Catalytic Hydrogenation by Noble Metals Nanocrystals

Catalysis
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Catalytic hydrogenation by noble-metal

nanocrystals with well-defined facets: a review
Cite this: Catal. Sci. Technol., 2015,
5, 2532 Wanting Zang,a Guozhu Li,*ab Li Wangab and Xiangwen Zhangab
Recent studies with better catalytic models show the structure sensitivity of noble-metals for catalytic
hydrogenation. The size and shape of noble-metal nanocrystals have a great impact on their reaction
performance in hydrogenation. Essentially, the exposed crystal planes, which primarily determine the mor-
phology of a nanocrystal, tremendously affect its catalytic behavior. Therefore, many new methods involv-
Received 6th December 2014, ing controllable nucleation and growth processes have been developed to prepare uniform noble-metal
Accepted 1st March 2015
nanocrystals with tunable sizes and shapes for catalytic hydrogenation. This paper presents a brief overview
DOI: 10.1039/c4cy01619j
of the activity and selectivity of noble-metal nanocrystals with well-defined facets in the field of catalytic
hydrogenation. High activity and controllable selectivity in hydrogenation have been achieved based on the
www.rsc.org/catalysis shaped noble-metal nanocatalysts.
1. Introduction structure sensitivity of hydrogenation reactions has been

studied in more recent studies using better catalytic models.
Catalytic hydrogenation is considered to be one of the most For instance, Somorjai’s group found that the crystal facets
important reactions in the pharmaceutical and specialty of single-crystal Pt surfaces1 and Pt nanoparticles (NPs)2
chemical industry. It refers to a large group of addition reac- strongly affected the selectivity of benzene hydrogenation.
tions of hydrogen to unsaturated bonds, which involves Herein, this review will give a brief summary of recent studies
simple addition reactions between hydrogen and alkenes, on hydrogenation catalyzed by noble-metal nanocrystals
alkynes, aldehydes, aromatic nitro-compounds and some un- (NCs) with well-defined facets.
saturated organics in the presence of relevant catalysts. The From a catalysis perspective, activity and selectivity have
always been two great challenges. In catalytic reactions, the
a
Key Laboratory for Green Chemical Technology of Ministry of Education, School structure of the nanocrystal catalyst is important for the activ-
of Chemical Engineering and Technology, Tianjin University, Tianjin 300072,
ity and selectivity and must be determined. Noble-metals,
China. E-mail: gzli@tju.edu.cn
b
Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), which were regarded as potential catalysts for hydrogenation,
Tianjin 300072, China have been studied extensively with promising prospects. A
Wanting Zang studied chemical Prof. Guozhu Li received his

engineering and technology at Ph.D. degree in chemical engi-
Beijing University of Chemical neering from Tianjin University
Technology, China and received in 2010. After working as a
her bachelor degree in 2013 then researcher for 2 years at core
was admitted to the master R&D of Dow chemical company
study by Tianjin University with- (Shanghai), he became an assis-
out examination. She presently tant professor of Tianjin Univer-
pursues her master degree under sity and was promoted as associ-
the supervision of Professor ated professor in 2014. He was
Xiangwen Zhang. Currently she a visiting scholar from 2007 to
focuses on the systematic investi- 2009 at the department of chem-
Wanting Zang gation of catalytic hydrogenation Guozhu Li ical engineering, University of
by both noble-metal and several Washington. His research inter-
non-noble metal nanocrystals. ests include catalytic hydrogenation, heterogeneous catalysis and
nanotechnology.
2532 | Catal. Sci. Technol., 2015, 5, 2532–2553 This journal is © The Royal Society of Chemistry 2015
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way of optimizing their performances and recyclability must For sub-10 nm NCs, the smaller the size the higher the sur-
be discerned because of their low abundance in nature. face to volume ratio will be. This means that the active site
Firstly, bulk single crystals of noble-metal catalysts with will be enhanced sharply as the particle size decreases.
certain facets exposed had been studied for surface chemical In essence, the arrangement of surface atoms and the
reactions (e.g., hydrogenation). For a molecular understand- exposed type of crystallographic planes play an important
ing of the catalytic process, extending reaction studies to role in the activity and selectivity of catalytic hydrogenation.
structure-sensitive reactions for which activity and selectivity In the following, we will focus on published examples of cata-
change with facets was carried out.3 Benzene hydrogenation lytic hydrogenation on shaped noble-metal nanocatalysts.
is an ideal reaction for such studies for its facet sensitivity, Many nanomaterials have been prepared and used in cata-
which has been investigated on single-crystalline Pt sur- lytic hydrogenation, not all of them can be evaluated as suit-
faces.1,4,5 Moreover, both experimental6–8 and theoretical9 able catalysts for hydrogenation. Recent studies of the synthe-
studies on the selective catalytic hydrogenation of CO sis of shaped noble-metal NCs and their use for catalytic
bonds in unsaturated aldehydes have suggested that such hydrogenation are summarized in Table 1.
reactions may be promoted by close-packed (111) surfaces.
The results provide the reference state needed to probe and 2. The synthesis of noble-metal NCs
compare more complex nanocrystal surfaces which are more
closely related to what is used industrially.
with well-defined facets for
The research mentioned above highlights the separate hydrogenation
roles that particle size and particle shape may play in defin-
It is generally recognized that the wet-chemical approach is a
ing the activity and selectivity in those catalytic processes.
practical strategy to synthesize uniform noble-metal NCs.
Accordingly, independent control of particle size and shape
There are two major stages (nucleation and growth) and four
(exposed facets) during catalyst manufacture may offer ave-
related components referring to: metal ion precursor, capping
nues for the design of good nanocatalysts. A lot of effort has
agent, solvent, and reducing agent, as described in Scheme 1.
been put into investigating the size effects of nano-sized
noble-metal catalysts. Recently, with the development of
nanotechnology, noble-metal nanocatalysts with well-defined 2.1 Precursor
facets have been prepared. In this way, the facet effects Metal salts, e.g., metal acetylacetonate, nitrate, halide
of these nanocatalysts on reaction activity and selectivity have (Cl−, Br−, I−), and acetate, are usually chosen to provide the
been investigated. For example, Somorjai’s group10 has stud- source of the corresponding noble metals. Of course potas-
ied much about the molecular factors affecting turnover sium chloroplatinate ĲK2PtCl6) can be substituted by chloro-
rates and catalytic selectivity including surface structure, platinic acid ĲH2PtCl6) in the synthesis, but the state of the
adsorbate-induced restructuring, reaction intermediates, sur- metal ion will affect the shape of the obtained metal nano-
face composition and so on. crystal. For instance, using K2PtCl4 as the precursor can pro-
Virtual progress in size/shape control of noble-metal NCs duce Pt nanocubes, while tetrahedral Pt NCs will be obtained
has been made by numerous scientific workers.11–14 But the from H2PtCl6.20,22,24 A complex of the metal precursor will
use of these shaped NCs as catalysts is still under way.11,15–17 form under some conditions. As in the presence of ĳPdCl4]2−
It is considered that the size of the noble-metal NCs affects and C14TABr, it has been reported that ĳPdCl4]2− ions interact
the activity while the multiple shapes, especially the well- with C14TABr to form the stoichiometric metal-surfactant
defined facets, make a contribution to the reaction selectivity. complex ĲC14TA)2PdBr4. The complex of ĲC14TA)2PtBr4 is
Prof. Li Wang received her Ph.D. Prof. Xiangwen Zhang received

degree in chemical engineering his B.S. and M.S. degrees in
from Tianjin University in 1999. chemical engineering from Tian-
After working as post-doctor for jin University in 1984 and 1987,
2 years at School of Chemical respectively, under the supervi-
Engineering, she became an sion of Prof. Hongfang Chen,
associated professor of Tianjin and then became a research
University and was promoted to assistant at the School of Chemi-
full professor in 2008. She was a cal Engineering. He received his
visiting scholar from 2006 to Ph.D. in 2003 and become a full
2007 at Institute of Chemical professor from 2006. His
engineering, RWTH Aachen Uni- research interests include fuel
Li Wang versity. Her research interests Xiangwen Zhang processing technology and reac-
include petrochemical technol- tion engineering.
ogy, reaction engineering and separation processes.
This journal is © The Royal Society of Chemistry 2015 Catal. Sci. Technol., 2015, 5, 2532–2553 | 2533
Table 1 Synthesis of faceted noble-metal NCs for hydrogenation
Reducing Noble
Minireview
Precursor Capping agent Solvent agent metal Facets Effects Hydrogenation of Reference
K2PtCl4 TTABa Water NaBH4, H2 Pt (111) Both cyclohexane and cyclohexene were formed Benzene 2
on (111)
NaBH4 (100) Only cyclohexane was produced on (100)
ĲNH4)2PtĲIV)Cl6 and PVPb and TTABa Ethylene Ethylene Pt (100) Ethylene hydrogenation rates were facet Ethylene 18
ĲNH4)2PtĲII)Cl4) glycol glycol, PVPb independent
(111) For pyrrole hydrogenation, the (100) facets Pyrrole
enhanced ring-opening ability and showed a
higher selectivity to n-butylamine as compared to
(111) facets.
H2PtCl6 3-HBc Water Ascorbic acid, Pt (100) Free-standing Pt NPs with (111) facets are more 4-Nitrophenol 19
NaBH4 active than those with (100) facets.
2534 | Catal. Sci. Technol., 2015, 5, 2532–2553

