Chem Soc Rev: Chemical Society Reviews

Volume 44 Number 21 7 November 2015 Pages 7431–7920
Chem Soc Rev

Chemical Society Reviews
www.rsc.org/chemsocrev
ISSN 0306-0012
REVIEW ARTICLE
Manoj B. Gawande, Radek Zboril, Rajender S. Varma et al.
Core–shell nanoparticles: synthesis and applications in catalysis and
electrocatalysis
Chem Soc Rev
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Core–shell nanoparticles: synthesis and

applications in catalysis and electrocatalysis
Cite this: Chem. Soc. Rev., 2015,
44, 7540
Manoj B. Gawande,*a Anandarup Goswami,abc Tewodros Asefa,bc Huizhang Guo,d
Ankush V. Biradar,e Dong-Liang Peng,d Radek Zboril*a and Rajender S. Varma*f
Core–shell nanoparticles (CSNs) are a class of nanostructured materials that have recently received
increased attention owing to their interesting properties and broad range of applications in catalysis,
biology, materials chemistry and sensors. By rationally tuning the cores as well as the shells of such
materials, a range of core–shell nanoparticles can be produced with tailorable properties that can play
important roles in various catalytic processes and offer sustainable solutions to current energy problems.
Received 26th April 2015 Various synthetic methods for preparing different classes of CSNs, including the Stöber method, solvothermal
DOI: 10.1039/c5cs00343a method, one-pot synthetic method involving surfactants, etc., are briefly mentioned here. The roles of
various classes of CSNs are exemplified for both catalytic and electrocatalytic applications, including
www.rsc.org/chemsocrev oxidation, reduction, coupling reactions, etc.
1. Introduction in chemistry.30–33 Besides offering solutions to the traditional

demands for catalysts to be efficient and selective for a particular
Nanomaterials have attracted enormous attention owing to catalytic reaction that will transform raw materials into valuable
their interesting properties as well as utility in the diverse areas chemicals, such as pharmaceuticals and fuels, these nanomaterials
including nanocatalysis,1,2 magnetite-supported catalysis,3–5 could assist in the development of green chemistry, offering the
nanoelectronics,6–10 integrated catalysis,11 etc.12–20 Rapid develop- advantages of waste reduction, atomic efficiency, higher reaction
ment of nanotechnology over the past few decades has allowed rates and also facile catalyst recovery.34–37
researchers to view conventional heterogeneous catalysts from Traditionally, composite nanomaterials constructed with cores
a new perspective.21–24 In particular, catalytic materials can (inner material) and shells (outer layer material), both at nano-
now be prepared with greater precision via nanotech-enabled scale, are broadly defined as CSNs (core–shell nanoparticles).38
processes.25–27 Nanoparticles (NPs) containing noble metals, Though, historically, the term was coined for the concentric
which often serve as active catalytic components, can now be multilayer semiconductor nanoparticles39,40 with the advancement
routinely synthesized with well-defined sizes, shapes, crystal in the field of core–shell nanomaterials, the definition of the core–
facets, structure and composition.28,29 Such controllability over shell nanomaterials can be extended to the class of nanomaterials
materials’ structures could potentially lead to the development having distinct boundary materials covering (either fully or
of new technologies for applications in green, sustainable and partially) the inner component as long as they can be separately
economically-viable chemical processes, which are currently identified. Depending on the compositions and arrangements of
regarded as among the most desirable yet challenging areas the two components in the materials, core–shell nanostructures
can be divided into several classes, including inorganic/inorganic,
a
Regional Centre of Advanced Technologies and Materials, Faculty of Science, inorganic/organic, organic/inorganic and organic/organic type
Department of Physical Chemistry, Palacky University, Šlechtitelů 11, 783 71, CSNs.41–43 As interest in task-specific nanomaterials with multi-
Olomouc, Czech Republic. E-mail: manoj.gawande@upol.cz, radek.zboril@upol.cz functional capabilities and/or enhanced properties is increasing,
b
Department of Chemistry and Chemical Biology, Rutgers, The State University of
core–shell nanostructures are increasingly attracting attention
New Jersey, 610 Taylor Road, Piscataway, New Jersey 08854, USA
c
Department of Chemical and Biochemical Engineering, Rutgers, The State
because of their conducive and versatile compositions and struc-
University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854, USA tures to serve such purposes.44–47 In addition, CSNs may have
d
Department of Materials Science and Engineering, College of Materials, properties that are synergistic between the cores and shells and/or
Xiamen University, Xiamen 361005, People’s Republic of China offer new properties depending on the interactions between the
e
Catalysis Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road,
cores and shells.48–52 Such unique, useful and tailorable proper-
Pune 411008, India
f
Sustainable Technology Division, National Risk Management Research Laboratory,
ties have also advanced CSNs as a very important class of
US Environmental Protection Agency, 26 West Martin Luther King Drive, MS 443, emerging nanomaterials for a wide range of applications in, for
Cincinnati, Ohio, 45268, USA. E-mail: Varma.Rajender@epamail.epa.gov instance, bio-nanotechnology,53–55 enhanced optical devices,56–58
7540 | Chem. Soc. Rev., 2015, 44, 7540--7590 This journal is © The Royal Society of Chemistry 2015
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Review Article Chem Soc Rev
tailored magnetic devices,59–63 electronic optical devices,42 superior catalytic performance of such a layer/shell, (2) synergism
bioimaging systems,64,65 energy storage materials,66 genetic between the shell and the core enabling to achieve higher efficiency/
engineering and stem cells,67,68 fuel cell,69,70 dye sensitized solar yield/selectivity in catalytic applications and (3) combination
cells71 and many important catalytic processes72–82 (Fig. 1). of the properties of the core and shell towards improved/
One important challenge, often faced by chemists working combined applications (e.g. magnetically separable nanocatalysts
in the area of catalysis, is the development of highly active and with the possibility of the repetitive use without the loss of the
selective, robust, low-cost and environmentally benign catalytic catalytic efficiency).

systems. This issue, as a whole or in part, could be addressed by The catalytic and electrocatalytic activity of such catalyst
developing catalytic systems with core–shell structural features. depends on its synergistic interactions between the core and
Among the possible advantages that these types of nanomaterials shell. Primarily there are three major effects (and in most cases
can offer, three major ones can be highlighted: (1) the use of a combined one) that can play important roles in deciding
the core as a support allowing the specific surface (shell) nano- the catalytic/electrocatalytic activity of a particular materials:
architecture in terms of porosity, surface area, etc., thus resulting in (a) ligand effect, which involves the interaction between the
Manoj B. Gawande received his Anandarup Goswami obtained his

PhD degree in Chemistry in PhD in organolithium chemistry
2008 from, Institute of Chemical under Prof. David B. Collum at
Technology (formerly UDCT), Cornell University (2010) and later
Matunga, Mumbai, India. He joined Prof. Kai C. Hultzsch’s group
was awarded several prestigious at Rutgers University to work on
fellowships, including BK-21 organometallic catalysis. He has a
Research fellowship, FCT Research keen interest in heterogeneous
fellowship and recently was catalysis, which he explored in
awarded Mahatma Gandhi Pravasi Prof. Tewodros (Teddy) Asefa’s
Samman, by Govt. of India and NRI group, with special emphasis on
Welfare Society of India. After silica/metal/carbon-based nano-
Manoj B. Gawande several research stints in Germany, Anandarup Goswami materials and their applications.
Portugal, Singapore, England and Presently, he is working as
USA, he is presently working as Senior Researcher and Head of researcher in the field of nanocatalysis at the Regional Centre of
Division of Nanocatalysis laboratory at RCPTM, Faculty of Science, Advanced Technologies and Materials, Faculty of Science, Palacky
Palacky University, Olomouc, Czech Republic. His research interests University, Olomouc, Czech Republic, with Dr. Manoj B. Gawande and
include core–shell/carbon/magnetic nanocatalysis. He has published Prof. Radek Zboril.
nearly 65 scientific papers including several reviews.
Tewodros (Teddy) Asefa is a Ankush V. Biradar received his

Professor in Departments of PhD in chemistry from the
Chemistry and Chemical Biology National Chemical Laboratory,
& Chemical and Biochemical Pune/University of Pune under
Engineering at Rutgers University the supervision of Dr Shubhangi
at New Brunswick, USA. He Umbarkar in 2009. After gradu-
received his MSc from SUNY- ating, he moved to Prof. Tewodros
Buffalo (1998) and his PhD from Asefa’s group, first at Syracuse
University of Toronto (2002). He University and then Rutgers
received fellowships to serve as University in New Jersey, USA,
Visiting Professor at Kyoto where he worked on the synthesis
University, Japan (2014); Maringá and catalytic properties of multi-
Tewodros Asefa State University, Brazil (2014– Ankush V. Biradar functional nanomaterials. In 2012,
2017); and ETH Zürich, Switzer- he moved back to India and joined
land (2015). He also received NSF CAREER award (2007–2012), NSF the National Chemical Laboratory, Pune, as a Scientist. His research
Special Creativity award (2011), Rutgers Board of Governors Research interests lie in the development of nanostructured catalysts (especially
Fellowship (2012), and NSF’s American Competitiveness Fellowship non-noble metal-based ones), and their utilization for oxidation and
(2010). He co-edited a book on Nanocatalysis (Wiley) and wrote 120 hydrogenation reactions.
papers and few book chapters.
This journal is © The Royal Society of Chemistry 2015 Chem. Soc. Rev., 2015, 44, 7540--7590 | 7541
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Chem Soc Rev Review Article
In addition to decreasing the amount of expensive material used

in the catalytic system by placing Pt only as a shell monolayer
over Co and Fe surfaces, the composite materials (Pt3Co and
Pt3Fe) could result in improved oxygen adsorption energy, and
thereby enhanced catalytic activity and stability.85,86
Additionally, rational design and applications of CSNs with
tailored structures and efficient catalytic activity can often be

