluster synthesis, a novel metal-exchange method
using gold nanoclusters as the template for bimetallic nanoclus-
ters with atomic precision have also been reported [54–58], in
which heterometal-thiolate complexes react with the presynthe-
sized homogold nanoclusters. In addition, Pradeep and coworkers
have also reported an inter-cluster reaction method for obtaining
bimetallic nanoclusters [59].
Catalytic properties
Homogold nanoclusters
Oxidation
CO oxidation. CO oxidation is the model reaction most widely stud-
ied due to its simplicity and significance [60]. More importantly, it
is the reaction that the superior activity of gold was discovered for
the first time [8], so it has been employed extensively as a proto-
typical reaction for understanding gold catalysis [60]. Besides, CO
oxidation can also readily reveal the ligand effect on the property of
Au nanoclusters. Therefore we first focus on CO oxidation catalyzed
by gold nanoclusters.
It is worth noting some results of bare gold cluster catalysts.
Valden et al. [61] found that layered Au nanoclusters with thickness
smaller than 3 atoms were very active for low temperature CO oxi-
dation. Herzing et al. [62] investigated several iron oxide-supported
gold catalysts by aberration-corrected scanning transmission elec-
tron microscopy and observed 0.5 nm bilayer Au clusters containing
about 10 gold atoms were responsible for the high activity for CO
oxidation. Besides, experimental and theoretical results showed
that partial electron transfer from the support surface to the gold
cluster and oxygen-vacancy/F-center defects of MgO accounted for
the unusual catalytic activity of Au8 /MgO in the low-temperature
oxidation of CO [63,64]. The aforementioned tailoring of the prop-
erties of small metal clusters by altering the cluster size and its
support has proven to be quite useful in design of nanostructured
materials for catalytic applications.
The advent of Au nanoclusters with uniform size and well-
defined structure has provided fundamental insights into Au
catalysis. For instance, the support-dependent activity of
thiolate-ligated Au25 (SR)18 (where R = CH2 CH2 Ph) nanoclus-
ters for CO oxidation reaction was observed in the order:
Au25 (SR)18 /TiO2 < Au25 (SR)18 /Fe3 O4 < Au25 (SR)18 /CeO2 (Fig. 3A)
[65]. Surprisingly, Au25 (SR)18 /TiO2 had no catalytic activity even
if the temperature was up to 200 ◦ C. This is significantly different
from conventional Au/TiO2 , which was considered to be one of the
most active catalysts [8]. The catalytic activity of Au25 (SR)18 /CeO2
was found to be related to the pretreatment atmosphere and

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Fig. 4. (A) Amount of CO2 production during the copulse (black squares) and sequential pulses (red squares) of CO and O2 at 80 ◦ C on the Au25 (SR)18 /CeO2 rod sample
pretreated at 150 ◦ C in O2 along with their ratios (blue squares). (B) Percentage of MvK and L−H reaction pathways on Au25 (SR)18 /CeO2 rod catalysts pretreated at different
temperatures with O2 . Reproduced with permission from ref [70]. Copyright 2014 American Chemical Society.
temperature. The O2 pretreatment at 150 ◦ C markedly increased
the activity, but higher temperatures (above the thiolate desorp-
tion temperature) led to no further increase in activity (Fig. 3B)
[65]. In addition, the thermal pretreatment in N2 had no signif-
icant effect on its activity. Characterizations of Au25 (SR)18 /CeO2
indicated that thiolate ligands remained on Au nanoclusters after
the pretreatment at 150 ◦ C. In others words, CO oxidation can
be catalyzed by intact Au25 (SR)18 supported on CeO2 , which is
also reported by the latest work [66]. These showed that O2
pretreatment was closely relevant to the product of active oxygen
species on CeO2 instead of ligand removal of Au nanoclusters. The
catalytic properties of Au38 (SR)24 [67,68] and Au144 (SR)60 [69] for
CO oxidation have also been evaluated.
It is noteworthy that thiolate ligands have a substantial influ-
ence on catalytic activity of gold nanoclusters for CO oxidation
[65–69]. For instance, the intact Au38 (SCH2 CH2 Ph)18 /CeO2 exhib-
ited low catalytic activity, while the Au catalysts after partial
removal of thiolates showed better activity. Surprisingly, complete
removal of ligands led to a decrease in activity [64]. To disclose the
role of thiolate ligands, Wu et al. [70] meticulously investigated the
catalytic property of Au25 (SR)18 /CeO2 -rod (where R = SCH2 CH2 Ph)
for CO oxidation reaction by a series of experiments and DFT cal-
culations. The intact Au25 (SR)18 /CeO2 -rod catalyst had no activity
due to the lack of exposed Au atoms for CO adsorption. As the thi-
olate ligands were partially removed, starting from the interface
between Au nanoclusters and CeO2 at 150 ◦ C and above, CO was
favorably adsorbed on exposed Au atoms and then reacted with
the lattice oxygen of CeO2 to generate CO2 . As ligands removal pro-
gressed to the top surface sites of Au nanoclusters, CO and O2 were
also co-adsorbed on exposed Au atoms and then led to CO oxi-
dation. Isotopic labeling and pulse experiments showed that CO
oxidation proceeded predominantly at the interfaces between the
ligands, Au, and CeO2 via Mar-van Krevelen mechanism by utiliz-
ing the lattice oxygen of the oxide support (Fig. 4). Activation of
CO and O2 at the exposed Au atoms made minor contributions to
CO oxidation via Langmuir-Hinshelwood mechanism (Fig. 4). The
mechanism of CO oxidation by Au25 (SR)18 /CeO2 -rod catalysts was
proposed (Scheme 3). It showed that the thiolate ligand acted as
a double-edged sword for gold nanoclusters in CO oxidation: On
one hand they retain the structural integrity of Au nanoclusters,
but they also block the catalytic sites for CO oxidation. The results
clearly provided the fundamental understanding of how the ligands
affected the catalysis of Au nanoclusters in CO oxidation.
Benzyl alcohol oxidation. Au nanoclusters are also an efficient
catalyst for the selective oxidation of alcohols. For example, poly(N-
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5
vinyl-2-pyrrolidone) (PVP) protected Au nanoclusters of less than
1.5 nm were found to exhibit superior activity for the aerobic oxida-
tion of alcohols compared with larger size Au nanoclusters [71]. The
catalytically active Au nanoclusters were revealed to be negatively
charged via electron donation from PVP. The increasing electronic
density of Au nanocluster with decreasing size led to the enhanced
catalytic activity. The electron was transferred from the anionic Au
nanoclusters to LUMO of O2 to generate superoxo or peroxo-like
species and subsequently facilitated the oxidation of alcohols. The
plausible mechanism was illustrated in Scheme 4 [71]. It is worth
nothing that PVP not only acts as a stabilizer but also modifies the
electronic structure of Au clusters, which are different from the role
of the thiolate ligand in Au25 (SR)18 /CeO2 [70].
Yoskamtorn et al. [72] synthesized Au25 (SC12 H25 )18 on hierar-
chically porous carbon sheets by the removal of ligands through
calcination under vacuum. The as-prepared catalysts were eval-
uated for the selective oxidation of benzyl alcohol. Interestingly,
the selectivity for benzaldehyde was significantly improved when
the amount of residual thiolates on Au nanoclusters increased,
although the activity was reduced, as shown in Fig. 5. TEM dis-
closed that the size of Au nanoclusters remained almost unchanged
after thermal pretreatment and EXAFS characterization indicated
that Au nanoclusters with residual thiolates was more positively
charged than the bare Au due to electron transfer from Au to S.
Therefore, the presence of thiolates on Au nanoclusters not only
reduced the oxidation of benzyl alcohol to benzaldehyde by elec-
tron withdrawal but also suppressed the esterification reaction
by site isolation effect. It confirmed that the catalytic proper-
ties of metal nanoclusters can be tuned through modulating their
electronic structure and the steric environment by chemical mod-
ification.
Subsequently, the water-soluble glutathione protected gold
nanoclusters supported on M3 Al-layered double hydroxide (LDH,
M = Mg, Ni, Co) were prepared, calcined and applied for the
oxidation of alcohols without basic additives [73]. AuNCs/Mg3 Al-
LDH-0.23 (where 0.23 is the gold content, similar hereafter) showed
far higher properties in the oxidation of 1-phenylethanol than
Au/Mg3 Al-LDH by the classical deposition-precipitation method.
The activity of AuNCs/Ni3 Al-LDH-0.22 and AuNCs/Co3 Al-LDH-0.20
could be further enhanced by the stronger synergy between
Au and the supports containing transition metal cations [73,74].
Phosphine-capped Au nanoclusters as the precursor for preparing
ultra-small and uniform Au nanocatalysts were also reported [75].
Styrene oxidation. The size evolution of ultra-small Au nanoclus-
ters provided a good opportunity for the selective oxidation of
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Scheme 3. CO Oxidation Mechanism on Intact, Partially and Fully Dethiolated Au25 (SR)18 /CeO2 Rod Catalysts. Reproduced with permission from [70]. Copyright 2014
American Chemical Society.