TAd (111) When loaded on SBA-15, Pt NPs with (100) facets
are more active than those with (111) facets.
H2PtCl6 PVPb Water H2 Pt (111) For particles with (111) facets, a dramatic switch Carbon–carbon 20
in selectivity of cis-to-trans and trans-to-cis double bond
conversions is seen at ≈500 K. cis-trans
K2PtCl4 SPAe Water H2 (100) The rates of both cis-to-trans and trans-to-cis isomerization
conversions are comparable for particles with of 2-butenes in H2
(100) facets,
K2PtCl4 ĲC14TA)2PtBr4 C14TABr f Water NaBH4, H2, Pt (111) and Pt NPs with (100) and (111) have comparable Ethylene 21
low pH (100) catalytic activity.
NaBH4 high (100)
pH
Ascorbic acid Porous Porous Pt NPs showed superior activity to those of
particle (111) and (100).
K2PtCl4 PAAg , NaI Water Argon, H2 Pt (100) TOF increases with increasing the ratio of the Olefin 22
H2PtCl6 PAAg Water H2 (111) (100) facet to (111) facet, (100) > (100) and (111)
K2PtCl4 PAAg Water H2 (111) and > (111) for stilbene hydrogenation
(100) Corner and edge affect minor influence for
hydrogenation activity.
H2PtCl6 CTABh Water, argon NaBH4 Pt (100) (111) facet is much more selective for partial Buta-1,3-diene 23
atmosphere NaBH4 with (111) hydrogenation of buta-1,3-diene to butenes.
H2
H2PtCl6 SPAe Water, Ar H2 Pt (111) PtĲ100)/C>PtĲ111)/C>Pt/C α,β unsaturated 24
K2PtCl4 bubbling (100) Pt(111)/C showed higher selectivity for aldehydes
unsaturated alcohol
PtĲacac)2 HCl/methanol OAMk FeĲCO)5 Pt (111) Excellent enantioselectivity up to 78%. α-Ketoesters 25
Effect of support and chiral modifiers
K2PtCl4 TTABa Water NaBH4 Pt (100) with Similar to the Pt single crystal, Ethylene 26
some (111) PtĲ100)/mesoporous silica core–shell NPs have an
order of magnitude higher TOF than the Pt@CoO
yolk–shell NPs
K2PdCl4 ĲK2PtCl4) R5 peptide Water NaBH4 Pt or Pd NA Effect of the metal/peptide ratio and the metallic Allyl alcohol 27
composition of the nanostructures
H2PdCl4 CO Anhydrous CO Pd (111) Surface-clean Pd nanosheets > PVP-capped Styrene 28
DMFi nanosheets
Na2PdCl4 PVPb , KBr Water PVP Pd (100) The removal of PVP by UVO treatment increased Acetylene 29
the activity 4-fold
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Table 1 (continued)
Reducing Noble
HAuCl4· ODA j Au, Pd, Pt (111) In toluene Activity: Pt nanorod aggregates (89%) > Citral 30
4H2OPdCl2H2PtCl6· AuPt alloy NPs (55%) > Pt NPs (111) (44%)
6H2O Selectivity to unsaturated alcohols: AuPt alloy NPs
35% > Pt nanorods 4% = Pt (111) monometallic
NPs 4%
In scCO2 Activity: Pt NPs (111) (82%) > Pt
nanorod aggregates (79%) > AuPt alloy NPs (46%)
Selectivity to undaturated alcohols: AuPt alloy NPs

56% > Pt nanorods 7% > Pt (111) monometallic
NPs 4%
Na2PdCl4 CTABh Water NaBH4 sodium Pd (100), (111), The activity and selectivity for butane increased 1,3-Butadiene 31 and
ascorbate nanorodĲ100) from (100) facets to (111) facets. 32
Pd nanorods with (100) lateral planes are highly

selective for butenes.
PdCl2 or H2PtCl6 PVPb, polyvinyl Water, NA Pd (100) Nanocubes with (100) facets are more active than Styrene oxide and 33
alcohol, ethanol spherical NPs. 2-butyne-1,4-diol
polymethylvinyl
ether
H2PdCl4 Ethyl alcohol, Water, Gamma ray Sphere
PVPb isopropanol
Na2PdCl4 and Pd PVPb, citric acid Water Citric acid Pd (111) Semihydrogenation of 2-methyl-3-butyn-2-ol 2-Methyl-3-butyn-2-ol 34
nanocubes (MBY) to (MBE) occurred preferentially at the
Na2PdCl4 PVPb, L-ascorbic Water PVPb (100) plane sites regardless of Pd (111) and Pd (100).
acid, KBr, KCl Overhydrogenation occurred mainly at the edge
sites
bisĲacetonitrile) Oleic acid, OAMk Toluene H2 Pd (113) Greatly improved catalytic performance because of Nitrobenzene 35
palladium dichloride the high surface area and high-index facets
Pd Electron beam evaporation Pd (111) and 1,3-butadiene hydrogenation is particle size 1,3-Butadiene 36
(100) independent. Well-faceted Pd NPs with (111) and
(100) ≥ 4 nm behave like bulk Pd(111).
relatively unstable OAMk OAMk Methanol Rh (111) 4.9 nm tetrahedral Rh NPs with (111) facets show Anthracene 37
compoundsl 5.8- and 109-times higher activity than spherical
NPs and commercial Rh/C.
RhCl3 TTABa Ethylene PVPb Rh (100) Rh nanocubes with (100) facets fully hydrogenated Pyrrole 38
glycol pyrrole to n-butane and ammonia between 303
and 343 K. The TOF did not strongly depend on
temperature.
RhĲacac)3 PVPb 1,4- 1,4-Butanediol Rh (111) Preliminary catalytic tests reveal that Rh Ethylene 39
Butanediol nanopolygons exposing (111) surfaces are active
for ethylene hydrogenation.
PtĲacac)2 and PVPb, benzoic acid Benzylalcohol Benzylalcohol, PtxNi1−x(0 < (111) & (100) The catalyst activity is positively related to the Benzalacetone, 40
NiĲacac)2 solvothermal x <1) percentage of exposed (111) facets. Bimetallic styrene, and
150 °C nanoalloy catalysts are more active than their nitrobenzene
monometallic counterparts. PVP as the capping
agent does not affect the catalyst's solubility,
activity, and recyclability.
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Catal. Sci. Technol., 2015, 5, 2532–2553 | 2535

Table 1 (continued)
Reducing Noble
Minireview
PtĲacac)2 and PVPb, Water, benzyl Benzylalcohol, Pt3Ni@M (111) The catalytic performance can be significantly Nitrobenzene 41
NiĲacac)2 dimethylglyoxime, alcohol solvothermal M = Au, Ag, improved by sophisticated decoration with the
HAuCl4Ĵ4H2O acetic acid, 150 °C Cu, Rh third metal.
RhĲacac)3, CuĲacac)2, benzoic acid
AgNO3, and FeĲacac)3
PtĲacac)2 and OAmk OAmk CO Pt3Co (111) (100) Amine-capped truncated octahedral Pt3Co-alloy α, β-Unsaturated 42
CoĲacac)2 NPs can be used as efficient catalysts for selective aldehydes (cinnam-
hydrogenation of α, β-unsaturated aldehydes aldehyde and citral)
Na2PdCl4, K2PtCl4 NaI, PVPb DMFi PVPb PtxPd1−x (100) Effect of shape and composition ĲPt51Pd49 Nitrobenzene 43
Na2PdCl4, K2PtCl4 NaCl, PVPb DMFi PVPb PtxPd1−x (111) highest) the (100)-facet-enclosed PtPd NCs
demonstrate higher activity than those with (111)
facets.
2536 | Catal. Sci. Technol., 2015, 5, 2532–2553