investigated by applying density functional theory (DFT) and
other theoretical considerations.49,87–89 DFT studies, which have
been successfully used to model various chemisorption and
desorption processes, primarily involve the d-band center model.90
In such a model, the ligand and strain effect from the core to
the shell components are assumed to affect the d-band width or
d-band filling.91,92 By harnessing such theoretical designs,
supported by experiments, CSNs catalysts can be prepared with
enhanced activity and selectivity.93
Fig. 1 Applications of CSNs in various areas of modern technology Recently, Tedsree et al. synthesized Ag NPs coated with a
especially in the field of catalysis.
thin layer of Pd atoms, which showed significantly enhanced
catalytic activity toward hydrogen evolution from formic acid at
core and the shell because of atomic vicinity affecting the charge ambient temperature.94 The improved catalytic activity of the
transfer between the components, thus altering the band-structures; materials was attributed to the fact that the Pd shell contains
(b) ensemble effects, which is governed by the material’s adsorption terrace sites and is electronically activated by the Ag core.
on the surface due to the presence of distinct atomic groups, Meanwhile, lattice strain has been found to be advantageous
and finally (c) geometric effects, originating from the difference for tuning the catalytic activity of core–shell structure.95 Xu75
in reactivity of the surface atoms because of their three dimen- and Li96 synthesized Au@Co CSNs that have efficient catalytic
sional structural constraints (e.g. surface strain). activity for the hydrolytic dehydrogenation of ammonia borane.
For instance, by coating precious metal catalysts (e.g., Au, Pt Similarly, Ag@Ni CSNs synthesized via a one-pot synthetic
or Pd), as a monolayer on the surfaces of non-precious metal- procedure showed enhanced catalytic activity towards hydrogen
based nanomaterials (e.g., Ni, Fe or Co), atom-economical and cost evolution from the dehydrogenation of sodium borohydride in
effective CSNs with good catalytic efficiency can be produced. This aqueous solutions97 and transfer hydrogenation reactions of
strategy has been successfully exploited by Son et al. via Ni@Pd aromatic nitro and carbonyl compounds.98 In another example,
core–shell NP-based catalysts that displayed high catalytic activity alumina-supported Cu@Ni and Ni@Cu CSNs were shown to have
for the Sonogashira coupling reactions.83 Similarly, carbon- comparable catalytic activity towards water-gas-shift reaction,
supported Pd@Co CSNs were synthesized by Wang et al. and giving significantly low undesirable methanation side-reaction,
used as electrocatalysts for the oxygen reduction reaction (ORR).84 than conventional supported Ni catalyst.72 In other words, the
Radek Zboril received his PhD Rajender S. Varma was born in

degree from Palacky University, India (PhD, Delhi University
Olomouc. After his PhD study, he 1976). After postdoctoral research
underwent several foreign stays at at Robert Robinson Laboratories,
universities in Tokyo, Delaware Liverpool, UK, he was a faculty
and Johannesburg. Currently, he member at Baylor College of
is a Professor at the Department of Medicine and Sam Houston State
Physical Chemistry and General University prior to joining the
Director of the Regional Centre of Sustainable Technology Division
Advanced Technologies and at the US Environmental
Materials at Palacky University, Protection Agency in 1999. He has
Olomouc. He has published more over 40 years of multidisciplinary
Radek Zboril than 250 papers in prestigious Rajender S. Varma research experience and is lately
journals with research interests engaged in greener assembly of
in nanomaterials area that include iron and iron oxide based nanomaterials and the sustainable applications of magnetically
nanoparticles (NPs), silver NPs, carbon nanostructures, and retrievable nanocatalysts. He is a member of the editorial advisory
magnetic NPs and their applications in biomedicine, environ- board of several international journals, published over 415 scientific
mental technologies, sensing and catalysis. papers, and has been awarded 14 US Patents.
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selectivity of the water-gas-shift reaction was improved by using of CSNs as well as different characterization techniques are
CSNs as catalysts. By incorporating magnetic materials, multi- briefly described in the following sections.
functional CSNs with catalytic as well as magnetic properties
(the latter being useful for the ease of recyclability/magnetic 3.1. Synthesis of core–shell nanocatalysts
separation of the CSNs after the reaction), could be synthesized As far as synthesis is concerned, the techniques that have been
in an analogous manner.99 This synthetic strategy has been
used to synthesize nanomaterials can generally be applied to

widely applied for the fabrication of various bifunctional nano- prepare the core and/or shell components of CSNs. Although
materials, e.g., magnetic and optically/photocatalytically active ‘‘top-down’’ approaches are possible, in which external controls
Fe3O4@ZnS NPs.57 Stark and co-workers have reviewed nano- like microfabrication techniques, mechanical stress, etc. are
materials comprising ferrite NPs and their use as a semi- utilized to break down the bulk materials to the desired
heterogeneous catalyst support.100 nanomaterials with different shapes and sizes, ‘‘bottom-up’’
Overall, the variety of CSNs with different sizes (5–500 nm), techniques are mostly preferred. In the latter case, the materials
morphologies (spherical, honeycomb, hollow, etc.), composi- are synthesized from molecular or atomic building blocks, relying
tions (organic, inorganic etc.), and their catalytic applications in on the inherent chemical properties of the individual constituents
various types of catalytic processes, organic reactions and and their mutual interactions to allow control over the shape
electrocatalysis are presented in detail. For instance, Fe2O3@Au and size of the nanomaterials. Using bottom-up synthetic
CSNs,101 carbon-coated cobalt,102 FeCo/graphitic core–shell methods, core and shell(s) of CSNs can be synthesized either
nanocrystals,55 and FePt@ZnO CSNs103 exhibit promising in a stepwise or one-pot fashion. Both of these approaches have
catalytic properties for various reactions. The noble metal (Au been used for the synthesis of CSNs. However, other new and
and Pt)-supported magnetic CSNs not only have strong mag- modified procedures are continuously being developed and
netic properties allowing excellent recovery of the catalysts after reported in the literature.
its use via magnetic separation but also exhibit enhanced 3.1.1. Classification. Inspired by the classification developed by
catalytic properties. The advantages pertinent to both shell Paria,122 the current section focuses on the syntheses of different
and the core materials, in addition to their nanoscale struc- CSNs according to type (rather than the procedures employed to
tures, has motivated worldwide research in the synthesis and make them) of the materials and categorizes CSNs in two main
investigation of multifunctional CSNs for the catalysis of classes: organics (Section 3.1.1.1) and inorganics (Section 3.1.1.2)
various chemical reactions (Fig. 1).104–121 (Fig. 2).134 The ‘‘organic’’ materials are related to carbon-based
materials (mostly polymers), whereas the ‘‘inorganic’’ class includes
metal, metalloid and metal salt NPs. Synthetic methods employed
2. Focus of review for each of these categories are discussed in this review with recent
The focus of the present review is to provide an up-to-date examples. Towards the end, a modern classification approach
appraisal of CSNs and their potential applications in catalysis based on the shell properties of the core–shell nanomaterials is
and electrocatalysis, encompassing oxidation, reduction, semi- included in view of the increasing importance of nanocatalysis
hydrogenation and carbon–carbon coupling reactions, oxygen (Section 3.1.1.3).
storage, etc.
In addition, the structure–property relationships of the 3.1.1.1. Organics. Although these types of CSNs are relatively
materials, especially the effect of shape and size of both core new compared to conventional CSNs, the advantages of using
and shell on the properties of the materials and their effects on carbon-based compounds, particularly with regard to the stability/
catalysis are discussed. The detailed preparative procedures for biocompatibility of the material, have generated a great deal of
various types of CSNs have been omitted in this review as they interest.135 The syntheses of such materials mostly rely on poly-
have been extensively covered earlier.122 However, representative merization techniques to prepare the organic core, shell or both.
methods, including basic general procedures for various classes The basic strategy of polymerization involves formation of 3D
of CSNs, are briefly mentioned, followed by more detailed network-like structures via addition of several units of appropriate
description of a modern classification approach with recent monomeric substrates with key functionalities. Although organic
examples.123–130 Moreover characterization techniques for CSNs cores are often synthesized first, organic shells can also be
are also mentioned briefly. prepared in situ. Additionally, surface modifiers, such as surfac-
tants, polyeletrolytes, etc., can be used to improve the coating
efficiency and stability. Recently, Asefa and co-workers success-
3. Synthetic and characterization fully demonstrated the preparation of polyaniline (PANI) inside
techniques of core–shell nanoparticles mesoporous channels of amine-functionalized SBA-15 using
persulfate as an oxidant and used the resulting composite
As mentioned earlier, the recent upsurge in the field of CSNs core–shell nanostructures to produce mesoporous carbons that
can be attributed to their diverse applications because of their can serve as an efficient metal-free electrooxidation catalyst for
unique structural, physical and chemical properties.122,131–133 various reactions.15,136 Chen and co-workers demonstrated facile
Although the review primarily focuses on the catalytic proper- syntheses of shells around metallic systems using (1) amphiphilic
ties of CSNs, the synthetic strategies, used to make assemblies block copolymers (polystyrene-block-poly(acrylic acid) (PSAA)),
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Fig. 2 General classification of CSNs based on material-type (along with the most prevalent synthetic methods) and properties of their shells.
and (2) conductive polymers (such as PANI, polypyrrole (PPy), etc.) to The broad class of ‘‘metal-based CSNs’’ requires further sub-
develop metal-based CSNs.38 Other carbon-based materials, such as classification as it covers the entire range of metal, metal alloys,
fullerenes, carbon nanotubes (single-walled or multi-walled), etc., metal oxides, metal salts, etc. and can thus be sub-divided into
have also been harnessed for different catalytic transformations. three parts: (i) metallic NPs, (ii) metal oxides, and (iii) metal salts.
Detailed discussion on the syntheses of these materials is In general, metallic NPs are synthesized via reduction of
beyond the scope of this section. However, in brief, most of their corresponding metal-salts, either using external reducing
them are prepared via doping or functionalization of carbon agents (such as NaBH4, hydrazine, etc.) or via trans-metallation
materials with different active species, which can also ultimately utilizing the intrinsic redox properties of the metal precursors.
result in hollow CSNs after removal of organic part either via The reaction medium, temperature and type of reducing agent
extraction or calcination;137–140 recent examples from the litera- influence the reaction kinetics, and any manipulation of these
ture are described in Section 3.1.1.3. parameters may lead to significant differences in particle growth,
size, shape, and thereby different chemical, physical, optical and
3.1.1.2. Inorganics. The ‘‘inorganic’’ materials can be categorized biological properties.
further into two main sub-categories, namely (a) silica-based Among the metal oxide NPs, titania-based materials, often
CSNs and (b) metal-based CSNs. obtained via the ‘‘sol–gel’’ method (similar to silica), possess a
Almost all the silica-based CSNs are synthesized using sol–gel range of chemical, physical and optical properties that render
chemistry, historically known as the Stöber method.141 This wet them useful in photo-, bio- and energy-related applications.
chemical method entails the hydrolysis and subsequent conden- Additional actions such as ‘‘thermal-treatment’’ may allow tuning
sation of silicon alkoxides or silicon halides in alcohol, water or a of the structures, physical robustness or porosity of the materials.
mixture thereof in the presence of a base catalyst, such as In general, the kinetics involving the formation of titania-based
ammonia, to afford uniform colloidal microspheres. Because of materials is faster than that of silica-based materials due to the
its simplicity, reproducibility as well as versatility, this method has relatively higher reactivity of the precursors in the former case.
been applied to synthesize different types of silica-based CSNs Nevertheless, because of the availability of various structurally and
with great success. Although most of the CSNs prepared using electronically different precursors, as well as the interesting
this method involve solid, non-porous SiO2, newer strategies have phase-behavior, the final structure and reactivity of the precursors
now been developed to generate porous materials using either can be modulated to produce different types of nanostructures.
template-based techniques or post-synthetic modifications. This, In the context of CSNs, several examples have recently been
in turn, allows not only increased surface area of the resulting reported where TiO2 in different forms was used as one of the
CSNs but also better accessibility of the cores as well as shells components (mostly as shell).133 Apart from the sol–gel method,
themselves. Moreover, the pores of the materials can further be co-precipitation or thermal decomposition methods are also
modified with different functional groups, providing the materials used to access other metal oxides depending on the chemical
with multi-functionality for various catalytic applications. properties of the metal precursors. Whereas the co-precipitation
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technique is mainly used for metal oxides/hydroxides that can by using different electrolytes or by varying the synthetic
be precipitated under basic conditions, thermal decomposition strategy. Last, but not least, recent developments in microwave
involves high temperature treatment or thermolysis of organo- technology have enabled the synthesis of either component of
metallic precursors in the presence of oxygen or air to afford CSNs in shorter time with moderate to large control over
the final product. Pertinent examples of the latter case include structural properties.148–150
magnetic core–shell nanocatalysts where the core is synthe- In addition to such classifications, some of the hybrid-
sized using a combination of hydrolysis and thermal treatment structures (e.g. metal–organic-frameworks,151 zeolite-based
of Fe-precursors.142–144 In addition, chemical vapor deposition structures,152 covalent-organic-frameworks,153 etc.) have also
(CVD) and pulse layer deposition (PLD) have also been employed been introduced recently in the literature, and hopefully a
to prepare metal oxides from gaseous precursors and are often special classification and major discussion may be warranted
applied for the in situ synthesis of metal oxides. in future for these classes of materials.
In the class of ‘‘metal-salt’’-based CSNs, metal chalcogenides/
3.1.1.3. Classification based on shell properties. Given the current
halides have found a range of applications in semiconductor-
status of core–shell nanocatalysis, we envision that a modern
based devices and (bio)imaging. They are commonly synthesized
classification based on the shell properties of the materials would
by precipitating metal salts from a mixture of metal precursors
be beneficial, particularly for comparison of different synthetic
and desired counter ions in the presence of stabilizer/capping
strategies leading to varied shell properties. Broadly, these materials
agents. In this case, the inherent reactivity of metal salts toward
can be divided into three major categories: (1) hollow-core–shell,
external parameters (e.g., oxygen, temperature, etc.) plays an
(2) core–multishell, and (3) core–porous-shell, each of which is
important role, rendering further modification. A relatively
discussed briefly in the following sections.
new method, named as ‘‘successive ionic layer adsorption and
reaction’’ (SILAR, first developed by Ristov145 but its acronym 3.1.1.3.1. Hollow-core–shell NPs. Although not essentially
was coined by Nicolau146) has been developed to synthesize CSNs by definition, hollow-core–shell type nanomaterials need
metal-salt-based CSNs, mainly for their semiconductor and to be mentioned here as the first step in their preparation is
photovoltaic properties. This method allows uniform and isotopic analogous to the one used for making normal CSNs described
growth of shell materials covering the core particles and mini- earlier. Once, the CSNs have been synthesized, the core is sacri-
mizes the formation of unwanted nanocrystals of just the shell ficed using a variety of conditions specific to the core materials:
material. Additionally, annealing between successive depositions organic core materials are removed either by calcination or
(which is particularly important for making multishell NPs) allows dissolution in organic solvents, whereas inorganic core(s) are
elimination of the possible biasness that might generate from purged with strong acid or base. The removal of core materials
either the core or shell materials. The progress on different SILAR offers some additional advantages depending on its application.
techniques have also been reviewed by Tolstoy.147 In the case of multiple shells (described later), the inner shells
Beyond such classifications and the aforementioned methods, can also be removed using specific methods.
depending on the applications as well as availability of sophisti- Possibly the most common examples of this category are the
cated techniques, alternate energy inputs, such as ultrasound-, inorganic oxide shell-based hollow core–shell particles, which
and microwave-irradiation, electrodeposition, etc., have been are prepared from their precursors either separately or during
used for the synthesis of various CSNs. In the case of sono- calcination of the organic cores. Silica, titania or ceria (some-
chemical synthesis, varying the sound frequency helps to (i) times in combination) are often used because of their versatility
form local microreactors/cavities in which reaction can occur, in crafting different nanostructures. For example, Zhang et al.
(ii) promote better mixing (therefore less agglomeration), and utilized a combination of sol–gel and hydrothermal action to
(iii) produce short-lived shock waves, which can generate synthesize Pd@hCeO2 (Pd NPs embedded in a hollow shell of
localized heating in order to produce smaller particles. The CeO2) starting from carbon microspheres and using the latter
electrodeposition method generally involves deposition of as a sacrificial core;154 Pd NPs, prepared via reduction (using
the substrate/core material on the surface of an electrode or alcohol) in the presence of poly-vinylpyrrolidone (PVP) as capping
supported matrix from a bulk electrolyte solution using an agent, were first adsorbed on carbon microspheres (generated via
electric field, followed by further decoration of the shell either thermal treatment of glucose). Hydrothermal treatment was then
Fig. 3 Schematic illustration of the fabrication of Pd@hCeO2 core–shell nanocomposite particles. Reprinted with permission from ref. 154. Copyright
2013 American Chemical Society.
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employed to coat CeO2 outside the Pd-NP-grafted carbon spheres,