Scheme 4. The proposed mechanism for the activation of O2 by Au:PVP. Reproduced with permission from ref [71]. Copyright 2009 American Chemical Society.

Fig. 5. Selectivity and conversion during benzyl alcohol oxidation over various supported Au25 NCs. Reproduced with permission from ref [72]. Copyright 2014 American
Chemical Society.

styrene, which is an important chemical transformation process.
Turner et al. [76] found that triphenylphosphane stabilized Au55
(not well-defined) clusters were an efficient and robust catalyst
for the selective oxidation of styrene by O2 . The particle size of
Au55 /BN and Au55 /SiO2 remained unchanged (∼1.4 nm), and both
catalysts achieved about 20% conversion of styrene and 80% selec-
tivity to benzaldehyde. In particular, only Au nanoparticles with
less than 2 nm in size were found to have activity, while tradi-
tional supported gold nanoparticles larger than 2 nm were inactive,
indicating a sharp size threshold in catalytic activity. The observed
activity originated from the modified electronic structure of Au
entities and the weak adsorption of styrene on Au nanoclusters.
Zhu et al. [77,78] investigated the catalytic activity of
Aun (SR)m /SiO2 and Aun (SR)m /HAP nanoclusters (R = CH2 CH2 Ph,
n = 25, 38, 144) in styrene oxidation under three different oxidation
conditions: (a) tert-butyl hydroperoxide (TBHP) as the oxidant, (b)
TBHP as the initiator and O2 as the oxidant, and (c) O2 as the oxidant.
The activity of three systems showed in the order: (a) > (b) > (c).
Using O2 as the oxidant, Au25 (SR)18 showed the highest activity
among the different sizes and it was related to its particularly effi-
cient activation of O2 . No drastic size effect was found when TBHP
was used as the oxidant because of its facile activation by Au, while
O2 activation is harder. In comparison with SiO2 , HAP had the role
to stabilize Au nanoclusters and then promoted the activity. The
calcined catalysts exhibited higher activity than the counterparts
without calcination. The proposed mechanism for the selective oxi-
dation of styrene catalyzed by Au25 (SR)18 is illustrated in Fig. 6
[77].