PtĲacac)2 NiĲacac)2 Oleic acid OAMk CO Pt3NiPtPtNi (100) The influence of replacing Pt atoms with Ni atoms α,β Unsaturated 44
Diphenyl ether (111) on (100) facet is more significant in the selectivity aldehydes
for hydrogenation than that on (111). Both (cinnamaldehyde)
monometallic Pt and bimetallic Pt–Ni
nanooctahedrons gave similar results. Selective
hydrogenation towards CO: Pt3NiĲ100)>
PtNiĲ100)>PtĲ100).
CoĲac)2Ĵ4H2O Oleic acid OAMk WĲCO)6 Pt3Co (410) (510) Concave structure with high-index crystal facets Styrene 45
PtĲacac)2 (610) exhibits enhanced catalytic activity in comparison
with low-indexed surface terminated Pt3Co nano-
cubes with (100) facets of similar size.
GaCl3, PdĲacac)2 THFm THFm LiHBEt3 GaPd NA The overall activity in comparison with the Acetylene 46
GaPd2 ground bulk material is enhanced by a factor of
90 in the case of GaPd2 and more than 180 in the
case of GaPd.
a
TTAB - tetradecyltrimethylammonium bromide. b PVP - polyvinylpyrrolidone. c 3-HB - 3-hydroxybutyric acid. d TA - tropic acid. e SPA - sodium polyacrylate. f C14TABr - tetra-
decyltrimethylammonium bromide. g PAA - polyacrylate. h CTAB - bromurede cetyltrimethylammonium. i DMF - N,N-dimethylformamide. j ODA - octadecylamine. k OAM - oleylamine.
l m
. THF - tetrahydrofuran.
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Recently, Zheng’s group28 synthesized ultrathin palladium

nanosheets (1.8 nm) through a facile method by simply
mixing ĳPd2Ĳm-CO)2Cl4]2− with H2O, as shown in Fig. 1. In the
synthesis of the ĳPd2Ĳm-CO)2Cl4]2− complex, a solution of
PdCl42− and anhydrous N,N-dimethylformamide (DMF) was
stirred under a CO atmosphere which served as both the

reductant and capping agent. This work further confirms the
importance of the precursor in controlling the shape of
noble-metal NCs.
2.2 Functional molecule