followed by calcination in presence of air to remove the carbon
core (Fig. 3). The resulting Pd@hCeO2 was shown to be highly
active toward the thermal and photocatalytic reduction of
aromatic nitro compounds with excellent recyclability.
The presence of the shell in Pd@hCeO2 prevents leaching
and aggregation of the Pd-NPs in the catalytic reaction. Following

an analogous pathway, core–void–shell anatase TiO2 was prepared
via solvothermal treatment of sucrose and TiO2, followed by
removal of the carbon-precursor via calcination.155 The final
material showed enhanced photocatalytic activity for the degrada-
tion of rhodamine B and improved lithium storage capacity.
A slightly different approach for the preparation of hollow-core–
shell mesoporous TiO2 has been reported156 using a stepwise
protocol based on seed-emulsion-polymerization, followed by
coating of the Ti-precursor and subsequent calcination to
generate hollow TiO2 materials for electrophoretic studies.157,158
Ohtani and co-workers adopted a similar procedure involving
solvothermal and calcination techniques for the synthesis of
SiO2/void/TiO2 (and also platinized SiO2/void/TiO2).159,160 These
photocatalytically active materials were used in the stereoselective
synthesis of pipecolinic acid. In a related example, SiO2/Mg(OH)2
spheres have been prepared using a modified Stöber method to
prepare SiO2 spheres (cores), followed by polyethyleneglycol
Fig. 4 Illustration of the fabrication process of the ‘‘wire-in-tube’’ type
(PEG) and sodium dodecyl benzene sulfonate (SDBS) mediated CoO@TiO2 nanostructure. Reprinted with permission from ref. 167. Copy-
coating of Mg(OH)2 onto the SiO2 spheres;161 depending on the right 2012 Royal Society of Chemistry.
ratio of precursors, different morphologies, including hollow
core–shell and honeycombed structures, were obtained. Apatite-
type La9.33(SiO4)6O2 hollow nanosphere catalysts were synthesized synthetic methods (to remove the sacrificial middle layer),
using a protocol that included a combination of hydrothermal followed by annealing to procure the porous material to produce
synthesis (to prepare the cores), modified Stöber method (to coat a hollow-core–shell microstructure (Fig. 4).167 In that case, a
the cores with silica shells), thermal treatment (to form a hollow CoO precursor was first synthesized on a nickel foam using a
structure via decomposition of cores) and finally solvothermal hydrothermal process, followed by coating of the ‘‘as-grown
treatment (for controlled etching of the silica layers); the resulting CoO nanostructure’’ with Al2O3 and then with TiO2 using ALD
material was shown to catalyze oxidative coupling of methane.162 method. The removal of sacrificial Al2O3 with strong base and
Another major class of oxides, i.e., zeolites (aluminosilicates), subsequent annealing afforded CoO@TiO2 CSNs that showed
has also been used as a component of numerous CSNs. Recently, enhanced activity as supercapacitor electrodes. The ALD method
morphological control of zeolites has been achieved using a provides better control over the thickness of the resulting coating
polymer network with special attention to the synthesis of hollow compared to other methods – an aspect particularly important
core–shell structures.163 for catalysis. A detailed study of the solvothermal synthesis
Besides silica, ceria or titania, other metal oxides have been of Co(OH)2 based flowerlike hollow core–shell structures has
explored for synthesizing hollow CSNs. For instance, the synthesis also been reported.168 Plasma polymerization was also used to
of hollow core–shell ZrO2@void@BiVO4 NPs that can serve as prepare hollow NPs from simple organic substrate.169
visible light photocatalysts for the photodegradation of methylene In another example related to biosensing, a ‘‘nano-sheet’’-
blue has been investigated.164 Their synthetic strategy involved based titania microsphere encapsulating horseradish peroxidase
initial hydrothermal treatment of aqueous Bi(NO)3 and NH4VO3 to (HRP) was synthesized by a hydrothermal method followed by
synthesize BiVO4 core, followed by successive coating of carbon trapping of the enzyme via adsorption.170 The resulting material
(glucose as carbon precursor) and ZrO2 (using ZrOCl2). Finally was used for mediator-free bio-sensing of H2O2 aided by the
calcination in the presence of air removed the carbon layer redox-active HRP enzyme. The structure of the material was
to afford ZrO2@void@BiVO4. Zhang et al. described a novel, shown to be dependent on the reaction time, while its hollow
one-pot synthesis of an iodine incorporated (core) BiOCl shell structure enabled better electron transfer as well as higher
structure. Depending on the ratio of inorganic precursors, they stability of the material. In a related example, the facile synth-
obtained hierarchical or pure hollow-structures, which showed esis of a hollow core–shell NiO microsphere has been reported,
catalytic activity towards the photodegradation of phenol and where hexamethylenetetramine was used as sacrificial carbon
rhodamine B.165,166 Fan and co-workers reported a combination source. A lamellar template-based mechanism involving Ni2+ ions,
of hydrothermal, atomic-layer-deposition (ALD) and solvothermal sodium citrate and ethanol leading to intercalated Ni-hydroxide
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the cores), encapsulation (via a second polymerization to make

outer shells), and finally selective dissolution (of the core).174 A
template-based synthetic method was used (involving emulsion
polymerization and subsequent hydrothermal technique) to prepare
hollow core–shell microspheres of spinel ferrites (MFe2O3, where
M = Zn, Co, Ni, Cd).175
In addition to metal oxides, different metal-based hollow