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Fig. 6. Proposed mechanism of selective oxidation of styrene catalyzed by a Au25 (SR)18 cluster. The thiolate ligands are not shown. (Dark gray: Au atoms of the core, light
gray: Au atoms of the shell). Reproduced with permission from ref [77]. Copyright 2010 Wiley-VCH.
Although it is confirmed that small amounts of P and Cl had
no negative effect on the activity of supported Au55 nanoclus-
ters [76], thiolate ligands were generally considered to restrict the
accessibility of reactants to Au atoms and thereby deactivate Au
nanoclusters [77,79]. Therefore, Liu et al. [79] removed the thiolate
ligands through calcination at 300 ◦ C and studied the activity of the
as-obtained Au25 /HAP. The ligand-off Au nanoclusters preserved
the cluster size with a flattened morphology. 100% conversion of
styrene and 92% yield of styrene oxide were obtained. It was noted
that the high performance was attributed to the choice of solvent
(benzene) and oxidant (TBHP).
Thermal removal of ligands is a destructive approach, which
may lead to the sintering of Au nanoclusters. Two strategies for mild
removal of thiolate ligands were developed recently, i.e. reductive
deprotection and oxidative stripping [80,81]. Mercaptopropyl-
modified SBA-15 was employed as the support to obtain the
supported Au25 (SCH2 CH2 Ph)18 and Au144 (SCH2 CH2 Ph)60 catalysts.
Controlled removal of thiolate ligands was accomplished by treat-
ing the above catalysts with the different concentration NaBH4
solution (Fig. 7) [80]. Characterizations showed that the Au size
remained almost no change with the efficient removal of lig-
ands. 100% conversion and 100% selectivity for benzaldehyde were
achieved in the oxidation of styrene over such catalysts, in com-
parison with the performances of the untreated catalysts with 30%
conversion and 100% selectivity for benzaldehyde [80].
Another strategy for ligand removal has been developed by
treatment with TBHP or H2 O2 as the oxidant [81]. The thiolate lig-
ands were removed after oxidation, while the size and intergity of
Au nanoclusters had almost no change. The as-prepared Au clusters
exhibited an enhanced activity in the selective oxidaiton of styrene.
Of note, 4-mercaptobenzoic acid was not removed by this method
[81].
Both the reduction and oxidation methods allow the efficient
removal of ligands from the metal nanoclusters, which promotes
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7
the understanding of the ligand effect on the catalytic activity and
the design of Au catalysts with high performance.
Cyclohexane oxidation. Selective oxidation of cyclohexane to cyclo-
hexanone and cyclohexanol is one of the most important reactions,
as the resulting compounds serve as the essential intermediates in
the nylon-related chemical industry. Liu et al. explored the cat-
alytic performances of Au10 (SG)10 , Au18 (SG)14 , Au25 (SG)18 , and
Au39 (SG)24 (where SG represents glutathionate) nanocluster sup-
ported on hydroxyapatite(HAP) as the precursors for the aerobic
oxidation of cyclohexane [82]. TEM revealed no appreciable aggre-
gation of Au nanoclusters after the calcination due to the strong
interaction between Au and PO4 3− moieties of HAP. Dramatic size-
dependent activity of Au nanoclusters was observed, in which Au39
had the highest activity with 14.9% of cyclohexane conversion and
99% selectivity to cyclohexanone and cyclohexanol (Fig. 8) [82]. The
activity of supported Au nanoclusters was related with the support
material and the treatment temperature [83].
Hydrogenation
Selective hydrogenation is one of the most important reactions
heavily applied in industry. The reaction is generally catalyzed by
VIII group metals such as Ni, Ru, Pd and Pt [1]. The pioneering work
by Bond and co-workers revealed that supported gold nanoparti-
cles exhibited excellent selectivity in the gas-phase hydrogenation
of 1, 3-butadiene to butane [84]. Despite the impressive results,
gold nanoparticle catalysts for selective hydrogenation was mostly
ignored in subsequent years until the supported gold nanoparti-
cles with the size of 3–5 nm was found to promote the selective
hydrogenation of carbonyl or nitro groups in the presence of other
reducible functional groups at high conversion [85,86]. Nowadays
gold nanoparticles [87] and Aun (SR)m nanoclusters [15] have also
been demonstrated to be capable of catalyzing the selective hydro-
genation reactions.
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Fig. 7. Illustration of enhanced catalytic activity in selective oxidation reaction with supported ultrasmall organothiolate-protected AuNP catalysts by mild chemical stripping
of their surface ligands. Reproduced with permission from ref [80]. Copyright 2014 Wiley-VCH.
Fig. 8. TOF values as a function of the cluster size n in the selective oxidation of
cyclohexane. Reproduced with permission from ref [82]. Copyright 2011 American
Chemical Society.
Hydrogenation of carbonyl compounds. Chemoselective hydrogena-
tion of unsaturated carbonyl compounds while maintaining the
reducible C C group is an important kind of reaction because the
resulting unsaturated alcohols are valuable chemical intermediates
in the production of fragrances, pharmaceuticals and agrichemicals
[88] (Scheme 5). Although gold catalysts exhibited high selec-
tivity for unsaturated alcohols, 100% chemoselectivity cannot be
achieved by using the conventional gold nanoparticles and bare
gold nanoclusters catalyst [86,89].
Zhu et al. [90–92] obtained 100% selectivity for unsaturated
alcohols in the hydrogenation of a range of ␣, ␤-unsaturated
ketones (except crotonaldehyde) over Au25 (SR)18 catalysts. For
instance, using supported Au25 (SCH2 CH2 Ph)18 as the catalyst, ben-
zalacetone in a mixture of toluene and ethanol was stirred at 0 ◦ C for
3 h under 1 atm H2 , and the complete selectivity was obtained with
40% conversion of benzalzcetone [91]. The catalyst showed only
a slight decrease in activity with 100% selectivity for unsaturated
alcohols after six circles. The proposed mechanism for the reac-
tion process is illustrated in Scheme 6 [91]. The electron-deficient
Au12 shell is considered to provide sites for H2 adsorption and dis-
sociation. After dissociation, the H atom is adsorbed in a bridge
position bonding to two low-coordinated gold atom. The electron-
rich Au13 core favors adsorption of C O via the interaction with the
Au atom and the O in carbonyl group, with partial electron transfer
from Au13 to the O atom. Subsequently, the weakly nucleophilic
attacks the activated C O group, thereby leading to the production
of unsaturated alcohols.
In addition to thiolate ligated gold nanoclusters, other ligands
like tert-butyl(naphthalen-1-yl)phosphine oxide ligated gold clus-
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Scheme 6. The proposed mechanism of the chemoselective hydrogenation of ␣,␤-
unsaturated ketone to unsaturated alcohol catalyzed by Au25 (SR)18 nanoparticles.
The thiolate ligands are not shown. Dark grey: Au atoms of the core; light gray:
Au atoms of the shell. Reproduced with permission from ref [91]. Copyright 2010
Wiley-VCH.
ters were also prepared and found to show high activity and nearly
complete selectivity in the hydrogenation of ␣, ␤-unsaturated alde-
hydes under mild conditions [93]. These studies suggested that
the complete selectivity for unsaturated alcohols can be attained
by employing ligand-on gold nanoclusters as the catalyst. Fur-
thermore, the mechanism of 100% selective hydrogenation of ␣,
␤-unsaturated ketones to unsaturated alcohols on Au25 (SR)18 have
been theoretically unraveled by first-principles density functional
calculations [94].
When the aldehyde group and nitro group co-exist in
the same substrate, the chemoselective hydrogenation of nitro
group was always preferred over conventional gold nanopar-
ticles and bare gold nanocluster catalysts [86,87,89]. However,
Li et al. [95] reported that water-soluble Aun (SR)m (where
SG represents glutathionate) nanoclusters could achieve 100%
selective hydrogenation of aldehyde group with moderate con-
version in the homogeneous chemoselective hydrogenation of
4-nitrobenzaldehyde in water. A drastic size dependence and lig-
and steric effect were observed. Larger gold nanoclusters or the less
bulky ligand protected gold nanoclusters are found to have higher
catalytic activity (Fig. 9).
Furthermore, using hydrophobic thiolate ligand-on gold nan-
oclusters supported on oxides like Au99 (SPh)42 /CeO2 as the
catalyst, about 93% conversion of 4-nitrobenzaldehyde and 100%
selectivity for 4-nitrobenzyl alcohol were attained in the presence
of pyridine using water as the solvent and H2 as the hydro-
gen source [96]. The catalyst also showed excellent durability
(no loss of catalytic reactivity after three circles) and good ver-
satility for a range of substrates with aldehyde and nitro groups
(Table 1). The complete chemoselective hydrogenation of the alde-
hyde group is remarkable, which is in sharp contrast with the
previously reported chemoselective hydrogenation of the nitro
group against the aldehyde group by conventional gold nanoparti-
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Scheme 5. Chemoselective reductions of unsaturated carbonyl compounds to unsaturated alcohols.