The functional molecule is a kind of special molecule which
forms specific interactions with certain crystal facets of a
noble metal, which is a critical element in both the shape
and the activity control of nanocatalysts. The capping agents,
additives, etching agents, polymer stabilizers, and some sur-
factants are all functional molecules. In the synthesis of NCs,
specific functional molecules need to be added to achieve
Scheme 1 A simple sketch of the synthesis of shaped noble-metal NCs.
the fine control of the nanocrystal's morphology. Actually,
the interaction between the metal surface and the functional
considered to be the real precursor during the reduction molecules may change the surface energy of the crystal
process.21 facets. Then each crystal face has its own growth rate by the
Li and He40 introduced PtĲacac)2 and NiĲacac)2 simulta- adsorption or selective etching of functional molecules,
neously as precursors in the synthesis of PtxNi1−x bimetal which determines the final shape of NCs. Meanwhile func-
nanocatalysts. The obtained Pt–Ni bimetallic NCs with vary- tional molecules are also used as stabilizers to prevent bulk
ing shapes (octahedral, truncated, octahedral, and cubic) aggregation and deposition of metal nanocrystals. Recent
were uniformly assigned to different crystal growth inhibition studies demonstrated that employing different functional
agents such as benzoic acid, aniline, and carbon monoxide. molecules could make NCs with various shapes by seed-
Then, their group chose RhCl3Ĵ3H2O and NiĲacac)2 to gain mediated growth.
another noble-metal/non-noble-metal catalyst ĲRhxNi1−x).47 PVP has been widely used as a steric stabilizer to protect
The partial substitution of a noble-metal with a non-noble- NCs from agglomeration in most chemical syntheses. As
metal shows both economic benefits and new properties and shown in Table 1, PVP with molecular weight (MW) ranging
capabilities due to their synergy. The catalytic performance of from 8000 to 360 000 is the most popular stabilizer for the
Rh–Ni NCs over a broad range of x values was evaluated with synthesis of shaped NCs for hydrogenation. Li et al. em-
the hydrogenation of arenes. The bimetallic nanocatalysts ployed a PVP polymer with MW 8000 for the synthesis of
also exhibited high performance in the hydrogenation of bimetal and trimetal NCs for hydrogenation.40,41 Somorjai
olefins and nitroarenes. These two good examples represent and co-workers used a PVP polymer of MW 29 000 to prepare
a novel kind of precursor which shows great potential in the Pt NCs for ethylene and pyrrole hydrogenation.18 A larger
synthesis of shaped NCs due to their unique properties in PVP polymer of MW 55 000 was introduced in the synthesis
the reactions. Moreover, Zheng’s group42 also prepared octa-
hedral Pt3Co NCs from PtĲacac)2 and CoĲacac)2. PtĲacac)2 or
NiĲacac)2 was also selected as the precursor for the prepared
uniform NCs in the work of Sun’s group44 and Fang’s group.45
Somorjai and Yang18 used ĲNH4)2PtĲIV)Cl6 and ĲNH4)2PtĲII)Cl4
together to generate sub-10 nm Pt NCs for ethylene hydroge-
nation. The formation of Pt nanocubes (85% cubes, 15%
tetrahedra or irregular crystals) was revealed by transmission
electron microscopy (TEM) images when the PtĲIV) salt was
used in the precursor solution. Furthermore, they also
successfully prepared Pt nanocubes using the precursor of
Pt2+ and Pt4+ together. In other words, faceted NCs can be
obtained with the addition of metal precursors with differ-
Fig. 1 (a) TEM image of the Pd nanosheets. The inset shows the size
ent valences in the same batch. Tilley’s group used distribution of Pd nanosheets. (b) TEM image of a single Pd nanosheet
bisĲacetonitrile) palladium dichloride as the precursor for attached to a carbon nanotube.28 Reprinted with permission from
the synthesis of highly branched Pd NPs.35 John Wiley and Sons.
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Minireview Catalysis Science & Technology
of Pd NCs and PtPd NCs with well-defined facets by Xia’s Other polymers, such as sodium polyacrylate (SPA), were
group29 and Huang’s group.43 Zaera’s group used a very large also usually used in the synthesis of uniform noble-metal
PVP polymer with a molecular weight of 360 000 for the prep- NCs. For example, Zaera’s lab employed SPA of MW 2100 for
aration of tetrahedral Pt NCs.20 the synthesis of cubic Pt NCs,20 and Miyake et al. used MW
The binding of surface capping agents (e.g., PVP) usually 8000 SPA to prepare various shaped Pt NCs for olefin hydro-
decreases the activity of a catalyst because of the coverage on genation.22 Besides, small molecules, such as I−,22,43 Br−,48
the active sites. Previous studies showed that the coverage of Cl−,43,48 oleylamine (OAM),35,42,44,45,47 oleic acid,35,44,45 benzoic
metal surfaces by large PVP polymers will decrease their acid,41 diphenyl ether,44 TTAB,2 bromurede cetyltrimethyl-
activity due to the fact that the capping or stabilizing agents ammonium (CTAB)23,32 and C14TABr21 were also introduced for
on the surfaces of the NPs hinder contact between the reac- the preparation of shaped metal NCs for hydrogenation.
tants and active sites of the noble metal. Similar results OAM proved to be an efficient functional molecule since it can
were obtained for catalytic hydrogenation. Based on the well- act as both the solvent and the capping agent at the same
defined Pd NCs prepared by Xia’s group using PVP as the time.30,42,47 Li’s group52 compiled the noble-metal-induced
stabilizer,48 Kiwi-Minsker’s group studied their catalytic reduction strategy with octadecylamine (ODA) to generate vari-
properties for acetylene hydrogenation.29 They found that ous bimetallic NCs.
PVP indeed affected the catalytic performance of Pd NCs. The Medlin’s and Schwartz’s groups have finished systematic
removal of PVP by UV-ozone showed a 4-fold increase in their research on the modification of traditional catalytic materials
activity. Therefore, some methods such as UV-ozone, calcina- using self-assembled monolayers (SAMs) to create a more
tion, plasma and electrochemical imposition at high voltages, favorable surface environment for specific product forma-
have been adopted to gain a clean surface of metal tion.53 They tuned the monolayer structure to improve the
NPs.20,29,49–51 However, there is an exception. Li’s group re- catalytic performance for hydrogenation reactions on palla-
ported that PVP as the capping agent does not affect the solu- dium and platinum catalysts. Each approach serves to direct
bility, activity, and recyclability of PtNi nanoalloy catalysts for selectivity by tuning a particular aspect of the system includ-
the hydrogenation of benzalacetone, styrene, and nitro- ing the availability of specific active sites (active-site selec-
benzene.40 Besides, different capping agents have their own tion), intermolecular interactions between the reactants and
effects on the catalytic activity. Somorjai’s group21 proved modifiers (molecular recognition), and general steric or
that the activity is higher for ethylene hydrogenation using crowding effects. On the uniform truncated nanooctahedral
tetradecyltrimethylammonium bromide (TTAB) as the cap- Pt3Co with (111) and (100) facets, Zheng’s and Fu’s groups
ping agent than for that using PVP. studied the selectivity of cinnamaldehyde hydrogenation
Fig. 2 Typical TEM images and size distribution of Pt NPs controlled by TA (a, b) and 3-HB (c, d). Reproduced from ref. 19.
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directed by oleylamine.42 Capping the Pt3Co (100) surface catalytic activity for the hydrogenation of styrene and α,
with amines that contain long carbon chains results in an β-unsaturated aldehydes, respectively.44,45 In Huang's work,43
ordered surface “array”, in which high selectivity towards nearly 100% conversion of nitrobenzene was achieved for
CO hydrogenation can be achieved because the CC bond the nanocubic Pt51Pd49 capped by I− and PVP under 1 atm
in cinnamaldehyde does not interact with the surface. hydrogen gas in 120 min at room temperature. But in other
A review of Zheng’s group12 has clearly demonstrated that cases, before the removal of strong adsorbates on their sur-
strong adsorption of several small adsorbates, like I− and CO, face, the as-prepared NPs typically lack good catalytic activ-
could serve as an effective factor to enrich not only the sur- ity.54 Overall, the influence of these small adsorbates in
face structure but also the shape of Pd and Pt NCs. Small hydrogenation is still not clear. Deep insight into the behav-
adsorbates on the surface will affect the catalytic activity of ior of the small capping agents in catalytic hydrogenation
the as-prepared NCs. In some cases, the small adsorbates should be carried out in the future.
does not largely suppress the catalytic activity of noble-metals In addition to the functional molecules mentioned above,
during hydrogenation. With the presence of small adsorbates biomolecules were also introduced for the controllable prepa-
on the surface of noble-metal nanocatalysts, outstanding ration of noble-metal NCs. Programmable biomolecules, such
activity for catalytic hydrogenation was still achieved. For as peptides, DNA and proteins, have been employed to
instance, CO-capped Pd nanosheets showed superior activity achieve controllable nanostructures of noble-metals. It has
to PVP-capped Pd nanosheets for the conversion of styrene to been reported that some of the bio-inspired NCs can be used
ethylbenzene.28 Moreover, Pt3Co concave nanocubes and as catalysts for hydrogenation. Knecht’s lab27 succeeded in
shaped Pt3Ni NPs capped by oleylamine and CO exhibit good producing Pt and Pd NCs of varying morphologies via a
Fig. 3 (a) TEM, (b) HRTEM (top-right and top-middle insets show the corresponding FFT pattern and the ideal structure model), and (c) HAADF-
STEM images of PtNi2 octahedrons, corresponding element maps showing the distribution of Pt (yellow) and Ni (red). (d) Size distribution of octa-
hedral particles (average size: 11.8 ± 1.2 nm, 95% octahedrons and 5% irregular shapes). (e) TEM, (f) HRTEM, and (g) HAADF-STEM images of PtNi2
truncated octahedrons. (h) Size distribution of truncated octahedral particles (average size: 12.5 ± 1.1 nm, 90% truncated octahedrons and 10%
irregular shapes). (i) TEM, (j) HRTEM, and (k) HAADF-STEM images of PtNi2 cubes. (l) Size distribution of cubic particles (average size: 16.1 ± 1.7 nm,
95% octahedrons and 5% irregular shapes).40 Reprinted with permission from the American Chemical Society.
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peptide-template-based approach. With the changed metal/ spherical dendritic polymers by Crooks et al.56,57 The results
peptide ratio employed during the synthesis, it is intriguing of high-resolution transmission electron microscopy (HRTEM)
to discover that the Pd nanomaterials exhibited various mor- showed that the mean particle sizes of the obtained forty-atom
phologies while the Pt NCs remained spherical at all times. Pt and Pd DENs which were nearly monodisperse were 1.4 and
The NCs of Pt or Pd directed by R5 peptide 1.5 nm, respectively, but the shape of the NPs cannot be well-
(SSKKSGSYSGSKGSKRRIL) were further used for olefin hydro- controlled due to such small sizes.
genation with good activity. Moreover, Pt-{100} and Pt-{111}
binding peptides were developed to synthesize uniform plati- 2.3 Reducing agent
num nanocubes and nanotetrahedra by Huang’s group.55 The reducing agent plays a key role in controlling the nucle-
Investigation of this process indicates the origin of the pep- ation and growth of NCs by way of the reduction kinetics.
tide recognition toward Pt (111) and Pt (100) surfaces. When reduction is at a sufficiently high rate, the final prod-
3-hydroxybutyric acid (3-HB) and tropic acid (TA) were identi- uct will have no choice but to take the thermodynamically
fied as the dominant motif to specific binding of Pt {100} favored shapes. When reduction becomes substantially slow,
and Pt {111} facets, respectively.13 Therefore, uniform cubic however, the nucleation and growth will be under kinetic
and tetrahedral NCs of Pt were prepared, directed by 3-HB control and the final product can take a range of shapes devi-
and TA, respectively (Fig. 2). Li et al. investigated the catalytic ating from the thermodynamic ones (e.g., a structure with
performance of these bio-inspired Pt NCs with uniform facets high-index facets).14 By controlling the reaction kinetics of
for the hydrogenation of 4-nitrophenol (4-NP).19 seed-mediated growth, various NCs have been successfully
In addition, dendrimers were also applied in the synthesis prepared with a wide variety of structures.
of noble-metal NPs. For instance, platinum and palladium NaBH4 is the most widely used strong reducing agent
dendrimer-encapsulated NPs (DENs) were prepared within in metal salt solutions which directs the noble-metal ion
Fig. 4 (a–c) SA-corrected HRTEM images of (a) Pt3Ni@Au0.5, (b) Pt3Ni@Au2, and (c) Pt3Ni@Au8. (d–f) Elemental maps of (d) Pt3Ni@Au0.5,
(e) Pt3Ni@Au2, and (f) Pt3Ni@Au8. (g) Schematic illustration of the evolution from octahedral PtNi3 to Pt3Ni@M8 (M = Rh, Au, Ag, Cu). (h) Schematic
illustration of the growth of Au on the Pt surface.41 Reprinted with permission from the American Chemical Society.
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growth to obtain metal NCs for hydrogenation applica- ODA is a useful all-in-one additive as a capping agent,
tions.2,19,21,23,24,27,32,57 Besides, alkanols and polyols are also solvent and reducing agent in the synthesis of NCs. Both Li’s
widely used in the synthesis of noble-metal NCs as a kind group47 and Zhang’s group30 used ODA for the direct thermal
of weak reducing agent. For example, benzylalcohol was decomposition of a noble-metal salt to fabricate various
used in the synthesis of shaped alloy NCs by Li’s group noble-metal NCs. A metal carbonyl, such as tungsten
(Fig. 3 and 4).40,41 Without the extra reducing agent, the alco- hexacarbonyl ĳWĲCO)6], was used as the shape-directing
hol plays the roles of both reducing agent and solvent. agent and reducing agent.45 As discussed by Fang’s group,
Hou’s group58 found that highly dispersed Pt NCs could it was believed that tungsten decomposed from tungsten
be fabricated on the surface of graphene oxide (RGO) by a hexacarbonyl ĳWĲCO)6] played a partial role in the formation
direct ethylene glycol reduction of PtCl62− without any addi- of the concave structure of Pt-based NCs. In addition, CO
tives in aqueous solution. Pt/RGO exhibited higher catalytic decomposed from metallic carbonyl will act as both reducing
properties for the selective hydrogenation of CO in cinnam- agent and capping agent absorbing on the surfaces of noble-
aldehyde than support-free Pt colloidal NCs. Studies found metal NCs.28,59
that the reducing power of an alcohol decreases as its alkyl
chain becomes longer. In a water-based system, the differ- 3. Activity and selectivity of faceted
ence in reducing power for these reagents enables one to
control the reduction kinetics, and thus the shape of noble-
noble-metal nanocrystals for
metal NCs. Moreover, PVP can also act like a long-chain alco- hydrogenation
hol and serve as a class of weak reducing agent.34,48
19,21,32,34 Size, morphology, and the residue of the additives on the sur-
L-Ascorbic acid (or sodium ascorbate) and citric
34,48 face of metallic NCs have been proven to be of immense
acid were also employed as reducing agents. L-Ascorbic
importance to their catalytic functionalities. Generation of
acid, which is commonly known as vitamin C, can serve as a
NCs with precise morphology and surface structure provides
strong reducing agent for the fast reduction of a noble-metal
a way to modify the proportion of different facets and the
precursor, while citric acid works as a reducing agent in a
number of atoms on the corners and edges. Then the activity
manner similar to the mechanism for a conventional citrate-
and selectivity of catalytic hydrogenation can be tuned, which
based synthesis of noble-metal NCs.
has been proven by many studies.32,60,61
Moreover, H2 (ref. 2,20,22–24 and 35) and CO28,42,44 were
employed as gaseous reducing agents for the synthesis of
noble-metal NCs for hydrogenation. With the introduction of 3.1 Pt nanocrystals
these gases, noble-metal NCs with clean surfaces can be Over the last decade, platinum has been widely studied due
easily obtained and the H2 or CO molecules adsorbed on the to its versatile and efficient catalytic properties. In this sec-
surface can be easily removed by applying a high temperature tion, we will briefly highlight recent important reports
or an electrochemical oxidation potential. concerning well-defined Pt NCs used in hydrogenation.
Fig. 5 TEM image of TTAB-stabilized (a) cubic particles (average size: 12.3 ± 1.4 nm, 79% cubes, 3% triangles, and 18% irregular shapes) and (c)
cuboctahedral particles (average size: 13.5 ± 1.5 nm, 90% cuboctahedra and 10% irregular shapes). TEM images of (b) cubic and (d) cuboctahedral
Pt NPs after reaction at 400 K for 10 Torr C6H6, 100 Torr H2, and 650 Torr Ar.2 Reprinted with permission from the American Chemical Society.
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In 2006, Somorjai’s group and Yang’s group62 prepared Pt while only cyclohexane was produced on cubic Pt NPs cov-
NCs (cuboctahedra, cubes, and porous particles) capped with ered by only (100) facets. These results are consistent with a
alkylammonium ions by manipulating the reduction kinetics. previous study for single-crystal bulk Pt surfaces.1 The appar-
They found that the catalytic activity of these NPs for ethyl- ent activation energies for cyclohexane and cyclohexene for-
ene hydrogenation is superior to that of NCs whose shape mation on cuboctahedral NCs in the temperature ranges of
was controlled with a polymeric capping agent and foreign 310–340 K and 330–360 K are respectively equal to 8.3 ± 0.2
metal ions. Then, Somorjai’s group2 successfully confirmed and 12.2 ± 0.4 kcal mol−1. For cubic NPs, the apparent activa-
that the catalytic selectivity is significantly affected by the tion energy for cyclohexane formation in the temperature
shape of the NCs with the noted example of benzene hydro- range of 330–370 K is equal to 10.9 ± 0.4 kcal mol−1. The sig-
genation. The Pt NCs used in their study are shown in nificantly lower apparent activation energies and higher turn-
Fig. 5a and c. After hydrogenation, the shape of the NCs was over rates obtained with Pt NCs compared to Pt single crys-
only changed slightly as shown in Fig. 5b and d. Fig. 6 shows tals may be attributed to the decreased size or changes in the
a comparison between the kinetic data of TTAB-stabilized electronic structure of the NCs compared to the Pt single
cubic and cuboctahedral Pt NCs in the temperature range of crystals, rather than the corner and edge sites on the NCs
310–400 K. Both cyclohexene and cyclohexane were obtained available for catalysis, because Miyake et al. found that cor-
on Pt cuboctahedral NCs with both (111) and (100) facets ners and edges have a minor influence on the olefin hydroge-
nation activity of Pt NPs.22
The subsequent work of Somorjai’s group and Yang’s
group further confirmed that the morphology of the noble-
metal is really important for the chemoselectivity of hydroge-
nation. They studied the hydrogenation of ethylene and pyr-
role catalyzed by sub-10 nm Pt NCs with well-defined facets.18
In the examination of catalytic properties, the NCs were
supported in MCF-17 mesoporous silica. In ethylene hydroge-
nation, they found that smaller Pt NCs with more active sites
showed higher activity. For the hydrogenation of pyrrole, the
results showed that the shape of the NCs led to clear selectiv-
ity differences. n-Butylamine was the dominant product for 5
and 9 nm Pt nanocubes, while for the 5 nm Pt nano-
polyhedra, pyrrolidine (up to 30%) and n-butylamine were
both formed at lower temperatures (<400 K).
Furthermore, Somorjai’s group63 studied the hydrogena-
tion of furan over Pt (111) and Pt (100) to elucidate the cata-
lyst structure effect. Furan is a kind of five-membered ring
molecule which is of particular importance in the chemical
industry for both fuel reforming and environmental con-
cerns. The catalytic study of furan hydrogenation was first
carried out in 1949 by Smith and Fuzek over Adams platinum
(platinum dioxide reduced in hydrogen).64 The reaction path-
way for furan hydrogenation is shown in Scheme 2. In the
study by Kliewer et al.,63 the reaction was carried out on Pt
NCs of 1 nm, 3.5 nm, 7 nm to help determine the effect of
catalyst size. A powerful surface analysis technique - sum fre-
quency generation vibrational spectroscopy (SFG-VS) was
applied to systematically study the surface adsorped species
Fig. 6 (a) Turnover rates of cyclohexane ĲC6H12) and cyclohexene