core–shell structures have been synthesized. Ye et al. demon-
strated the phase-transfer based synthesis of Ag@Ru hydrosol
(with ruthenium shell) via a ligand exchange reaction.176 The
Ag-core was finally removed by treatment of the material with
aqueous NaCl solution, which was followed by an additional
phase-transfer recovery step to afford hollow Ru NPs. Niu and
Fig. 5 Schematic of the theoretical model for the lamellar template and
co-workers reported the synthesis of hollow Ag@Pd core–shell
morphology evolution of hollow core–shell NiO. Reprinted with permis-
sion from ref. 166. Copyright 2013 Elsevier Ltd. nanowires (NWs) that can catalyze formic acid oxidation. The
material was synthesized using a seed-mediated growth method
(successive chemical reduction), in which galvanic displacement
layers during an alkalization process was suggested (Fig. 5);166 was suggested to be responsible for the formation of the hollow-
the final product, obtained via calcination in the presence of structure in the material.177 A similar strategy was employed to
air, was shown to have excellent supercapacitive properties. synthesize hollow Au@Pd and Au@Pt core–shell nanocatalysts
The advantages of utilizing the intrinsic magnetic properties for ethanol oxidation.178 Also, a one-step pyrolysis method was
have been thoroughly demonstrated for Fe-oxide based materials. developed for the synthesis of hollow carbon nanospheres with
For instance, a two-step solvothermal synthetic method has been a supported PtRu electrocatalyst for methanol oxidation.179,180
developed to synthesize ferrimagnetic bisphthalonitrile–Fe3O4- The synthesis of hollow core–shell and flower-like Au–TiO2
hollow-core–shell microspheres.149 In the first step, Fe3O4 NPs nanocomposite materials with photocatalytic activity towards
were formed by the reduction of FeCl3 using ethylene glycol in adsorption and photon-assisted desorption of thiol is another
an autoclave; high boiling ethylene glycol was used because example, where a simple, controllable, wet chemical synthetic
of its ability to reduce the metal-salts, whereas sodium acetate method was employed.181
and polyethylene glycol (PEG) were added to prevent particle One of the major applications of the hollow-core–shell archi-
agglomeration. Next, bisphthalonitrile (BPHR) solution and tecture is in the development of anode materials for lithium ion
Fe3O4 NPs were stirred to coat the Fe3O4 with BPHR molecules batteries. Li and co-workers have summarized recent progress in
via physical adsorption, followed by another solvothermal procedure the synthesis of Si@C core–shell composite materials, particularly
to polymerize BPHR molecules into iso-indole on the surface of for lithium ion battery applications, with an additional discussion
Fe3O4. During this process, aggregation of Fe3O4 NPs resulted in on their future perspectives.182 Owing to the potential of hollow
hollow hybrid microspheres. Earlier, a less complicated synthesis core (silicon)–shell (carbon) nanocomposites as an anode material
was reported to prepare hollow core–shell a-Fe2O3 hierarchical in lithium ion batteries, several variants of similar structures have
nanostructures, which were used for the photocatalytic degradation been prepared.183 For instance, in the procedure, reported by Liu
of phenol.171 A similar synthetic strategy was also reported for and co-workers, first Si nanospheres were calcined in the presence
the synthesis of magnetic hollow core–shell structures for drug of air to coat their surfaces with an oxide layer. Next, carbon
delivery, where their formation was suggested to occur via a was coated using chemical vapor deposition method.183 Finally,
possible Ostwald ripening mechanism (Fig. 6).172 etching of the silica layers around the NPs delivered hollow Si@C
The synthesis of iron oxides@SnO2 ‘‘quasi’’ hollow-structures nanocomposite particles. A coaxial electrospinning method has
has been reported using a seed-mediated hydrothermal method also been employed to synthesize Si(core)–hollow carbon nano-
to produce a photocatalytically active material.173 In another fibers (sheath), that were shown to be a promising anode material
study, Fe3O4-embedded hollow polymer spheres were synthe- in lithium-ion batteries.184 The mechanistic details of the
sized using a combination of various techniques: polymerization core–shell interaction in coaxial electrospinning were previously
(to synthesize the cores), adsorption (to graft the Fe3O4 NPs on explored,185 focusing mainly on carbon nanotubes (CNTs).
Fig. 6 Illustration of the possible formation mechanism of core/shell hierarchical nanostructures via Ostwald ripening process in the presence of various
precursors. Reprinted with permission from ref. 172. Copyright 2008 American Chemical Society.
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Fig. 7 Preparation of Sn@carbon NPs encapsulated in hollow carbon nanofibers. Reprinted with permission from ref. 187. Copyright 2009 Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim.
Beyond silicon, combining alcoholysis and subsequent calcina- Hollow nanostructures were also synthesized by employing bio-
tion involving SnCl2 and glycerol as metal and carbon precursors, polymeric systems as precursors. Lipid–polymer–lipid-hybrid
respectively, hollow SnO2@C CSNs, with enhanced lithium-ion hollow nanostructures were synthesized using a combination
battery storage capacity has successfully been synthesized.186 of a double-emulsion and solvent evaporation technique and
A similar synthetic method has been used to make Sn@carbon self-assembly route.190 Another study described the synthesis of
NPs in bamboo-like carbon nanofibers for a similar potential a pH-sensitive hollow polymer microcapsule via sequential steps
application in lithium-ion batteries (Fig. 7).187 Lately, ‘‘dealloying’’ of involving two-stage distillation, precipitation polymerization,
Li from a Li–Sn alloy using an electrochemical method produced followed by removal of the core.191 Nakashima and co-workers
hollow CSNs along with other different bicontinuous micro- reported several synthetic routes involving core–shell-corona
structures depending upon the composition, size of particles type polymeric micelles as a versatile template for the synthesis
and also kinetics of the process.188 of inorganic hollow nanospheres.192
Apart from the conventional ‘‘inorganic’’ precursors based More sophisticated techniques were recently developed for
techniques, an ‘‘all-organic’’ based synthesis of hollow NPs has the assembly of unique nanostructures. For example, He et al.
been reported, which involved synthesis of poly(N-isopropyl- used g-ray assisted polymerization (Fig. 8).193 By applying a combi-
acrylamide) (PNIPAM) cores by controlled heating above the nation of laser-induced deposition and self-assembly synthetic
LCST (lower critical solution temperature) of polymers in the procedures, Lei reported carbon nitride-based materials with
presence of a small amount of sodium dodecyl sulfate, followed different microstructures, including flower-like, hollow core–
by the formation of shells via radical copolymerization using shell and nanorod structures.194
2-hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol)- Though, the detailed discussion is out of the scope of this
dimethacrylate (PEG-DMA) as cross-linking agents.189 Subsequent current manuscript, multiwalled carbon nanotubes (MWCNTs)
partial removal of the PNIPAM cores by dialysis resulted in the can be combined with various materials to produce diverse hollow
final material. In another study, the synthesis of two-layered CSNs displaying interesting properties. Since the discovery of
hollow chiral NPs using a combination of polymerization, sol– single and multiwalled carbon nanotubes, interest in this class
gel, and extraction methods has been reported and the materials of materials has increased because of their potential applications,
have been employed in the enantioselective crystallization of alanine. ranging from catalysis to nanoelectronics, and also for the
Fig. 8 Schematic illustration of the synthesis of polymer microspheres with a hollow core/porous shell structure. Reprinted with permission from
ref. 193. Copyright 2005 American Chemical Society.
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option of affixing various classes of functional groups via chemical synthesized by the SILAR approach in which individual layers
or physical methods.195–197 As far as syntheses of such materials are synthesized starting with metal-salts/metal–chalcogenides
are concerned, arc-discharge, laser-ablation, electrolysis, chemical- on the core materials. The first synthesis of multilayered QDs
vapor-deposition and, to some extent, sonochemical and hydro- was reported by Shi and co-workers,201 subsequently followed
thermal procedures have been deployed depending on the by several synthetic strategies for preparing multishell QDs. For
desired application; further modifications are also possible.198 example, Park group has incorporated a PbxCd1xS interlayer
Another similar hollow CSNs involving fullerenes (another form between a PbS and CdS layer in a PbS/CdS/ZnS quantum-dot-
of carbon nanomaterials) can be made using aforementioned sensitized solar cell using the SILAR method.202 A more complex
technologies. Although typical synthetic procedures mostly rely on CdSe/CdS/CdS/Cd0.75Zn0.25S/Cd0.5Zn0.5S/Cd0.25Zn0.75S/ZnS/ZnSQDs/
arc-discharge, different metals can be incorporated either via vapor PMMA bulk nanocomposite has been synthesized using a combi-
or solution phase doping.199 Encapsulation of various molecules nation of SILAR method (to prepare layered QDs) and photo-
inside the fullerene cage (known as ‘‘endohedral fullerenes’’) polymerization (to synthesize the outer organic shell) using
has recently been exploited and the synthetic approaches mainly 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO) as the
entail trimetallic-template, ion-bombardment, high-pressure and initiator (Fig. 9).203 In their synthetic scheme, the authors reported
the relatively new CAPTEAR (chemically adjusting plasma tempera- modification of the QDs with the amphiphilic polymer poly(ethylene
ture, energy, and reactivity) synthetic methods to produce carbon- glycol)-oleate (PEG-oleate) in order to make a homogeneous
based core–shell type nanostructures.200 dispersion. Meyer also reported a similar approach to synthe-
size QDs followed by photopolymerization of the shell materials
3.1.1.3.2. Core-multishell NPs. In lieu of removing some parts on a glass surface and showed the application of the materials as
of the materials for forming ‘‘hollow NPs’’, coating the core solar-concentrators.204 Peng,205 Li,206–209 Han,210 Masumoto,211,212
materials successively with similar or different types of materials Hollingsworth,213 Dai,214 Cho215 and Mews216 have employed
can result in so-called ‘‘core–multishell NPs’’, which have been similar stepwise successive deposition methods to synthesize
explored recently for a number of applications ranging from QDs for different photovoltaic applications. Gamelin and
catalysis to biology. These types of NPs are generally synthesized co-workers reported an analogous technique for Mn-based
in a stepwise manner and mostly designed to utilize different water-soluble dual-emitting core–multishell QD nanocrystals
functionalities of the multishell rather than just to protect the for optical thermometry applications.217 A combination of
core materials. Furthermore, the inner layers of such NPs can MW-assisted synthesis and the SILAR method was employed
sometime shield the core from outer layers, which may otherwise to generate core–shell and core–multishell materials, and
not be compatible with each other. the final nanocrystals (NCs) were shown to be useful for cell
Until recently, most of the research efforts on core–multi- imaging applications.148 The surface chemistry of core–multi-
shell nanomaterials were concentrated on applications based shell InP (Indium Phosphide) QDs (comprising of an InP core
on the optical and electronic properties of the materials rather coated with a zinc blende bulk structure surrounded by an
than catalysis. As a consequence, most of the materials belong organic coating), prepared via the SILAR method was exten-
to the inorganic type and are mainly synthesized using strate- sively studied by Chaudret to explore the intricate interaction
gies similar to those described in earlier sections. In addition, between the different layers.218
due to the advancement and availability of various sophisti- Another method of utilizing the above-mentioned ‘‘layer-by-
cated instrumentation, many other novel materials with unique layer’’ approach for generating multishell materials involves
properties can also be made. In the following section, recent successive deposition of either a liquid or vapor of the materials
examples of core–multishell nanomaterials along with their onto a surface. For example, vertical heterostructures, composed
respective synthetic strategies are described to provide a holistic of core–multishell Ga(In)P/GaAs/GaP grown on a flat Si(111)
picture of this important area. surface, were synthesized by a layer-by-layer vapor–liquid–solid
Perhaps the most prevalent literature under this category (VLS) synthetic method involving a conventional bottom-up
belongs to quantum dots (QDs). These are the nanoparticles, mostly approach.219 A successive layer-by-layer (SLBL) strategy was also
Fig. 9 In situ polymerization method for the generation of transparent QDs/PMMA nanocomposites. Adapted with permission from ref. 203. Copyright
2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Fig. 10 (A) SLBL synthetic procedure for core@shell UCNPs (up-conversion nanoparticles). (B–D) Schematic of the synthesis of shell thickness
controllable b-NaGdF4:Yb,Er@NaYF4 CSNs. Reprinted with permission from ref. 220. Copyright 2013 American Chemical Society.
employed to fabricate core–multishell NPs using Re–OA (rare-