Table 1
Chemoselective Hydrogenation of a Range of Substrates with Nitro and Aldehyde Groups Using Au99 (SPh)42 /CeO2 as the Catalyst.

a
Reproduced with permission from ref [96]. Copyright 2014 American Chemical Society.

cles and bare gold nanocluster catalysts [86,89]. These new, unique
catalytic properties were possibly related to the selective adsorp-
tion of the aldehyde group onto the surface gold atoms of Aun (SR)m
nanoclusters [96]. More details on the mechanism require future
experimental and theoretical works.
Subsequently, Li et al. [97] found that the addition of a Lewis
acid markedly enhanced the catalytic performance of Au25 (SR)18
(where R = CH2 CH2 Ph) for the chemoselective hydrogenation of 4-
nitrobenzaldehyde and its derivatives in the presence of base under
mild conditions. Among the Lewis acids tested, Co2+ yielded the
best catalytic property. The conversion was significantly improved
to 90.1% at 50 ◦ C when Co(OAc)2 was added, while only 13.4% con-
version was obtained without a Lewis acid. The above catalytic
system also showed good recyclability with no appreciable loss of
catalytic reactivity after three circles. In the presence of Lewis acid,
new species Au24 (SR)17 was generated, which originated from the
adsorption of Mz+ onto “-SR-”of Au25 (SR)18 and the resulting step-
wise detachment of an “Au-SR” unit. This led to the exposure of
Au13 -core to reactants and possibly provided the catalytic sites.
Besides, Lewis acids bound on the Au13 -core possibly functioned
as the different active sites for the hydrogenation reactions [97].
In gold nanoparticle and nanocluster catalyzed hydrogenation
reactions, pyridine was usually added and acted as an efficient
additive for activation of reactants [96–99], but it is toxic and
unfriendly even at low concentrations. Recently, the diphenyl-2-
pyridylphosphine ligand protected gold clusters were designed
and found to have excellent properties in the chemoselective
hydrogenation of nitrobenzyldehyde to nitrobenzal alcohol in the
absence of pyridine [99]. It avoided the use of toxic pyridine by
introducing the pyridine group close to gold surface to assist the
reactant activation.
Hydrogenation of nitro compounds. Aniline and its derivatives are
important chemical intermediates for pharmaceuticals, dyes, agro-

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Fig. 9. Hydrogenation of 4-Nitrobenzaldehyde Catalyzed by Unsupported Aqueous
Soluble Aun (SG)m Nanoclusters as Catalysts. Reproduced with permission from ref
[95]. Copyright 2014 American Chemical Society.
chemicals and polymers. They are generally produced through the
hydrogenation of nitro compounds over metal catalysts [100]. Due
to good catalytic activity and unparalleled selectivity, gold nanocat-
alysts have attracted intensive attention [85–87]. It was reported
that ligand-on gold nanoclusters were catalytically active for the
reduction of 4-nitrophenol to 4-aminophenol by NaBH4 [101–103].
It also showed that Au25 (SR)18 retained the structural integrity
during the catalytic process and was stable and recyclable [102].
Moreover, the nature of ligand had a significant impact on the
catalytic property of gold nanoclusters [103]. The shorter chain thi-
Fig. 10. HAADF-STEM images of the catalysts: a) Au25 /ZnAl-HT; b) Au25 /ZnAl-HT-300; c–d) Au25 /ZnAl-HT-600. Reproduced with permission from ref [106]. Copyright 2017
Wiley-VCH.
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olate ligated Au25 (SR)18 displayed better accessibility and activity
than those bearing a longer chain. The aromatic ligands increased
the accessibility of Au25 (SR)18 and thus led to an enhanced activity
[103]. Recent studies indicated that ligands modulated the catalytic
active-sites of gold nanoclusters and then directed the reaction
pathway for the hydrogenation of 4-nitrophenol [104]. It suggested
again that ligand engineering can be an efficient tool for tuning the
catalytic property of gold nanoclusters.
However, other studies showed that thiolate protected Au nan-
oclusters supported on oxides and HAP were inactive for the
hydrogenation of nitro group with H2 [105]. After the removal
of thiolates, both bared Au25 /HAP and Au/TiO2 displayed good
activity for the hydrogenation of nitrobenzene to aniline, in agree-
ment with the earlier literature [86,89]. Especially, gold catalysts
with well-controlled size (2.0 nm) were obtained through the load-
ing of cysteine-capped Au25 nanoclusters onto ZnAl-Hydrotalcite
(ZnAl-HT) and then the calcination of the resulting precatalysts
(300–500 ◦ C) (Fig. 10). It was unprecedented that the catalyst
exhibited excellent selectivity (>98%) to 3-vinylaniline at complete
conversion of 3-nitrostyrene over broad reaction duration and tem-
perature windows (Fig. 11) [106]. No loss of catalytic activity and
selectivity was found after five circles for 3-nitrostyrene hydro-
genation. The outstanding properties possibly depend on the small
size of Au and unique nature of oxide support derived from ZnAl-HT
[106].
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Table 2
Homocoupling of aryl iodides using the Au25 (SR)18 /CeO2 catalyst a.