ĲC6H10) formation on TTAB-stabilized cubic and cuboctahedral Pt NPs
for 10 Torr C6H6, 100 Torr H2, and 650 Torr Ar, and (b) corresponding
Arrhenius plots. Deviation from Arrhenius behavior above 340 K for
cyclohexane and above 370 K for cyclohexene formation is attributed
to changes in the nanoparticle surface coverage caused by gas-phase
adsorbates. The dotted lines are drawn as visual aides.2 Reprinted with Scheme 2 Hydrogenation of furan.63 Reprinted with permission from
permission from the American Chemical Society. the American Chemical Society.
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present on Pt (111) and Pt (100) during the selective hydroge- catalysts in a H2 atmosphere. Their investigation indicates
nation. As a result, in the spectra on Pt (111) the furan ring potential application to the hydrogenation of many unsatu-
is lying parallel to the metal surface upon the coadsorption rated hydrocarbons (olefins, aldehydes, ketones, organic
of furan and hydrogen. acids, imines, etc.).
Somorjai’s group in collaboration with Yang’s group pre- Pham Minh et al.23 prepared well-defined Pt NCs which
pared Pt nanocubes, nanocuboctahedra, and nanooctahedra were deposited on alumina for the selective hydrogenation of
by the addition of silver ions which enhanced the crystal buta-1,3-diene. In their synthesis, the morphology of the Pt
growth rate along <100>.65 They encapsulated the Pt NCs in NCs was dependent on the synthesis conditions such as tem-
mesoporous silica (SBA-15) by in situ hydrothermal growth. perature, atmosphere and the ratio of cationic surfactant and
The catalysts are active for ethylene hydrogenation.62 Then, a Pt. The Pt nanocatalyst (polyhedric morphologies) exposed
procedure was developed for the selective etching of silver mainly the (111) crystallographic plane and had the highest
from these shaped Pt NCs, resulting in the formation of selectivity for the hydrogenation of buta-1,3-diene to butenes
nearly elementally pure Pt nanocubes, nanocuboctahedra, or with a drastic decrease of further hydrogenation to n-butane.
nanooctahedra, with a largest vertex-to-vertex distance of Sepúlveda-Escribano and co-workers24 evaluated the effect
~9.5 nm from the Ag-modified Pt NCs. Subsequently, they of uniform Pt NCs with (100) or (111) crystal faces on the cat-
found that the activity of these Pt NCs for ethylene hydrogena- alytic hydrogenation of crotonaldehyde and cinnamaldehyde,
tion increased exponentially with a decreasing Ag/Pts ratio.66 respectively (Scheme 4). They found that Pt(100)/C showed
Their results confirmed that Ag used in the synthesis of the best catalytic activity among the Pt/C and Pt(111)/C cata-
shaped Pt NCs is confined to the surface and could be selec- lysts for crotonaldehyde hydrogenation at 333 K, as shown in
tively removed to produce highly active surface-clean Pt nano- Fig. 7. The conversion of cinnamaldehyde hydrogenation
catalysts for hydrocarbon conversion. followed the trend Pt/C > Pt(100)/C > Pt(111)/C.
Then, Somorjai and Yang67 discussed the catalytic proper- The effects of shape and support on the catalytic activity
ties of uniform Pt NCs which were deposited on the surface of Pt NCs for 4-nitrophenol (4-NP) hydrogenation were stud-
of capping-agent-free CeO2 nanooctahedra and nanorods ied by our group by comparing kinetic results. The catalytic
using an electron beam (e-beam) evaporation strategy. Cover-
age of the Pt nanocluster layer can be controlled by adjusting
the e-beam evaporation time. Finally, the results of hydroge-
nation of ethylene and cyclohexene clearly showed similar
activation energies for both Pt/CeO2 nanooctahedra and
Pt/CeO2 nanorods, but their results are not conclusive enough
to determine the dominant crystal facets of the Pt NCs.
Additionally, their groups reported the preparation of
Pt/mesoporous silica core–shell (Pt@mSiO2) NPs with ther-
mal stability at high temperatures (Scheme 3). The synthe-
sized Pt@mSiO2 nanopartices that consist of 14 nm Pt cores
and 17 nm-thick mesoporous silica shells have high thermal
stability and are as catalytically active as bare Pt metal for
ethylene hydrogenation.26
Zaera’s group used colloidal and sol–gel procedures to
prepare platinum NCs with narrow size distributions and well
defined shapes dispersed on high-surface-area silica sup- Scheme 4 Reaction pathways for cinnamaldehyde hydrogenation.24
ports.20 Double-bond isomerizations were studied on the Pt Reprinted with permission from Elsevier.
Scheme 3 Schematic representation of the synthesis of t@mSiO2 NPs. Pt NPs were synthesized using TTAB surfactant as the capping agent, and
used as the core particle. Second, as-synthesized Pt@SiO2 particles were prepared by polymerizing TEOS around the TTAB-capped Pt cores. RT:
room temperature. The as-synthesized Pt@SiO2 particles were subsequently converted to Pt@mSiO2 particles by calcination.26 Reprinted with per-
mission from the Nature Publishing Group.
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Fig. 7 TOF for crotonaldehyde hydrogenation at 333 K as a function