earth metal chlorides in oleic acid at 140 1C to make the cores)
and Na-TFA–OA (sodium trifluoroacetate dissolved in oleic acid
at room temperature to make the shells) (Fig. 10).220 In the latter
case, the authors showed the versatility of the synthetic method,
accommodating different phases as well as allowing better
control over the shell thickness and dopant positions via simple
variation of the reaction conditions and precursor solutions.
Takashi and co-workers used a phosphine-free method entitled
‘‘Selective Area Metal Chemical Vapor Epitaxy (SA-MOVPE)’’ (a
variation of chemical vapor deposition for achieving selective
and controlled deposition) to synthesize core–multishell NWs
involving In, Ga, As, Si, P, etc. for solar cell, photoluminescence
and other photovoltaic applications.221–228 An analogous synthetic Fig. 11 (a) Fabrication procedure for a thermoresponsive NW forest, used
approach for generating epitaxial core–multishell nanopillars as one mate of the proposed unisex fasteners. (b and c) Scanning electron
based on GaAs (doped with nitrogen and phosphorous) and InGaP microscopy (SEM) images of Ge/parylene NW forests before and after
deposition of the PNIPAM outer shell. Reprinted with permission from
has been described.229 A similar approach was adopted by Gutsche
ref. 232. Copyright 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
et al. for the synthesis of n-GaAs/InGaP/p-GaAs core–multishell
nanowire diodes,230 and by the Lieber group for the preparation
of CSNs with n-GaN cores and InxGa1xN/GaN/p-AlGaN/p-GaN wire-in-wire and/or tube-in-tube or wire-in-tube nanostructures.236,237
shells.42,231 A thermoresponsive chemical connector based on Kempa et al. used a gold nanocluster catalyzed growth process
Ge/perylene/PNIPAM (PNIPAM = poly(N-isopropylacrylamide)) to obtain coaxial Si- and B-based multishell NWs using SiH4 as
was developed by Javey and co-workers via a combined deposi- the silicon precursor, B2H6 as the p-type dopant and PH3 as the
tion and photopolymerization method (Fig. 11).232 Solid-state n-type dopant for the application as ultrathin photovoltaic
lithium-ion nanobatteries were synthesized using a combi- materials.238
nation of gold-catalyzed growth of Si-NWs followed by stepwise More traditional methods have also been used for synthesizing
coating of different layers (10 nm Ti, 30 nm Pt, 40 nm Ti, and core–multishell nanomaterials. For example, Fe3O4@Ag/SiO2/Au
E180 nm of LiCoO2) by sputter deposition techniques under an microspheres were prepared starting from Fe3O4 (prepared via
inert atmosphere.233 Similar growth techniques have been used solvothermal method) and using reduction, sol–gel process and
by Picraux234,235 for making core/multishell germanium/silicon interfacial growth chemistry.239 In another example, CaCO3 (PAH/
nanowire heterostructures and also by Patolsky for creating astralen)x/Ag (where x = 1–3, PAH = polyaniline hydrochloride)
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core–multishell microparticles composed of a solid carbonate prepared by depositing Ag on silica supporting cores followed by
core coated with silver NPs and astralen (polyhedral multishell additional coating of titania.248 First, silica microspheres were
fullerene-like structure) have also been synthesized using a treated with a solution containing Sn2+ ions, followed by another
conventional approach. The synthetic procedure involved precipi- solution containing Ag+ ions to obtain silver NPs outside the core
tation (to make the CaCO3 core) followed by layer-by-layer via galvanic replacement. Then electroless-plating using Ag+ and
assembly of astralen with polyallylamine hydrochloride (PAH) formaldehyde solution resulted in the formation of Ag shells
and finally deposition of Ag-NPs by means of the silver mirror outside the silica microspheres. The resulting NPs were then
reaction.240 Xiong and co-workers241 demonstrated that incorpora- coated with titania shells via the traditional sol–gel method along
tion of ‘‘gain’’ material (fluorophore dye) into core–multishell using PVP (poly-vinylpyrrolidone) as stabilizer. A flow synthesis of
Au/silica/silica spherical nanocavities allows resonance energy- core–double–shell Au/Ag/Au NPs with narrow size distribution has
transfer from the gain media to the plasmon, thereby compen- also been reported where tetradecane was used as carrier medium
sating loss due to energy dissipation. In their synthesis, a Au-NP to generate segmented flow.249 Further, multishell hydrogel NPs
core was first synthesized using conventional reduction of a with a Ag-NP core, protective citrate capping, pH indicator dye
Au-salt by sodium citrate. This was followed by coating the shell and polyacrylamide cladding have been prepared.250
surfaces of the Au-NPs with silica shells using a mixture of Mainly comprising ‘‘organic’’ materials, special types of core–
tetraethyl orthosilicate (TEOS) and 3-(aminopropyl)trimethoxy- multishell NPs have been introduced recently involving supra-
silane (APTMS). Then, using a controlled etching technique (by molecular dendritic assemblies, which have potential applications
treating the sample with strong base at elevated temperature), in drug/dye/metal ions delivery251–257 as well as catalysis258–260 etc.
allowed formation of a thin shell surrounding the Au-NP core. In a typical synthetic procedure, a polar inner core (mostly PEG
Finally, a modified Stöber method using a mixture of fluor- related materials, PEG = polyethylene glycol) was chemically
ophore dye and TEOS afforded the final product, where the dye attached (typically via simple esterification between mPEG (methoxy-
particles were doped only in the outer layer (Fig. 12). In their poly(ethylene glycol)) and diacid based linkers) to a non-polar
recent report,242,243 Catala et al. demonstrated a surfactant-free intermediate shell. The ensuing material was then conjugated via
one-pot multistep procedure to obtain core–multishell magnetic/ amidation using EDC (1-ethyl-3-(3-dimethylaminopropyl)carbo-
photomagnetic co-ordination NPs specifically composed of face- diimide) coupling to a hydrophilic outer core (generally PEI, poly-
centered-cubic Prussian blue analogs (PBAs) of the general ethyleneimine) to produce the final material (Fig. 13). This synthetic
formula AIxMII[M0 III(CN)6](2+x)/3, [where A is an alkali-metal cation strategy is attractive, because depending on the desired application
and MII and M0 III are transition-metal ions].244 The particle-size the synthetic procedure, polarity and sequence of layering can all
(and also shell thickness) was shown to be easily controllable and be easily altered along with the chain-length and molecular
in good agreement with calculated values. Zeng and co-workers weight of each of the precursors. Regarding catalysis, these
reported the sol–gel synthesis of Zn1xCoxO/Co1yZnyO core– dendritic core–multishell composites could be used to incorpo-
multishell NPs that could be used as a catalyst for CO oxidation rate catalytically active metal ions/NPs for assorted organic
at relatively low temperature.245 transformations (including enantioselective reactions) with high
A step-by-step synthetic method has been used to obtain reactivity and excellent recyclability.258–260
hetero-epitaxial growth of core–shell and core–multishell nano-
materials containing Pd and Au NPs.246,247 Ming and co-workers 3.1.1.3.3. Core–porous-shell NPs. Although it is difficult to
have reported the synthesis of silica/Ag/TiO2 nanocomposites completely separate the category ‘‘core–porous-shell’’ from the
Fig. 12 Core–shell/multishell plasmodia nanocavities. Schematic of (a) Au (yellow)/silica (green) and (b) Au/silica/dye silica core–multishell nano-
structures. Dye molecules (shown as red stars) are dispersed in the outermost silica shell (shown as green shell). (c–g) TEM images of Au/silica core–shell
structures with different shell thickness. (h) TEM images of Au/silica/dye (rhodamine 6G) silica core–multishell nanostructures. Reprinted with permission
from ref. 241. Copyright 2012 American Chemical Society.
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of styrene with good recyclable property and almost no leaching

of the metals.
In another related example, Yu et al. developed a synthetic
strategy involving sol–gel, hydrothermal, polymerization, and
carbonization to synthesize silicalite-1 (core)/mesoporous shell
structures.269,270 Chen and co-workers reported the synthesis of
Pd/SiO2 and Ca–Pd/SiO2 egg–porous-shell nanomaterials via an