Fig. 11. The conversion, selectivity, and TOF values (line) over the Au25 /ZnAl-HT
catalysts calcined at different temperatures. The TOF value was measured below 20%
conversion.Reproduced with permission from ref [106]. Copyright 2017 Wiley-VCH.

a
Adapted with permission from ref [111]. Copyright 2012 Royal Society of Chem-
Semihydrogenation of alkynes. The semihydrogenation of alkynes is istry.

a valued approach to alkenes, which are useful building blocks of

fine chemicals [107]. Gold nanoparticles were reported to be an
efficient catalyst for the reaction [87,108]. Li et al. [109] inves-
tigated the catalytic properties of the spherical Au25 (SR)18 and
rod-shaped Au25( PPh3 )10 (C CPh)5 X2 nanoclusters supported on
oxides for sehihydrogenation of terminal alkynes to alkenes. About
100% conversion of the alkynes with complete selectivity to alkene
products was achieved under mild conditions. The open triangular
Au3 facet on the spherical Au25 (SR)18 (R = CH2 CH2 Ph) nanoclus-
ters and the waist sites of the rod-shaped Au25 (PPh3 )10 (C CPh)5 X2
(X = Br/Cl) nanoclusters were considered to be the active sites
in the semihydrogenation process. The mechnism of the semi-
hydrogenation process was proposed [109], see Fig. 12. Besides,
the semihydrogenation of the internal alkynes did not proceed
over the ligand-on nanoclusters, while they can be catalyzed by
the ligand-off nanoclusters. Combining with FT-IR spectrocopy, a
unique activation pathway of terminal alkynes was identified. The
terminal alkynes followed a deprotonation activation pathway by a
Rı́-C C-[Aun Lm ] (where L represents the ligands on the cluster) and
it was in contrast with the case of conventional gold nanoparticles
catalysts.
Carbon–Carbon coupling reaction
The carbon–carbon coupling reactions are the mostly used
approaches to prepare biaryl or propargylamines, which are valu-
able synthetic building blocks in the manufacture of biologically
active compounds, natural products, and pharmaceutical organic
compounds [110]. Gold nanoparticle catalysts have been employed
in the carbon–carbon coupling reactions [110]. Likewise, gold nan-
oclusters have good catalytic activity [111–116]. For example, Li
et al. found that the Au25 (SR)18 /CeO2 (R = CH2 CH2 Ph) nanocluster
catalyst exhibited high activity in the homocoupling of aryl iodides
(Table 2) [111]. It also showed good stability since only a slight
decrease in catalytic activity was observed after five circles (within
5%). The positively charged surface Au atoms of Au25 (SR)18 were
considered to be catalytic sites for activating iodobenzene, while
the electron-rich, redox-active Au13 kernel participated the elec-
tron transfer process in the catalytic reaction.
Au25 (SR)18 /CeO2 also achieved about 96% conversion
of iodoanisole and 88% selectivity for 1-methoxy-4-(2-
phenylethynyl)benzene in the sonogashira cross-coupling reaction
between iodobenzene and phenylacetylene [112]. DFT calcina-

Fig. 12. Proposed mechanism for the ligand-on Au25 nanocluster catalyzed semihydrogenation of terminal alkynes to alkenes using H2 (20 bar). Left panel: Au25 (SR)18
nanocluster. Right panel: Au25 (PPh3 )10 (C CPh)5 X2 (X = Cl, Br) nanocluster was drawn according to the crystal structure of the Au25 (PPh3 )10 (C CPh)5 X2 nanocluster. Color
code: Au, green; S, yellow; C, gray; P, pink; X, cyan. Hydrogen atoms are omitted for clarity. The areas marked in orange are the Au3 active sites (left panel) and the waist
active sites (right panel) in the alkyne semihydrogenation reaction, respectively. Reproduced with permission from ref [109]. Copyright 2014 American Chemical Society.
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

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Fig. 13. (a) Top view of one of the two open facets of Au25 (SCH2 CH2 Ph)18 clusters where three external gold atoms are exposed; the other facet is on the back side. (b)
Side view of the two facets which are at top and bottom. (c) Top view and (d) side view of the co-adsorption of phenylacetylene and iodobenzene on the surface of the
Au25 (CH2 CH2 Ph)18 clusters. Au, yellow; S, blue; C, gray; H, white; I, green. Reproduced with permission from ref [112]. Copyright 2013 Elsevier.

tions suggested that iodobenzene and phenylacetylene together

adsorbed on the open gold atoms of Au12 shell: iodobenzene
adsorbed one gold atom, phenylacetylene adsorbed the second
gold atom, and the C CH group of phenylacetylene and the −I
group of iodobenzene pointed towards the third atom (Fig. 13).
The co-adsorption configuration, in which its adsorption energy is
about the sum of the individual adsorption energies, favored the
coupling between reactants and led to the product. The supported
Au25 (SR)18 was also applied in the Suzuki crossing coupling
reaction [113].
Besides, Au nanoclusters such as Au38 (SR)24 (where
R = CH2 CH2 Ph) were found to be an efficient catalyst in the
three-component coupling of an aldehyde, an alkyne and an
amine to synthesize propargylamines [114]. Oxides as the support
made no contribution to the catalytic performance of Au38 (SR)24 .
Furthermore, ligand-off Au38 /CeO2 had a lower catalytic activity
than ligand-on Au38 (SR)24 nanoclusters (Fig. 14), in comparison Fig. 14. Conversion of benzaldehyde, phenylacetylene and piperidine as a function
with the traditional view that the more bare surface atoms exhib- of reaction time over Au38 (SCH2 CH2 Ph)24 , Au38 (SCH2 CH2 Ph)24 /CeO2 , and ligand-off
Au38 /CeO2 catalysts. Reproduced with permission from ref [114]. Copyright 2016
ited higher catalytic property. It demonstrated the importance of
Royal Society of Chemistry.
the entire structure of Au38 (SR)24 nanoclusters, indicating that
the synergistic effect of the electron-deficient Au␦+ (0 < ␦+ < 1)
shell and the electron-rich Au23 core was critical for the catalytic Au25 (SCH2 CH2 Ph)18 and Au25 (S-Nap)18 clusters have the same
reaction. structural framework, although a slight expansion of the Au13
Recently, Li et al. [116] prepared an aromatic-thiolate- kernel induced by the aromatic-thiolate was observed in Au25 (S-
protected gold nanoclusters Au25 (S-Nap)18 (where S-Nap = 1- Nap)18 nanoclusters. More importantly, the catalytic activity and
naphthalenethiolate) and observed that aromatic ligands had selectivity of Au25 (SR)18 clusters (R = Nap, Ph, CH2 CH2 Ph, n-
distinct effects on the electronic and catalytic properties. Both C6 H13 ) are largely influenced by the chemical nature of thiolate
ligands in the Ullmann heterocoupling reaction. Among them,