of time on stream for Pt/C, Pt(111)/C, and Pt(100)/C catalysts.24
Reprinted with permission from Elsevier.
Fig. 8 Comparison of the kinetic data of catalysts with different

supports. Reproduced from ref. 19.
activity was found to be strongly affected by the shape of the
Pt NCs and the supports (SBA-15 and Al2O3). An L–H model
involving a surface-reaction controlling mechanism was used nanotetrahedron, nanowires). Their results suggested that
to fit the experimental data. Then the apparent activation cubic Pt showed the highest catalytic activity without signifi-
energy was calculated over cubic Pt(3-HB) and pseudo- cant shape change after repeated reaction. Kou’s group68 pre-
tetrahedral Pt(TA), which was 74.23 kJ mol−1 and 40.98 kJ pared new Pt nanoclusters stabilized by an ionic-liquid-like
mol−1, respectively (Table 2). When the Pt NCs were loaded copolymer for the hydrogenation of chloronitrobenzene. The
on SBA-15, the apparent activation energy decreased to Pt NPs (1.7 nm) exhibited excellent activity (total turnover
52.05 kJ mol−1 for cubic Pt(3-HB) NPs, while that of Pt(TA) @ number > 25 900) and selectivity for o-chloronitrobenzene
SBA-15 increased to 61.29 kJ mol−1. As compared to the (o-CNB) hydrogenation to the desired product, o-chloroaniline
SBA-15 loaded Pt catalysts, the corresponding Al2O3 sup- (o-CAN).
ported Pt catalysts showed lower activity, as shown in Fig. 8. Asymmetric catalysis with excellent selectivity is a signifi-
Interestingly, Pt(TA) on Al2O3 has higher activity than that of cant concept in catalytic hydrogenation. It makes the process
Pt(3-HB), while Pt(3-HB) on SBA-15 showed better perfor- more effective for producing chiral products in industry. Ying
mance than Pt(TA) on SBA-15. In addition, when the support et al. reported the application of modified platinum nano-
was changed, the kinetic behavior of supported Pt(3-HB) and wires in the enantioselective hydrogenation of α-ketoesters.
Pt(TA) NPs was altered. It can be concluded that the interac- The Pt nanowires were of uniform length and had a diameter
tions between Pt NPs of different shapes and the support are of ~1 nm with cinchona alkaloids, as displayed in Fig. 9.
different when the support is changed from SBA-15 to Al2O3. Excellent yields and moderate-to-excellent enantioselectivities
The special interaction between cubic Pt(3-HB) NPs and were achieved in the asymmetric hydrogenation, as indicated
SBA-15 was further confirmed, which increases the catalytic in Scheme 5.25
activity of PtĲ3-HB)@SBA-15. Overall, there are promising results that encourage us to
Miyake and coworkers22 investigated olefin hydrogenation develop Pt nanocatalysts with high reactivity and controllable
in the liquid phase by using several kinds of Pt NCs with selectivity via finely tuning their size and exposed facets. In
different shapes (nanocubes, nanocuboctahedron, the future, more systematic investigation and deeper insight
Table 2 Parameters of the L–H model obtained at 25 °C, 40 °C and 70 °C under 0.4 MPa and corresponding apparent activation energy for cubic
Pt(3-HB) NCs and pseudo-tetrahedral Pt(TA) NCs.19
dC A k1K A K B3CACB3
r1  
1  K ACA  1  K B1/ 2CB1/ 2 
6
dt
Catalyst T/K k1/s−1 KA/L mol−1 KB/MPa−1 R2 Ea/kJ mol−1

Cubic Pt(3-HB) NPs 298.15 0.0032 0.7761 65 0.999581 74.23
313.15 0.0058 0.4178 62 0.999423
343.15 0.1414 0.023 56 0.995713
Pseudo-tetrahedral Pt(TA) NPs 298.15 0.0024 1.0877 110 0.992943 40.98
313.15 0.0032 1.5219 50 0.996617
343.15 0.0193 0.3536 39.9998 0.999005
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Fig. 9 TEM images and (inset) selected area electron diffraction (SAED) of (A, B) FePt and (C, D) Pt nanowires and (E) XRD patterns of the as-
synthesized (—) FePt and (—) Pt nanowires.25 Reprinted with permission from the Royal Society of Chemistry.
Scheme 5 Asymmetric hydrogenation of ethylbenzoyl formate over alkaloid-modified Pt nanowires.25 Reprinted with permission from the Royal
Society of Chemistry.
Fig. 10 (a) Schematic illustrations of the shaped Pd NPs and their two types of active sites involved in the hydrogenation of MBY. Atoms on
the planes, regardless of their crystallographic orientations, constitute the first type of active site, σ1. Low-coordination atoms, or atoms at the
edges, represent the second type of active site, σ2. (b) Modified reaction network for the hydrogenation of MBY, showing the active sites involved
in each path. (c) Optimization of Pd nanocrystal size and shape based on productivity of MBE.34 Reprinted with permission from the American
Chemical Society.
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in this research area should be continued, and then noble- Recently, Knecht’s lab27 succeeded in producing Pt and
metal nanocatalysts with superior performance in hydrogena- Pd NCs of varying morphologies using R5 peptide which were
tion will be fabricated. highly reactive for allyl alcohol hydrogenation. They found
that peptides do not inhibit the reactivity of Pt and Pd NCs.
In addition, the material templates are efficient tools
3.2 Pd nanocrystals exploited to overcome the issue that the stabilizing agents
Pd NCs have been employed as catalysts for a variety of reac- prejudice the reagent diffusion. Actually a variety of material
tions including the hydrogenation of 4-nitrophenol, olefin, templates such as resins and polyelectrolytes were used to
and so on. As early as 2004, Chaudhari’s group33 reported maintain an open/porous structure of metal nanocatalysts to
that much higher turnover frequencies were found for the facilitate the catalytic reactivity.
hydrogenation of 2-butyne-1,4-diol with Pd nanocubes (5–7 nm) Tilley’s group synthesized highly branched palladium
than nanospheres (1–7 nm). They showed that both catalytic nanostructures in toluene solution with organic surfactant at
activity and selectivity was affected by the shape of Pd NCs for room temperature.35 As shown in Fig. 11, high index (113)
the hydrogenation of 2-butyne-1, 4-diol into 2-butene-1,4-diol.
Crooks’ lab69 studied the particle size effect for hydroge-
nation over unsupported Pd NPs in the size range of 1.3–1.9 nm.
They demonstrated that the rate of hydrogenation of allyl
alcohol is a function of the diameter of the Pd NPs. The
hydrogenation kinetics are dominated by electronic effects
for the smallest particles (<1.5 nm diameter) and by geomet-
ric effects for larger particles (1.5–1.9 nm diameter).
Previous studies showed that the hydrogenation of buta-
1,3-diene is a structure-sensitive reaction. Berhault’s group31
synthesized uniform Pd NCs by a “seeding-mediated” meth-
odology and applied them to the selective hydrogenation of
buta-1,3-diene. CTAB was exploited as both a capping and
structure-directing agent in the process, which induced the
anisotropic Pd nanorods to expose (100) facets preferentially.
The results showed that Pd (100) surfaces are particularly
selective for the hydrogenation of dienes to alkenes without
further hydrogenation to alkanes. In comparison, previous
studies on bulk Pd surfaces indicated that Pd (110) exhibits a
higher selectivity for butene formation than Pd (111) facets.70
It can be deduced that the facet effect may be totally different
between nanocrystals and bulk material in hydrogenation.
Kiwi-Minsker’s group and Xia’s group34 prepared Pd NCs
with well-defined shapes and used them in the selective
hydrogenation of 2-methyl-3-butyn-2-ol (MBY). In their work,
semihydrogenation of MBY to 2-methyl-3-buten-2-ol (MBE)
occurred preferentially at the plane sites regardless of the
crystallographic orientation, while overhydrogenation to
2-methyl-3-butan-2-ol (MBA) occurred mainly at the edge
sites, as displayed in Fig. 10. Obviously, the selectivity was
then associated to the fraction of edge sites on each type
of NC. Coupled with the kinetic simulations, 3–5 nm cubic
Pd NCs were an optimal catalyst for the highest production
of MBE.
Zheng’s group28 mixed a Pd carbonyl complex, ĳPd2Ĳμ-
CO)2Cl4]2−, and H2O without any organic capping agents to
fabricate ultrathin Pd nanosheets (1.8nm). The surface-clean
Pd nanosheets supported on carbon nanotubes (CNT) Fig. 11 Analysis of the surface of one of the highly branched
showed higher activities for the hydrogenation of styrene in nanostructures. (a) HRTEM image of one of the particle branches; (b)
HRTEM image of the particle branch showing clear atomic packing. The
comparison to the PVP-capped Pd nanosheets. Further experi-
black arrows point to atomic vacancies on the particle surface.
ments proved that PVP partially blocks the active sites, which (c) Schematic showing how the atomic vacancies lead to high index
is consistent with the results of Kiwi-Minsker and co-workers29 (113) facets.35 Reprinted with permission from the American Chemical
reported in 2010. Society.
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Table 3 Comparison of catalytic activity and selectivity of Rh on charcoal for the hydrogenation of anthracenea
Entry Cat.b P t Conv.c Selectivity[%]