impregnation method to explore their catalytic prowess in CO
hydrogenation to methanol with high selectivity.271 Porous
Fe3O4/Fe/SiO2 and Fe3O4/SnO2 core/shell nanorods possessing
Fig. 13 Schematic of the structure of a core–multishell NP synthesized magnetic and electromagnetic properties were synthesized by
using a combination of esterification and amidation reactions. Reprinted Chen and co-workers using a combination of hydrothermal,
with permission from ref. 251. Copyright 2012 American Chemical Society. sol–gel, and annealing methods.150,272 Commercially available
films composed of Ag65Au35 (based on atom %) were used to
synthesize nanoporous gold by chemical etching with 70% HNO3
aforementioned two classes of CSNs because porosity in the aqueous solution at room temperature. Subsequent controlled
materials can be brought about either directly or after synthesizing incorporation of Ag into the nanopores of the material was carried
the particles using earlier described protocols, this section out using an electroless-plating method.273 A combination of a
includes recent and exclusive examples of porous-shell NPs, hydrothermal and layer-by-layer deposition technique has also
the associated synthetic strategies and applications. In addition been applied to synthesize a-Fe2O3@SnO2@C porous core–shell
to chromatographic separation,261–265 these particles have been nanorods.274 The resulting materials showed excellent perfor-
explored for diverse catalytic applications. mance when used as an anode for lithium-ion batteries. Wang’s
The techniques for utilizing the pores of core–porous shell group reported a simple oxidation-based method to generate
nanomaterials depend on the intrinsic chemical reactivity of the porous core–shell structured Ni/NiO anode materials for lithium
shells and compatibility with cores. In most cases, a mild variant ion batteries.275 Using a similar approach, Mathur and co-workers
of the strategy employed to remove the shell completely (as synthesized porous Ni/Ni3S2 core–shell nanotubes via a hydro-
described for hollow-shell nanomaterials) can be used to partially thermal method followed by controlled oxidation.276 A general
‘‘etch’’ the shells to render them porous. The most prevalent galvanic displacement approach has also been employed to
examples here are the inorganic oxides, which can be easily synthesize porous core–shell Au–M (M = Au, Pd, and Pt) nano-
etched by treatment with strong base/acid. structures that served as efficient electrocatalysts for EtOH
Asefa and co-workers have reported the synthesis of both oxidation as well as the oxygen reduction reaction.277
core–shell and core–porous-shell type silica-based microparticles The synthetic strategies for porous CSNs have been extended
together with their applications for catalysis.266,267 The synthesis to relatively sophisticated unconventional methods. For example,
involved a combination of (1) the Stöber synthesis of silica the synthesis of hierarchical porous core–shell carbon nano-
core microparticles, (2) grafting of different functional groups structures using detonation-assisted-chemical-vapor-deposition
(e.g., amine, thiol, amine based dendrimer, etc.) on the surfaces has been reported.278 In this process, picric acid was assumed
of the core NPs, (3) incorporation of metal-ions or metallic NPs to create the required high temperature environment by detona-
using the different surface functional groups on the micro- tion, where the premixed carbon(phenol)/catalyst(cobalt acetate)
particles as ligands, (4) coating the resulting materials with a precursors decompose to form carbon nanostructures. In another
layer of metal oxides using another sol–gel (Stöber-like) pro- study, a coaxial electrospinning system with a ‘‘water-immersed
cess, and finally (5) base-assisted partial etching of the metal collector’’ was used to synthesize polycaprolactone and gelatin
oxide shells to produce porous shells. The pore size of the based highly porous core–shell nanostructures (Fig. 15).279
materials was shown to be easily controllable by varying exter- A combination of electrostatic spray deposition (ESD) and high
nal reaction parameters (e.g., reaction temperature, etching temperature treatment was also successfully employed by Wang
time, etc.). The porous shells around the NPs thus enabled and co-workers to obtain three-dimensional porous core–shell
selective transport of substrates/product. Fig. 14 shows a schematic Sn@carbon anode materials on nickel foam.280 Using a proto-
of the procedural route for porous SiO2–AuNP–SiO2 core–shell– col involving electrodeposition (to make Ni nanowire), plasma
shell materials,268 which were used for the selective oxidation annealing (to make Ni@NiO) and finally hydrothermal reduction,
Fig. 14 Schematic representation of the synthesis of a porous SiO2–AuNP–SiO2 core–shell–shell microsphere catalyst. Reprinted with permission from
ref. 268. Copyright 2012 Springer.
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Zhang’s group made porous silica CSNs via the sol–gel method
and used them as a fluorescent sensor for the detection of very low
concentrations of Zn2+ ions by employing rhodamine 101 adsorbed
on the solid cores and 8-aminoquinoline impregnated onto the
porous silica shells.284 Weitz and co-workers used a microfluidic
and ‘‘porogen-templating’’ techniques to prepare NPs with a
hydrophobic porous core and hydrophilic porous surface.285

While the hydrophilic surface allowed good dispersibility in water,
the hydrophobic cores enabled adsorption of organic molecules
into the NPs from the surrounding aqueous environment, thus
enhancing their high adsorption capacity (Fig. 16).
As opposed to repeating the different synthetic strategies
Fig. 15 Electrospinning system for creating core–shell and porous core–
shell fiber networks. (A) core–shell electrospinning system for core–shell for core–shell nanoparticles, already extensively covered in
nanofibers. (B) Electrospinning setup in a water-immersed collector for other reviews, the aforementioned classification hopefully have
preparing porous core–shell fiber networks. Reprinted with permission provided some thoughts to the readers for possible extension/
from ref. 279. Copyright 2011 American Chemical Society. development in the field of core–shell nanocatalysts.
The above section described different synthetic strategies
used for making CSNs according to the types of materials.
one-dimensional Ni@NiO/Pt hybrid NWs were synthesized.281 A novel classification system based on the shell-properties has
The resulting material showed excellent catalytic activity for been introduced considering recent upsurge in their applica-
the electrooxidation of ethanol in alkaline media and high tions. In contrast to the archaic literature precedence, most of
tolerance against CO-poisoning. Porous metal oxide (Co3O4@NiO the recent methods are primarily application-driven. Based on
and ZnO@NiO) core–shell NWs with excellent supercapacitive the compatibility between the layers as well as their utilizations,
properties have been prepared by Fan and co-workers using hydro- combinations of different synthetic methods or simplification
thermal, chemical bath deposition and finally thermal annealing.282 of relatively complicated and time-consuming methods are
A similar technique was used to synthesize Co3O4@NiO, which becoming routine practices. With such enhanced synthetic
displayed a high catalytic efficiency towards methanol oxidation.283 prowess, core–shell nanomaterials with hybrid structures and
Fig. 16 (a) Schematic of the mechanism of mixing driven phase separation, precipitation polymerization and subsequent pore formation after removal
of porogen PDMS oil. (b–e) SEM images of the surface and the three different layers within the porous particle. Reprinted with permission from ref. 285.
Copyright 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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unique functionalities can be obtained in a relatively shorter time microscopy (SEM) and transmission electron microscopy (TEM)
to find their utility in varied applications, especially in catalysis. images are usually used to determine the size, morphology and
homogeneity of the NPs. However, because signal collection in
3.2. Characterization techniques for core–shell nanoparticles SEM usually involves collecting secondary electrons and there-
The above sections described common synthetic strategies and fore generating only a surface image, it is difficult to distinguish
some recent examples of different types of CSNs. However, the core from the shell with SEM analysis. High resolution
before discussing the catalytic applications, it is important to TEM (HRTEM) enables the simultaneous observation of lattice
provide an overview of the techniques available for characterizing fringes with different spacings in the core and shell from a single
such systems. In this section, some common techniques related particle. Additionally, energy dispersive spectrometry (EDS),
to CSNs (or nanomaterials in general) are mentioned. which is typically attached as an accessory to TEM instruments,
The properties and performance of nanomaterials, especially as can serve as a powerful method for determining the distribution
nanocatalysts, relies heavily on their size, morphology, structure of elements within specified region. Thus, EDS can be reliably
and composition. In the case of CSNs, the combination of the used to characterize the chemical nature of the core and shell
inner core and outer shell, dispersion of catalytic groups on the within a core–shell nanosystem. Another important technique
surface of the materials and diffusion of the NPs in the reaction used for core–shell nanomaterials, particularly for their compo-
have crucial effects on their properties and catalytic activities. sition, elemental mapping and also sometimes depth-profiling,
Therefore, characterization of CSNs to obtain information regard- is electron energy loss spectroscopy (EELS) – a technique often
ing their structural features and physical properties are not only considered complimentary to EDS. This technique has been
important for understanding their structure–catalytic activity routinely used for core–shell nanocatalysts to obtain valuable
relationships but also for gaining deeper insights into the catalytic information regarding their structure activity relationships (see
mechanisms involving these nanosystems. Consequently, a range Section 5 on electrocatalysis). In high angle annular dark-field
of parameters that define CSNs needs to be characterized and STEM (HAADF-STEM), regions with larger average atomic number
assessed (Fig. 17). To describe CSNs as completely as possible, it is are indicated by brighter contrast in images, as long as this
necessary to elucidate the chemical and physical properties of the area has the same thickness. Therefore, Z-contrast (Z is the average
materials, i.e., the size and shape of the particles, surface char- atomic number) images can be used to detect the element
acteristics, nature of surface coating and presence of impurities/ distribution visually and directly. More advanced electron micro-
dopants (which are often incorporated by combining a series of scopy methods, such as aberration-corrected STEM operating at
complimentary analytical methods). Below, the major character- a lower voltage (100 kV), has recently been developed to give
ization techniques used to probe the structures, compositions and the images at atomic-resolution.286 In fact, annular dark field
properties of CSNs are briefly described. scanning transmission electron microscopy (ADF-STEM) and
X-ray diffraction (XRD) has long been the method of choice atomic-resolution spectroscopic mapping are nowadays routinely
for studying the crystal phases or microstructures of a range used under various suitable conditions. By taking advantage of the
of materials, including CSNs. Particularly for CSNs, XRD is an unique optical properties, such as plasmonic, absorption and emis-
important tool that can shed light on the presence of core–shell sion properties, of NCs (which are quite sensitive to their surface
structures in the NPs. Even separated phases belonging to the core modification), several spectroscopic techniques have been developed
and shell could be detected simultaneously. Scanning electron to directly or indirectly, characterize CSNs. UV-Vis spectroscopy
is one of the most commonly used spectroscopic techniques for
the analysis of different types of NPs, especially those capable of
absorbing in the UV-Vis region of electromagnetic radiation. For
organic type core@shell nanostructures, infrared spectroscopy
can be used for the identification of the organic molecules/
moieites present in the nanostructures.
Raman spectroscopy is also another important technique for
studying the surface characteristics of core–shell nanomaterials.
Additionally, surface enhanced Raman spectroscopy (SERS) can
be used for studying CSNs containing SERS active metals, such as
Au, Ag, and Cu, and for the detection and monitoring of surface
processes relevant for catalysis by core–shell nanomaterials. Gas
adsorption/desorption machinery equipped with an automated
analyzer, which allows multilayer adsorption/desorption of gas
(mostly nitrogen) over a material’s surface as a function of relative
pressure, is also useful for the characterization of core–shell nano-
materials, especially those containing porous structures. In particu-
lar, the Brunauer–Emmett–Teller (BET) method is commonly used
Fig. 17 Structural and compositional features of CSNs that can affect for determination of the specific surface area of porous core–shell
CSNs catalytic properties. nanomaterials, whereas the Barrett–Joyner–Halenda (BJH) method
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can be employed to determine the pore volume and pore size of and Henry reactions, aerobic oxidative esterifications and
the materials; the choice being dictated by the pore sizes and synthesis of bulk chemicals (e.g., adipic acid), etc.
structures in the materials.
The above section highlights the key tools used to character- 4.1. Hydrogenation reactions
ize CSNs by providing information about their physicochemical Hydrogenation reactions are important in the industrial syntheses
properties. In the context of current review, these tools are
of dyes, biologically active compounds, pharmaceuticals, rubber