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Fig. 15. The photocatalytic mechanisms of Au25 (SR)18 /TiO2 under visible light irra-
diation. Reproduced with permission from ref [118]. Copyright 2013 American
Chemical Society.
Au25 (S-Nap)18 /CeO2 gave the best catalytic performances with 91%
conversion and 82% selectivity for the heterocoupling product. It
showed the effective of ligand engineering for tailoring the catalytic
properties of nanoclusters.
Photocatalysis
Thiolate-protected gold nanoclusters possess molecule-like,
discrete electronic transitions in optical properties (such as visible
light absorption), which are very different from the optical prop-
erties of larger nanoparticles [117]. What is more, these properties
can be tuned through the exact atom number, composition and lig-
ands, so they hold great potential for applications in the fields of
photocatalysis, energy and chemical sensors [117–124]. Here we
discuss briefly their applications in photocatalysis.
Yu et al. [118] reported that loading of Au25 (SR)18
(R = CH2 CH2 Ph) nanoclusters onto TiO2 gave rise to a 1.6 times
increase in the visible light photocatalytic activity for the degra-
dation of methyl orange. However, Au25 (SR)18 /TiO2 offered no
drastic increase in photocatalytic activity under UV light irradiation
compared with plain TiO2 . The enhanced photocatalytic activ-
ity may be related to quantum confinement within Au25 (SR)18
nanoclusters with a HOMO-LUMO gap of Eg ∼ 1.3 eV, which is
similar to a small-band-gap semiconductor. Under the visible
light irradiation, the photogenerated electrons from Au25 (SR)18
were transferred to the conduction band of TiO2 , thereby leading
to the electron-hole efficient separation. The produced hole can
further generate hydroxyl radicals, which are responsible for the
decomposition of the dye. Singlet oxygen (1 O2 ), generated from
Au25 (SR)18 nanoclusters under visible light, also participated in
the decomposition of the dye. Two mechanisms were proposed
to explain the significantly promoted photocatalytic activity of
Au25 (SR)18 /TiO2 under visible light (Fig. 15) [118].
Sakai et al. found that Au25 (SG)18 clusters (where SG represents
glutathionate) was efficiently adsorbed onto the surface of TiO2 via
the carboxylic group in GSH. The photogenerated electrons from
Au25 (SG)18 clusters were injected into the TiO2 conduction band
with 60% internal quantum yield under visible light irradiation
[119]. The photocatalytic material was used in the photooxidation
of phenol derivates and ferrocyanide, and reduction of Ag+ , Cu2+
and dissolved oxygen [119,120].
Subsequently, Chen et al. [121] prepared
Au25 (PPh3 )10 Cl2 (SC3 H6 SiO3 )5 /TiO2 by hydrolysis of
Au25 (PPh3 )10 Cl2 (SC3 H6 SiO3 )5 in the presence of P25 support.
The as-obtained catalyst exhibited good photocatalytic properties
for the selective oxidation of amines to imines under visible light.
The turnover frequency of methylbenzylamine oxidation was
1522 h−1 , which is considerably higher than that of conventional
gold catalysts (Table 3). The enhanced activity was related to its
Please cite this article in press as: J. Zhao, R. Jin, Heterogeneous catalysis by gold and gold-based bimetal nanoclusters, Nano Today
(2018), https://doi.org/10.1016/j.nantod.2017.12.009
13
Fig. 16. Time course of water splitting over (red) Au25 –BaLa4 Ti4 O15 photocata-
lyst (0.1 wt% Au) prepared by the present method and (black) AuNP–BaLa4 Ti4 O15
photocatalyst (0.5 wt% Au) prepared by the conventional photodeposition method.
Reproduced with permission from ref [124]. Copyright 2013 Royal Society of Chem-
istry. (For interpretation of the references to colour in this figure legend, the reader
is referred to the web version of this article.)
unique electronic structure and framework. It indicates that visible
light photocatalytic selective organic transformations proceed
efficiently over gold nanoclusters, which is also confirmed by the
recent literature [122].
Besides, gold nanoclusters also have an enormous potential
application in clean hydrogen production [123,124]. For instance,
Negishi et al. [124] investigated glutathione-protected Au25 clus-
ters (1.2 ± 0.3 nm) onto BaLa4 Ti4 O15 as precatalysts for water
splitting. The photocatalytic property of as-prepared material was
determined to be 2.6 times higher than that of BaLa4 Ti4 O15 loaded
with larger gold nanoparticles (10–30 nm) by the conventional
photo-deposition method (Fig. 16). The enhanced activity was asso-
ciated with the increased surface area-to-mass ratio and specific
electronic structure of ultra-small gold clusters.
Gold-based bimetal nanoclusters
In the subnanometer regime, every atom can exert a substan-
tial effect on the catalytic properties, thus precise control over the
size of a nanocluster has been proven to be an efficient approach
for tuning the activity and/or the selectivity in a catalytic process
[8,61,62,82,95]. Besides, heteroatom substitution in homometal
nanoclusters also provides good opportunities to tune the catalytic
properties of nanoclusters at the atomic level [20]. Herein, we show
the catalytic applications of the heteroatom-doped Au25 (SR)18 clus-
ters.
Oxidation
CO oxidation. Li et al. [125] investigated Ag and Cu
doped Au25 (SR)18 (where R = CH2 CH2 Ph) nanoclusters sup-
ported on CeO2 as catalysts for CO oxidation. These
catalysts exhibited the catalytic activity in the order of
Cux Au25-x (SR)18 > Au25 (SR)18 > Agx Au25-x (SR)18 . The exposed
metal atoms (Au, Ag and Cu) in the clusters were considered to
be the catalytic active sites. The observed activity is related to
the ability of CO adsorption and metal exchange between the
icosahedral core and the staple motif of the clusters at higher
temperature. This example demonstrates the effectiveness of
tuning the catalytic property of gold nanoclusters by heteroatom
doping at the atomic level. Further research is needed to explore
the details of CO oxidation pathway and how the amount of doping
may influence the activity.
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14 J. Zhao, R. Jin / Nano Today xxx (2018) xxx–xxx

Table 3
Photocatalytic oxidation of a range of amine substrates over [Au25 ]/P25 catalyst a.

a
Adapted with permission from ref [121]. Copyright 2017 American Chemical Society.