[atm] [h] [%] B C D
1 ▲/C 10 0.5 100 0.7 0.0 99.3
2 ▲/C 1 2 100 2.0 0.0 98.0
3 ●/C 1 2 99.5 6.7 76.3 17.0
4 Rh/C 10 0.5 57.3 6.4 81.0 12.6
5 Rh/C 1 2 4.8 35.4 45.8 18.8
a
Reaction conditions: 1.00 mmol of anthracene and 1 mol% of Rh/C (based on ICP analysis) in methanol at room temperature. b (4.9 ± 0.4) nm
tetrahedral rhodium NPs on charcoal (▲/C), (4.8 ± 0.4) nm spherical rhodium NPs on charcoal (●/C), and commercial Rh/C. c Conversion
determined by GC-MS.37 Reprinted with permission from John Wiley and Sons.
facets exist on the nanostructure. They demonstrated control 3.3 Rh nanocrystals

over the reaction kinetics and hence the shape of the nano- Son’s group37 reported that tetrahedral Rh NCs preferentially
structures by varying the nature of the organic stabilizer sys- exposing (111) planes were prepared by thermal decomposi-
tem. Investigations into the structural evolution of the nano- tion of Rh complexes in OAM and supported on charcoal.
structures indicated that ultrafast growth lead to highly These supported (4.9 ± 0.4) nm Rh nanotetrahedra showed a
branched nanostructures. The nanostructures then show 5.8- and 109-fold increase in activity for the hydrogenation of
excellent catalytic activity for the hydrogenation of nitroben- anthracene compared to spherical Rh NPs and commercial
zene to aniline. Rh/C catalyst, respectively, as shown in Table 3.
Somorjai’s group39 synthesized monodisperse and well-
shaped Rh NCs in the range of 5–15 nm at temperatures of
170–230 °C under an Ar atmosphere (Scheme 6). TEM mea-
surements showed Rh polygons dominated by hexagons, pen-
tagons, and triangles exposing catalytically active (111) sur-
faces (>65% in yield) (Fig. 12). Preliminary catalytic tests for
ethylene hydrogenation revealed that the Rh nanocrystal
monolayers formed on silicon wafers by the Langmuir–
Blodgett method are active nanocatalysts.
Scheme 6 Schematic illustration of one-step polyol synthesis of
Later, their group38 reported the synthesis of monodis-
monodisperse well-shaped Rh NPs.39 Reprinted with permission from perse Rh nanocubes with sizes of less than 10 nm by a seed-
the American Chemical Society. less polyol method. The {100} faces of the Rh NCs were
Fig. 12 TEM and (a) HRTEM (b–e) images of 13.5 nm Rh NCs.39 Reprinted with permission from the American Chemical Society.
View Article Online
effectively stabilized by chemically adsorbed Br− ions from

TTAB. They also deposited the Rh nanocubes onto silicon
wafers to catalyze the hydrogenation of pyrrole. The results
showed that pyrrole was fully hydrogenated to n-butane and
ammonia between 303 K and 343 K, and the TOF did not
strongly depend on temperature, as shown in Fig. 13.

Schaak’s group71 prepared magnetically separable hydro-
genation nanowire catalysts decorated by metal NPs (Rh, Ru,
Pd) and assembled by intriguing biological molecules and
organisms. They chose the M13 bacteriophage as the scaffold
because of its ability to bind selectively to a variety of distinct
Scheme 7 Hydrogenation of benzalacetone, styrene, or nitrobenzene
crystal faces of several types of materials. The Rh-coated
catalyzed by octahedral, truncated octahedral, and cubic Pt–Ni NCs.40
phage NCs showed excellent catalytic viability for the hydro- Reprinted with permission from the American Chemical Society.
genation of styrene and methyl red.
exhibited the best performance with respect to both activity

3.4 Bimetal or trimetal nanocrystals and selectivity among the as-prepared trimetallic multifunc-
Bimetal and trimetal NCs with well-defined facets were also tional nanocatalysts, as displayed in Fig. 14.
prepared and used for catalytic hydrogenation. Enormous Similarly, Sun’s group and Zhu’s group synthesized cubic
economic benefits of the substitution of noble-metals to form (enclosed by six {100} facets) and octahedral (surrounded by
these bimetallic or trimetallic catalysts will be gained. eight {111} facets) Pt, PtNi and Pt3Ni NCs and used them for
The groups of He and Li40 synthesized various PtxNi1−x(0 < the hydrogenation of α,β-unsaturated aldehydes.44 Compared
x < 1) NCs with uniform octahedral, truncated octahedral, or with monometallic Pt and PtNi cubic/octahedral shapes,
cubic shapes (Scheme 7). It is interesting to note that the cat- Pt3Ni cubes enhanced the selective hydrogenation of the
alyst activity for the hydrogenation of benzalacetone CO double bond and suppressed that of the CC double
increases with the increased percentage of (111) facets, corre- bond of α,β-unsaturated aldehydes. The results indicated that
sponding to the shape evolution from cube through trun- the octahedral shape of Pt, Pt3Ni, or PtNi is an unfavorable
cated octahedron to octahedron. They also demonstrated that structure for CO hydrogenation. The (111) facet enables
the catalytic activity for the hydrogenation of benzalacetone the activation of the whole conjugated system of the mole-
and styrene followed the order PtNi2 > PtNi ≈ PtNi3 > Pt3Ni > cule, which leads to complete hydrogenation to form the sat-
PtNi10 > Pt > Ni. In addition, PtNi2 octahedra were also the urated alcohol product. The synergistic effects of the surface
best catalysts for the hydrogenation of nitrobenzene. structure and electronic properties of Pt or PtNi NCs play a
Then, Li and co-workers41 successfully designed trimetallic key role in controlling the selective hydrogenation of CC
Pt3Ni@M core–shell structures (M = Au, Ag, Rh, Cu) with more and CO bonds of α,β-unsaturated aldehydes.
reactive sites to significantly increase the catalytic performance For the hydrogenation of α,β-unsaturated aldehydes,
for hydrogenation, as summarized in Fig. 4. For the reduction Tsang et al.72 synthesized the Pt NCs with tailored sizes deco-
of nitrobenzene to aminobenzene using formic acid as the rated with Co atoms in a controlled manner. The bimetallic
hydrogen source, Pt3Ni@Au0.5 (containing 0.5 atom % Pt)
Fig. 14 Conversion as a function of time in the reduction of