also important for checking the integrity of the nanocatalysts and agricultural chemicals.299–301 Nanomaterial-catalyzed hydro-
after catalytic reactions and often provide insights into the genations of alkynes, alkenes, aromatic nitro compounds and
interactions of different components of the catalyst with the ketones have received much interest in the last decade because
reactant molecules. of their use in the synthesis of important raw materials along
with the remarkable effectiveness of nanomaterials in catalyz-
4. Applications of core–shell ing such reactions.300,302–304 Hydrogenation reactions are often
performed using traditional catalysts for several important
nanoparticles in catalysis drug intermediates and pharmaceutical precursors,305–307 for
The systematic design and synthesis of core–shell nanocatalysts which the selectivity of the reactions is the biggest concern.
comprising active metal NPs in the core and closely assembled Among such processes, catalytic transfer hydrogenation (CTH)
structures with nano-gaps in the shell to permit substrates access reaction is becoming increasing popular because of its wide
to the core metal can allow access to highly selective nanocata- usage and versatility. The practical use of CSNs for CTH often
lysts.287–297 In this section, various catalytic reactions by CSNs298 stems from the fact that these materials offer high selectivity
are described, such as hydrogenation reactions, oxidation reac- (both regio- and chemo-selectivity) along with their enhanced
tions, cross-coupling reactions, tandem deprotection-Knoevenagel ease of separation and recyclability; several types of core–shell
nanocatalysts have been successfully employed for various
transfer hydrogenation reactions.308–311
4.1.1. Chemoselective reduction reaction. Kaneda and
co-workers have reported the synthesis of Ag@CeO2 core–shell
nanocatalysts using the reverse micelle method and showed
their catalytic properties in chemoselective reduction reactions.312
The material (denoted as the core–shell nanocomposite
AgNPs@BM) consisted of AgNPs covered with a basic material
(BM) (Fig. 18). It is worth emphasizing that a hydrogen mole-
cule was cleaved heterolytically at the junction between AgNPs
and basic sites (or BM) of the materials, thereby suppressing
the unfavorable homolytic fission of the hydrogen molecule
Fig. 18 (a) Representation of Ag/HT (HT represents hydrotalcite support) on the bare AgNPs. The resultant Ag hydride and proton
reacting with H2; both polar and nonpolar hydrogen species are formed.
species enable the complete chemoselective reduction of nitro
(b) Representation of AgNPs@BM; AgNPs are covered with a basic material
(BM), which reacts with H2 to result in exclusive formation of polar compounds while retaining the CQC bonds intact (Fig. 19).
hydrogen species. A basic site of HT and BM is represented by BS. Similarly, AgNPs@CeO2 was shown to catalyze the deoxygena-
Reprinted with permission from ref. 312. Copyright 2012 Wiley-VCH Verlag tion of epoxides to alkenes with excellent (99%) selectivity
GmbH & Co. KGaA, Weinheim. (Fig. 20).
Fig. 19 Chemoselective reduction of various organic substrates on silver@cerium dioxide core–shell nanocatalyst.
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Table 1 Semihydrogenation of internal alkynes using Pd@MPSO/SiO2-1a
T Yieldb (%)
Entry Alkyne Product (h) Alkenes Z : E Alkanes
1 2 97 97 : 3 3
2c 8 95 97 : 3 5
3d 6 98 97 : 3 2
Fig. 20 Electron micrographs of AgNPs@CeO2: (a) SEM and (b) HRTEM
images of a AgNPs@CeO2 nanocomposite particle, (c) line-scan STEM-
EDS across the AgNPs@CeO2 nanocomposite (Ag: red squares, Ce: green 4d 6 99 98 : 2 1
squares). The circled areas correspond to the spherical CeO2 NPs. Reprinted
with permission from ref. 312. Copyright 2012 Wiley-VCH Verlag GmbH &
Co. KGaA, Weinheim.
5d 6 98 98 : 2 2
6e 6 98 95 : 5 2
AgNPs@CeO2, has also been shown to catalyze the chemo-
selective reduction of unsaturated aldehydes to the corresponding
unsaturated alcohols with H2;313 the nanogaps among adjacent 7d 8 98 97 : 3 2
CeO2 NPs within the shell allow better access of reactants to the
active Ag sites in the core. Exploiting the interaction between the a
Reaction conditions: alkyne (0.5 mmol), Pd@MPSO/SiO2-1 (0.02 g, Pd:
basic sites of CeO2 and Ag NPs effectively induced the heterolytic 0.2 mol%) and MeOH (5 mL). b Determined by Gas Chromatography
(GC) yield using an internal standard. c Pd@MPSO/SiO2-1 (0.1 g, Pd:
cleavage of H2 to Ag–hydride and proton species, allowing the 0.05 mol%), 1 (10 mmol), MeOH (40 mL), H2 (1 atm.), 30 1C. d Reaction
highly chemoselective reduction of unsaturated aldehydes to was conducted at 40 1C. e THF was used as a solvent.
the corresponding allylic alcohols.
4.1.2. Semihydrogenation of alkynes by Pd@MPSO/SiO2. The
nanocatalysts, namely Pd@MPSO/SiO2-1 (where MPSO : Pd = 7 : 1)
semihydrogenation of alkynes is an important synthetic protocol
and Pd@MPSO/SiO2-2 (where MPSO : Pd = 100 : 1). The material
for preparing (Z)-alkenes, which are important building blocks
Pd@MPSO/SiO2-1 was successfully employed as a catalyst for the
for fine chemicals and pharmaceuticals, such as flavors, natural
semihydrogenation of a wide range of internal alkynes (aromatic
products and bioactive molecules.314 A core–shell nanocatalyst
and aliphatic alkynes) to the corresponding alkenes, affording
consisting of Pd NPs shielded within a DMSO-type matrix on the
497% yield (Table 1). Pd@MPSO/SiO2-2 also catalyzed the
surface of SiO2 producing Pd@MPSO/SiO2 CSNs (MPSO = methyl-
selective semihydrogenation of a variety of terminal alkynes,
3-trimethoxysilylpropylsulfoxide) has been designed and shown
such as ethynyl benzenes, bearing electron-withdrawing and
to catalyze the selective semihydrogenation of alkynes.315 The
electron-donating groups to the corresponding terminal alkenes
shell containing an alkyl sulfoxide network acted as a macroligand
with excellent selectivity (Fig. 22).
and permitted the selective entrance of alkynes to the active center
4.1.3. Reduction reactions with magnetically separable core–
of the Pd NPs, encouraging the selective semihydrogenation
shell nanocatalysts. Magnetically separable NPs are increasingly used
of alkynes (Fig. 21).315,316 Varying the molar ratios of MPSO to
as robust catalysts for various organic transformations because
Pd during the synthesis resulted in two different core–shell
they are easily recoverable and reusable as catalyst for multiple
catalytic runs. Such nanomaterials can easily be synthesized via
a stepwise or an in situ synthetic method. For example, a simple
Fig. 21 Schematic showing the principles behind the synthesis of

Pd@MPSO/SiO2 core–shell nanocatalyst. Adapted from ref. 315. Fig. 22 Semihydrogenation of terminal alkynes using Pd@MPSO/SiO2-2.
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Fig. 23 (A) Ag–Ni CSNs: (a) low-magnification TEM image (at 50 nm), (b) SAED pattern, (c) HRTEM image, and (d) EDS spectra recorded from the center.
(B) Hydrogen transfer reactions of aromatic nitro and carbonyl compounds on Ag@Ni core–shell nanocatalyst. Reprinted with permission from ref. 98.
Copyright 2013 Royal Society of Chemistry.
one-pot process has been developed where oleylamine serves as