Fig. 17. Catalytic Performances of Au25 /CNT and Pd1 Au24 /CNT for Benzyl Alcohol
Oxidation. Reproduced with permission from ref [126]. Copyright 2012 American
Chemical Society.

Benzyl alcohol oxidation. Compared with homogold Au25 nanoclus-

ters, single-palladium doped Pd1 Au24 catalysts [126] displayed Fig. 18. Catalytic performances of Au34 Ag28 (PhC C)34 supported on XC-72 in the
hydrolytic oxidation of triethylsilane before and after thermal treatment at dif-
higher activity in the benzyl alcohol oxidation reaction (Fig. 17).
ferent temperatures. Reproduced with permission from ref [133]. Copyright 2016
The former gave a 22% conversion of benzyl alcohol, while the lat- American Chemical Society.
ter offered a significantly higher conversion (74%). TEM imaging
showed that both clusters had a similar size in the range 1.1–1.2 nm.
Styrene oxidation. It was reported that the heteroatom doped gold
The remarkably enhanced activity was ascribed to the modulation
nanoclusters as the catalyst efficiently facilitated the transfor-
of the electronic structure by electron transfer from Pd to Au [126]
mation of styrene oxidation and/or tuned the selectivity for the
(Fig. 18).
products [129–131]. The Pt1 Au24 (SR)18 /TiO2 catalyst was found
Cd1 Au24 (SR)18 nanoclusters were prepared by the metal
to exhibit higher catalytic performance than the homogold Au25
exchange method and characterized by x-ray single crystal diffrac-
nanocluster in the selective oxidation of styrene [129]. The con-
tion [55]. The Cd1 Au24 (SR)18 nanoclusters inherits the same
version of styrene and the selectivity for benzaldehyde were
core-shell structure as that of Au25 (SR)18 and the Cd is in the center
90.8% and 89.9% over the doped clusters catalysts, compared
of the 13-atom icosahedral core. It was found that the Cd dop-
with 58.9% styrene conversion and 54.0% benzaldehyde selec-
ing significantly enhanced the stability of the nanocluster under
tivity over the Au25 catalyst, respectively [129]. In recent work,
O2 environment [127]. More importantly, the Cd1 Au24 (SR)18 nan-
Wang et al. synthesized 70-atom Ag46 Au24 bimetallic nanoclus-
oclusters supported on CNT exhibited higher activity than the
ters, which consisted of a 40-atom bimetallic Ag2 @Au18 @Ag20 core
corresponding homogold catalyst in the selective oxidation of
protected by a Ag24 Au6 (SR)32 shell [130]. The bimetallic nanoclus-
benzyl alcohol (63% and 33% conversion of benzyl alcohol, respec-
ters showed higher selectivity for benzaldehyde (96.3%) than that
tively), but both catalysts exhibited similar selectivity for the
of homogold Au25 (SR)18 nanoclusters (66.4% only), but with sim-
benzaldehyde product [127]. Besides, the Cu doping into Au nan-
ilar conversion of styrene in the styrene oxidation reaction. The
oclusters was reported to enhance the catalytic property in the
surface composition and structure of the bimetallic nanoclusters
selective oxidation of benzyl alcohol [128].
were responsible for the enhanced selectivity of products [130].
Although the detailed mechanism for how the heteroatom doping