Fig. 13 Turnover rate for pyrrole hydrogenation to n-C4H10 catalyzed nitrobenzene using formic acid as the hydrogen source catalyzed by
by Rh nanocubes.38 Reprinted with permission from the American trimetallic catalysts containing 0.5 atom % Pt.41 Reprinted with
Chemical Society. permission from the American Chemical Society.
View Article Online
heterostructures exhibit extraordinarily high selectivities for NCs demonstrated a higher activity than the {111}-facet-
carbonyl reduction in α,β-unsaturated aldehydes (such as bounded PtPd NCs. In comparison, {111}-facet-covered
cinnamaldehyde and citral). The results showed that terminal PtxNi1−x(0 < x < 1) showed higher activity than that with
CO hydrogenation can be achieved with high activity, while {100} facets in the hydrogenation of benzalacetone.40 More-
the undesirable hydrogenation of the CC group can be over, tetrahedral Pt NCs with (111) facets were more active
totally suppressed by certain Co decoration on Pt NPs. Later, than cubic Pt NCs with (100) facets in the hydrogenation of
amine-capped truncated octahedral Pt3Co nanocatalysts were 4-nitrophenol.19 Therefore, it can be deduced that the active
synthesized and used by the groups of Zheng and Fu.42 facets are totally different for various compositions of noble-
Capping a Pt3Co (100) surface with amines that contain long metal NCs in different hydrogenation reactions.
carbon chains results in an ordered surface “array” (see Furthermore, Fang and colleagues reported the synthesis
Scheme 8), in which high selectivity towards CO hydroge- of high-quality Pt3Co concave nanocubes terminated with
nation can be achieved because the CC bond in cinnam- high-index crystal facets (Fig. 16).45 These Pt3Co concave
aldehyde does not interact with the surface. The results nanocubes as a new class of nanocatalysts exhibited enhanced
showed the longer the carbon chains in the amine, the catalytic activity in comparison with low-indexed surface
higher the selectivity.
Huang and co-workers43 prepared single-crystalline PtPd
NCs with controllable shapes (namely {111}-terminated and
cubic shapes) and tunable compositions. The obtained PtPd
NCs exhibited high activity in the hydrogenation of nitroben-
zene, and their performance is highly shape- and composition-
dependent with Pt in ∼50% showing the optimum activity
(Fig. 15). It is interesting that the {100}-facet-enclosed PtPd
Fig. 16 (a) TEM image of the as-prepared Pt3Co concave nanocubes;

(b) 3D perspective illustration model of a concave cube; (c) HRTEM of
a single Pt3Co concave nanocube. (d) Fourier transform pattern of the
Scheme 8 Optimized structure of cinnamaldehyde adsorption (ball- concave nanocube shown in (c); (e) stepped surface highlighted from
and-stick) on the Pt3Co (100) surface capped by OAm (line) for the the HRTEM image; (f) scheme of the stepped surface composed of a
selective hydrogenation of cinnamaldehyde.42 Reprinted with mixture of high-index facets with {100} terraces and {110} steps.45
permission from John Wiley and Sons. Reprinted with permission from John Wiley and Sons.
Fig. 15 Catalytic results of nitrobenzene hydrogenation using various PtPd NCs.43 Reprinted with permission from the American Chemical
Society.
View Article Online
2. The synergetic effect between the facet and the capping

agent on the catalytic performance should be investigated.
If the surfactant blocks the active sites of the catalyst, the
removal of surfactants without changing the size, shape and
stability of NCs should be applied. Therefore, effective tech-
nology for obtaining clean surfaces of nanocatalysts should

be developed. Otherwise, surfactants that can increase the
activity or control the selectivity of certain noble-metal nano-
crystals for hydrogenation should be investigated.
3. Different compositions of metal(s) behave individually
in various hydrogenation reactions. Therefore, systematic
investigation on a certain composition of metal(s) and a
selected reaction should be carried out to gain a database of
noble-metal catalyzed hydrogenation. How the structures of
noble-metal NCs influence different hydrogenation reactions
Fig. 17 Conversion of styrene hydrogenation as a function of reaction should be investigated. Then, deep insights into the intrinsic
time by using Pt3Co concave nanocubes and Pt3Co nanocubes. Inset: connection between catalytic properties and structures will
TOFs of the catalysts in units of [mol converted styrene]/[mol catalyst × be achieved.
h].45 Reprinted with permission from John Wiley and Sons. 4. More work should be done on the support of these
faceted NCs. Supports with high specific area and stability
should be selected. Then, a facile and effective method for
terminated Pt3Co nanocubes with similar size in the hydroge- loading of the NCs without losing their well-defined facets
nation of styrene, as summarized in Fig. 17. should be developed. In the future, support effects should be
In addition, Armbrüster et al. prepared single-phase and figured out for the preparation of industrial noble-metal
nanoparticulate GaPd and GaPd2 (3 and 7 nm respectively) nanocatalysts with high performance.
in two steps. The unsupported NPs possess high catalytic Therefore, the most crucial challenge is to develop facile
activity and excellent selectivity in the semihydrogenation of fabrication methods to precisely control the size and shape
acetylene.46 of noble-metal NCs. Moreover, the production of uniform
NCs on a large scale should also be investigated. In the future,
4. Conclusions and outlook a database should be established to correlate the properties
of noble-metal NCs and their activity/selectivity for hydroge-
By means of versatile synthetic methods, uniform noble- nation. Then, it is reasonable to expect the development of
metal NCs with a variety of sizes and shapes have been pre- the shaped noble-metal nanocatalysts with high efficiency,
pared and used for catalytic hydrogenation, including not controllable selectivity, and convenient recyclability.
only simple shapes (sphere, cube, tetrahedron, and octahe-
dron), but also unconventional shapes with high-index facets.
Moreover, some scientists have come up with several treat- References
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Catalytic Hydrogenation by Noble Metals Nanocrystals

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Catalysis

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Catalytic hydrogenation by noble-metal

1. Introduction structure sensitivity of hydrogenation reactions has been

Wanting Zang studied chemical Prof. Guozhu Li received his

Catalysis Science & Technology Minireview

Prof. Li Wang received her Ph.D. Prof. Xiangwen Zhang received

Table 1 Synthesis of faceted noble-metal NCs for hydrogenation

2534 | Catal. Sci. Technol., 2015, 5, 2532–2553

This journal is © The Royal Society of Chemistry 2015

Selectivity to undaturated alcohols: AuPt alloy NPs

This journal is © The Royal Society of Chemistry 2015

Catal. Sci. Technol., 2015, 5, 2532–2553 | 2535

2536 | Catal. Sci. Technol., 2015, 5, 2532–2553

This journal is © The Royal Society of Chemistry 2015

Catalysis Science & Technology Minireview

Recently, Zheng’s group28 synthesized ultrathin palladium

stirred under a CO atmosphere which served as both the

2.2 Functional molecule

Minireview Catalysis Science & Technology

Catalysis Science & Technology Minireview

Minireview Catalysis Science & Technology

Catalysis Science & Technology Minireview

Minireview Catalysis Science & Technology

Fig. 6 (a) Turnover rates of cyclohexane ĲC6H12) and cyclohexene

Catalysis Science & Technology Minireview

Minireview Catalysis Science & Technology

Fig. 7 TOF for crotonaldehyde hydrogenation at 333 K as a function

Fig. 8 Comparison of the kinetic data of catalysts with different

Catalyst T/K k1/s−1 KA/L mol−1 KB/MPa−1 R2 Ea/kJ mol−1

Catalysis Science & Technology Minireview

Minireview Catalysis Science & Technology

Catalysis Science & Technology Minireview

Entry Cat.b P t Conv.c Selectivity[%]

facets exist on the nanostructure. They demonstrated control 3.3 Rh nanocrystals

Minireview Catalysis Science & Technology

effectively stabilized by chemically adsorbed Br− ions from

strongly depend on temperature, as shown in Fig. 13.

exhibited the best performance with respect to both activity

Fig. 14 Conversion as a function of time in the reduction of

Catalysis Science & Technology Minireview

Fig. 16 (a) TEM image of the as-prepared Pt3Co concave nanocubes;

Minireview Catalysis Science & Technology

2. The synergetic effect between the facet and the capping

nology for obtaining clean surfaces of nanocatalysts should

Catalysis Science & Technology Minireview

of the hydrogenation of crotonaldehyde over Pt/SiO2 and 2009, 64, 697–706.

Minireview Catalysis Science & Technology

Atmospheric pressure studies of selective 1,3-butadiene 50 B. Gehl, A. Frömsdorf, V. Aleksandrovic, T. Schmidt, A.

Catalysis Science & Technology Minireview

65 H. Song, F. Kim, S. Connor, G. A. Somorjai and P. Yang, Pt 4510–4511.

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