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affects the catlaytic properties remians unclear, the above cases
have certainly benefited the understanding of the structure-related
catlaytic property of bimetallic gold nanoclusters at an unprece-
dented level.
Crotyl alcohol oxidation. Bimetallic AuPd nanoclusters supported
on alumina were obtained from Au25 (SR)18 nanoclusters through
activation with mild thermal treatment or LiBH4 treatment fol-
lowed by selective deposition of Pd via ascorbic acid reduction
[132]. Characterizations showed that AuPd nanoclusters derived
from LiBH4 -activation had a small avarage particle size of 2.5 nm
with Au core-Pd shell structure. The bimetallic AuPd nanoclusters
exhibited higher catalytic activity and selectivity for crotonalde-
hyde than the homometallic Pd catalyst in the liquid oxidation
of crotyl alcohol, the turnover number (TON) of the former being
about 10–20 times higher than that of the latter, while pure Au cat-
alysts were catalytically inert under the investigated conditions.
The promoted catalytic activity of AuPd nanoclusters was ascribed
to the strong electronic interaction between Au and Pd and their
small particles size [132]. It provided a novel and efficient method
to design gold-based bimetallic nanoclusters using ligand-on gold
nanoclusters as a precursor.
Organosilane oxdation. Recently, Wang et al. obtained alkynyl-
protected intermetallic nanocluster Au34 Ag28 (PhC C)34 by co-
reduction of gold and silver salts with tert-butylamine borane
complex [133]. The clusters displayed a four-concentric-shell
Ag@Au17 @Ag27 @Au17 structure, and the exterior 17 gold atoms
were linearly coordinated with phenylalkynyl ligands to form
staple-like “PhC C−Au−C CPh” motifs. Ligand-on AuAg nanoclus-
ters supported on carbon were found to exhibit far higher activity
than those with ligand-off for the hydrolytic oxidation of triethylsi-
lane (Fig. 18) [133]. It showed the important role of surface ligands
in promoting the catalytic reaction. Future research should focus on
the fundamental understanding of the intriguing promotion effect.
Selective hydrogenation
Zhu et al. [134] found that the Pd1 Au24 (SR)18 /Fe2 O3
(R = CH2 CH2 Ph) catalyst exhibited similar catalytic activity
compared to that of Au25 (SR)18 /Fe2 O3 in selective hydrogenation
of benzalacetone (42% conversion vs 40%). It indicated that the
central palladium atom exerted no significant effect on the cat-
alytic hydrogenation activity of homogold nanoclusters, while it
contributed to their remarkably increase in the catalytic oxidation
activity [126].
Besides, the nature of the ligand can significantly influence
the catalytic hydrogenation performance of bimetallic gold nan-
oclusters. For instance, Yang et al. [128] found that the presence
of the small size 2-pyridylthiolate on the surface of Au13 Cu8
nanoclusters still exposed the active sites of Au atoms to small
molecules, and then the hydrogenation of 4-nitrophenol to 4-
aminophenol by NaBH4 efficiently took place in the presence of
Au13 Cu8 nanoclusters. In comparison, the larger size ligands such
as triphenylphosphine and 4-tert-butylbenzenethiol on the sur-
face of Au13 Cu2 and Au13 Cu4 nanoclusters completely blocked the
Au active sites, so the above hydrogenation did not proceed over
Au13 Cu2 or Au13 Cu4 nanoclusters.
Carbon–Carbon coupling reaction
Li et al. [135] found that gold-based bimetallic Mx Au25−x (SR)18
(M = Pt, Ag and Cu; R = CH2 CH2 Ph) nanoclusters (supported on
TiO2 ) displayed distinct activity and selectivity for the Sonogashira
cross-coupling product in the carbon–carbon coupling reaction of
p-iodoanisole and phenylacetylene. Au25 (SR)18 gave 79.5% conver-
sion of p-iodoanisole and 65.7% selectivilty for the Sonogashira
cross-coupling product. Using Agx Au25−x (SR)18 and Pt1 Au24 (SR)18
Please cite this article in press as: J. Zhao, R. Jin, Heterogeneous catalysis by gold and gold-based bimetal nanoclusters, Nano Today
(2018), https://doi.org/10.1016/j.nantod.2017.12.009
15
as the catalysts, 83.0% and 48.5% conversion were obtained with
54.4% and 67.2% selectivity for the Sonogashira cross-coupling
product, respectively. However, Cux Au25−x (SR)18 preferred the
Ullmann homo-coupling reaction of p-iodoanisole, and so 52.4%
conversion of p-iodoanisole and only 28.3% selectivilty for the Sono-
gashira cross-coupling product were attained. Characterizations
and DFT calculations showed that the catalytic activity was largely
determined by the electronic effects in the bimetallic nanoclusters’
13-atom core, and that the selectivity was dominated by the type of
atoms on the Mx Au12−x shell (M = Ag, Cu and Au) in the bimetallic
nanocluster catalysts [135].
Recently, a novel Au26 Cd5 nanocluster has been prepared using
the thiolate-protected Au25 nanocluster as a precursor by peeling
and doping [136]. The Au26 Cd5 nanocluster catalyst was found to
exhibit high catalytic activity and good reusability in the three-
component coupling reaction of alkynes, aldehydes and amines.
In contrast, homogold Au25 clusters showed no catalytic activity
under the conditions. The high catalytic activity was related to the
cooperation between doping cadmium atoms and the neighboring
gold atoms in bimetallic nanoclusters [136]. These works provide
insight into the fundamental relationship between the composi-
tions of bimetallic nanoclusters and their catalytic properties, and
will stimulate more future research on the fine tuning of nan-
oclusters’ compositions and structures to improve their catalytic
performance.
Future perspective
Nanoclusters with a precise number of atoms display unique
and even unexpected properties. Herein, we have illustrated the
case of gold nanoclusters as the catalyst. The synthetic method-
ologies [26,27] could be extended to the cases of Pd, Pt and other
metals. Undoubtedly, the controlled synthesis of metal nanoclus-
ters with atomic precision will offer new exciting opportunities for
achieving fundamental insight into nanocatalysis and correlation
of the catalytic properties with their atomic level structure.
Due to ultra-small size, the properties of nanoclusters are very
sensitive to the number of atoms in the clusters. Significant changes
in the properties may occur when even a single atom is added or
removed [137,138], and such catalysts are particularly useful in
revealing the dependence on the structure and electronic proper-
ties of nanoclusters [139]. Future work should further explore such
unique properties.
Bimetallic nanoclusters hold great potential in catalysis. Distinct
improvements in catalytic properties of bimetallic gold nanoclus-
ters compared to homogold ones were observed when another
element is introduced [125–132,135,136]. It is an efficient method
for fine tuning of the catalytic property of Au nanoclusters. As
respect to Ag or Cu doped gold nanoclusters, pure Agx Aum–x (SR)m
or Cux Aun–x (SR)m clusters with a specific value of x should be sep-
arated and obtained, and then the precise correlation the doping
amount and sites in heteroatom doped nanoclusters with the cat-
alytic property should be explored in future work.
Ligand not only retains the structural integrity of gold
nanoclusters but also imposes the unnegligible effect on the cat-
alytic properties [65–72,93,96–98,106,109,114,116,133,140,141].
Ligand-protected gold nanoclusters have been found to be cat-
alytically active for many reactions, and they even exhibit unique
property in some cases [95–97,109,114,116,133], but the detailed
role of ligand remains unclear in many reactions and should be
studied carefully in future research. Based on the reported results,
ligand engineering is an efficient approach to tailoring the catalytic
property of gold nanoclusters.
Besides, ligand is usually considered to be an adverse factor
in catalysis as it prevents reactants from accessing the catalytic
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16 J. Zhao, R. Jin / Nano Today xxx (2018) xxx–xxx
sites. So the removal of ligand is often required to obtain high per-
formance on gold nanocluster catalysts. Several methods for the
removal of ligand have been developed, and the size of the as-
prepared gold catalysts was reported to be preserved in many cases
[65,79–82,142]. Of note, TEM can characterize whether the size of
gold nanocluster is preserved, but the precise composition (such
as the number of gold atoms) of nanoclusters was not identified
[81,82,143]. Determining the gold atom number of supported gold
nanoclusters is still a challenge because of the limitations of the
current characterization tools. Thus, characterization of the precise
size of supported nanoclusters should be explored in future study.
Although ligand-on or ligand-off gold nanoclusters have been
found to exhibit high catalytic properties in many chemical reac-
tions, detailed catalytic mechanisms have not been revealed yet
in many cases. Identifying the catalytic sites and exploring the
reaction mechanisms should be pursued in future research. It is
noted that the structure of gold nanoclusters may be dynamic in
some harsh reactions (e.g. under high temperatures); thus, moni-
toring the structure under the reaction conditions is important for
understanding the mechanism. More efforts should be focused on
utilizing in-situ or operando techniques, such as DRIFT-IR, XANES
and EXAFS [70,144,145], to determine how the characteristics
of metal nanoclusters change under working conditions. Besides,
applying gold nanoclusters in other important reactions such as
propylene epoxidation should also be considered in future study.
Acknowledgements
J.Z. acknowledges the financial support from the National Nat-
ural Science Foundation of China (21576248) and a research fund
from the doctoral program of Zhengzhou University of Light Indus-
try (2014BSJJ007). R.J. acknowledges the funding support from the
U.S. National Science Foundation (DMREF-0903225).
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