both solvent and reducing agent for the Ag+ and Ni2+ ions and
triphenylphosphine as surfactant.98 TEM images of the nano-
catalyst showed particles with spherical morphology of diameter
ca. 14.9 nm (Fig. 23A) and narrow size distribution (s = 1.14 nm).
The selected area electron diffraction (SAED) pattern (Fig. 23A(b))
acquired for the NPs displayed diffraction rings, which could be
indexed to face-centered cubic (fcc) corresponding to both Ni
and Ag. The compositional scan profile red line marked in the
HAADF image (Fig. 23A(d)) on a single particle clearly showed
two types of strong signals: one corresponding to Ni at the edge
and the other corresponding to Ag at the center of particle,
typical of a core–shell structure.
The above mentioned nanomaterials can serve as catalysts
for the reduction of functional groups (e.g., nitro, azido and
carbonyl compounds), that are of high importance for organic
synthesis300,301,317 and the synthesis of many biologically active
compounds for medical applications. Specifically, Ag@Ni CSNs
have been deployed for the hydrogen transfer reactions of
Fig. 24 Synthesis of the heterogeneous catalyst Cp*RhTsDPEN-CSSDMSS
aromatic nitro compounds using isopropyl alcohol (IPA) as
(3). Reprinted with permission from ref. 318. Copyright 2013 Royal Society
hydrogen donor (Fig. 23B, right); both, electron withdrawing of Chemistry.
and electron donating groups, such as –Cl, –Br, –F, and –OCH3,
were found to have no significant influence on the reaction. In
addition, the catalytic performance of the CSNs was evaluated the core of mesoporous silica spheres. The detailed synthetic
for the reduction of carbonyl compounds and found to provide protocol used for making these core–shell nanostructured
good to excellent yields (90–94%). mesoporous silica nanospheres with Cp*RhTsDPEN functionality
4.1.4. Asymmetric transfer hydrogenation of aromatic ketones is shown in Fig. 24. First, the TsDPEN-functionalized internal core
on immobilized rhodium catalyst. Core–shell nanostructured (2) was obtained via co-condensation of a chiral silica resource and
mesoporous silica microspheres have successfully been used as tetraethoxysilane (TEOS) in the presence of a mixture of cetyltri-
a support material for making nanocatalysts for asymmetric methylammonium chloride (CTAC) and triethanol amine (TEA). TEA
synthesis. The core of silica spheres enables the assembly of various helps to promote high nucleation and slow growth of the generated
chiral functionalities while the shell of silica spheres prevents seeds, resulting in mesoporous silica NPs. The continuous growth of
leaching of chiral organometallics. Li and co-workers used such the external shell around the nanospheres was made possible using
an immobilized rhodium catalyst for asymmetric transfer hydro- additional TEOS along with CTAC. Finally, direct complexation of
genation reaction,318 wherein a chiral Cp*RhTsDPEN complex [Cp*RhCl2]2, followed by the removal of the CTAC templates via
(Cp* = pentamethyl cyclopentadiene, TsDPEN = 4-methylphenyl- Soxhlet extraction afforded the mesoporous catalyst Cp*RhTsDPEN-
sulfonyl-1,2-diphenylethylenediamine) was assembled within CSSDMSS (3) as a light red-colored powdered material (Fig. 24).
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The resulting nanocatalyst was successfully employed as a The surfaces of the silica microspheres were then modified using
catalyst for the asymmetric transfer hydrogenation of aromatic 3-aminopropyltrimethoxysilane (APTMS) to form aminopropyl-
ketones in aqueous medium in the absence of any phase terminated SiO2 microspheres. Finally, Pd NPs were supported
transfer catalyst (PTC), affording excellent conversion and high on the aminopropyl-terminated silica microspheres by reducing
enantioselectivity. The nanocatalyst demonstrated its versatility an aqueous solution of Pd salt with citric acid. In the second
in accommodating various substrates with electron donating as step, the SiO2/Pd core microspheres were coated with a silica
well as electron withdrawing groups. Moreover, the catalyst was shell, thus producing SiO2/Pd/SiO2 core–shell–shell microspheres,
successfully recycled up to twelve times with no significant loss which were further coated by a surfactant/ZrO2 shell. The ZrO2
of catalytic activity. shell was prepared by mixing SiO2/Pd/SiO2 core–shell–shell micro-
4.1.5. Vapor-phase cyclohexene hydrogenation by Au–Rh spheres in an aqueous solution containing polyethylene glycol
core–shell nanoparticles. Humphrey and co-workers have dodecyl ether (Brijs 30) surfactant and zirconium butoxide
reported a MW-assisted method for the synthesis of Au–Rh CSNs [Zr(OBu)4], and aging the solution for 12 h. The ensuing solid
in which AuNP seeds were coated by Rh shells in a one-pot product was calcined at 1073 K for 2 h to afford the SiO2/Pd/SiO2/
procedure.319 The Au NPs were prepared by NaBH4 reduction of h-ZrO2 core–shell–shell microspheres. Finally, the controlled etching
HAuCl4H2O in the presence of poly(vinylpyrrolidone) (PVP) in of the silica shell with an aqueous NaOH solution generated the
ethylene glycol at 150 1C for 30 min under MW irradiation and then hollow SiO2/Pd/h-ZrO2 core–shell–shell microspheres (or core–shell
left for an overgrowth step without further modification. Based on microsphere catalysts). The formation of the hollow shell was closely
the desired thickness of the shell, a specific quantity of RhCl3xH2O monitored by taking TEM images (Fig. 26B, right) of samples
in ethylene glycol was added at a rate of 20.0 mL h1 to the collected from solutions during etching of the inner silica shells of
suspended Au NPs under MW heating. In situ reduction of Rh(III) SiO2/Pd/SiO2/ZrO2, which gradually produced yolk–shell-type SiO2/
by ethylene glycol facilitated the isotropic overgrowth of Rh(0) onto Pd/h-ZrO2 microspheres. The images showed that SiO2 microsphere-
the AuNP seeds under MW irradiation at 150 1C (Fig. 25). supported Pd NPs were encapsulated within a hollow and nano-
The catalytic activity of the resulting CSNs was assessed using porous ZrO2 shell (yolk–shell type catalytic microreactors). The
vapor-phase cyclohexene hydrogenation as a model reaction in a hollow and nanoporous ZrO2 shell was permeable enough to allow
down flow reactor. Before packing the catalyst in the reactor, Au, reactants to reach the Pd-anchored-SiO2 cores, while at the same
Rh and Rh–Au CSNs were supported on amorphous silica using time robust enough to keep the Pd NPs intact and give high
the reported procedure.320 Next, a few milligrams of each catalyst conversion and recyclability for the hydrogenation of olefins.
(material) were studied using a single-pass reactor, in which a The catalytic activity of the generated core–shell micro-
low pressure stream of H2/He and cyclohexene were passed over spheres was then investigated toward the hydrogenation of
the catalyst at 30 1C, while the exhaust mixture was monitored styrene as a model reaction. The reaction proceeded at room
with an automated GC to evaluate the progress of the catalytic temperature and under 2 MPa H2 pressure, giving high yield in
reaction. The results revealed that the catalytic activity of the 30 min. The versatility of the catalysts was exemplified for
materials was highly dependent on the thickness of the shell of various styrenes and recycling experiments (Table 2).
the core–shell nanomaterial. The same group reported the synthesis of CSNs containing
4.1.6. Hydrogenation of alkenes by SiO2/Pd/h-ZrO2 and SiO2/ dendrimers in the structure, where core–shell microspheres
Pd-PAMAM type core–shell–shell microspheres. Asefa and containing SiO2 cores and dendrimer-encapsulated ultra-small
co-workers have reported the synthesis of stable catalytic core– Pd were assembled, producing SiO2@Pd–PAMAM microspheres.266
shell type microreactors, which comprise SiO2 microsphere- In the synthesis, SiO2 microspheres were first prepared by the Stöber
supported metal NPs embedded in multicores of hollow and method and then functionalized with vinyl groups by grafting their
nanoporous ZrO2 shell.321 The catalyst, SiO2/Pd/h-ZrO2, was surfaces with vinyltriethoxysilane (VTS). Afterwards, the vinyl groups
synthesized in three main steps (Fig. 26A). In the first step, were converted into epoxides by using m-chloroperoxybenzoic acid.
silica microspheres were prepared by the Stöber method. Upon treatment with amine terminated G4 poly(amidoamine)
Fig. 25 Schematic of the synthesis of Au–Rh CSNs using a microwave (MW)-assisted synthetic method: yellow/orange = Au; blue/violet = Rh. Reprinted
with permission from ref. 319. Copyright 2013 Royal Society of Chemistry.
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Fig. 26 (A) Schematic of the synthesis of SiO2/Pd/h-ZrO2 core–shell–shell microspheres or microsphere catalysts. (B) TEM images showing
the structural evolution of SiO2/Pd/SiO2/ZrO2 core–shell–shell–shell microspheres after etching with dilute NaOH solution for different etching times:
(a) 2 h, (b) 6 h, (c) 9 h, (d) 12 h, (e) 15 h, (f) 20 h, (g and h) 24 h, (i) 27 h, and (j) 48 h. Reprinted with permission from ref. 321. Copyright 2012 Wiley-VCH
(PAMAM) dendrimers, the SiO2-supported epoxides underwent functional groups under 10 bar hydrogen pressure at room
ring-opening and afforded SiO2@PAMAM core–shell micro- temperature (RT) (Fig. 28). The SiO2 microspheres supported
spheres. Pd NPs within the cores of the SiO2-supported PAMAM the permeable core–shell structures and the ultrasmall Pd NPs
dendrimers were generated by reducing Pd(II) ions in the cores embedded in the attached dendrimer contributed to high catalytic
of the dendrimers with NaBH4. TEM images and size distribu- activities. The catalysts showed excellent recyclability without loss of
tion of the resulting SiO2@PAMAM core–shell microspheres are catalytic activity. These CSNs microspheres retained their catalytic
shown in Fig. 27. activity better than in control samples, including SiO2@Pd core–
The SiO2@Pd–PAMAM core–shell microspheres were evalu- shell microspheres that contained no dendrimers or contained
ated for hydrogenation (or reduction) reactions toward various a commercially available Pd/C (1 wt%) catalyst.
4.1.7. Magnetic core–shell Au nanocatalyst for the reduction of
4-nitrophenol. Zhu and co-workers have reported a magnetic core–
Table 2 Hydrogenation of various substrates by SiO2/Pd/h-ZrO2 core– shell Au nanocatalyst for the reduction of 4-nitrophenol under
shell–shell microsphere catalysts benign reaction conditions.292 The as-synthesized Au–Fe3O4@
Time Conversion Selectivity TOF metal–organic framework (MOF) nanocatalyst had a magnetic
No. Substrate Product (h) (%) (%) (h1) Au–Fe3O4 core and a porous MOF shell. The nanocatalyst was
synthesized by a versatile layer-by-layer assembly protocol, and
1 0.3 B100 B100 5145 the shell thickness in the CSNs was controlled by adjusting the
number of cycles employed for the self assembly. The ensuing
Au (3–5 nm) NPs were located between the magnetite core and
2 1.5 93 B100 1187
MOF shell and were evenly dispersed on the surface of the
3 3 94 B100 492 magnetite NPs (Fig. 29).
Furthermore, the Au–Fe3O4@MOF nanocatalyst was shown
Reaction conditions: substrate (1 mL); methanol (20 mL); catalyst (10 mg,
5.42 wt% Pd in the SiO2/Pd/h-ZrO2 core–shell–shell microspheres); reaction to be the best candidate among other reported Au-based
temperature (25 1C); and reactor pressure (2 MPa H2 pressure). catalysts toward the reduction of 4-nitrophenol as it could be
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Fig. 27 (A) Schematic of the synthesis of SiO2@Pd–PAMAM dendrimer type core–shell microspheres or nanocatalysts. (B) (a and b) Low magnification and
(c) high magnification TEM images of etched SiO2 microspheres. (d and e) Enlarged TEM images of SiO2@Pd–PAMAM core–shell microspheres. (f) Size
distribution of Pd NPs in SiO2@Pd–PAMAM core–shell microspheres. Reprinted with permission from ref. 266. Copyright 2013 American Chemical Society.
Fig. 28 SiO2@Pd–PAMAM core–shell microspheres catalyze hydrogenation reactions of various functional groups.
recycled for several runs due to the magnetic Fe3O4 core.292 Such stabilized on a representative MOF (ZIF-8) (Au–Ag-ZIF-8). The
type of nanocatalyst can be employed in large-scale synthesis of 3D scaffold of ZIF-8 (Zn(MeIM)2, MeIM = 2-methylimidazole)
various compounds in industry, where isolation, separation and provides high thermal and chemical stability with pore size and
reusability are essential to reduce the total synthetic cost. surface area conducive for depositing metal NPs.325 The size
Recently, bimetallic CSNs have been developed where of Au@Ag NPs was successfully controlled at 2–6 nm without
chemical reactions occurring on the shell and core metal can the need for surfactant by a sequential deposition reduction
distinctly modify the performance of the whole core–shell approach (Fig. 30). Changing the Au/Ag ratio altered the com-
nanocatalysts. Smart design of such core–shell materials by varying position whereas reversing the Au/Ag deposition order changed
the reaction conditions can control their physicochemical proper- the structure of the Au–Ag NPs. Applying a post treatment
ties and catalytic activity.322–324 For example, Xu and co-workers procedure converted the core–shell structure to an Au–Ag alloy.
synthesized Au@Ag CSNs decorated on a metal–organic frame- The Au–Ag-ZIF-8 core–shell nanocatalyst was employed for
work (MOF) by a sequential deposition reduction method.295 In a the catalytic reduction of 4-nitrophenol (4-NPh) using NaBH4
typical synthesis of Au–Ag core–shell catalysts, Au–Ag NPs were as reductant in water. The reduction kinetics were followed by
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Fig. 29 (a) Synthesis of magnetic core–shell Au–Fe3O4@MOF nanocatalyst, (b) TEM images of Au–Fe3O4, (c) single particle of core–shell Au–Fe3O4
showing mappings for Au, C, Fe and O elements. Reprinted with permission from ref. 292. Copyright 2015 The Royal Society of Chemistry.
Fig. 30 (a) Schematic illustration of the preparation methods used for Au–Ag core–shell nanocatalysts. (b) Catalytic conversion of 4-NPh over ZIF-8 stabilized
catalysts: 2Au (I20), 2Au–1Ag (I21), 2Au–2Ag (I22), 2Au–3Ag (I23), 2Au–4Ag (I24), 2Ag (II02), 2Ag–1Au (II12), 2Ag–2Au (II22), 2Ag–4Au (II42), and post treated I22.
(b) Arrhenius plot of the rate constant for the reduction of 4-NPh over I22. Reprinted with permission from ref. 295. Copyright 2011 American Chemical Society.
UV-Vis absorption spectroscopy after the addition of the as confirmed in the latter case by TEM/HAADF-STEM analysis
catalyst;295 the absorption peak of 4-nitrophenolate at B400 nm after catalysis.295
decreased along with a concomitant increase of the B300 nm This section described various important chemoselective
peak corresponding to 4-aminophenol. reductions performed by core–shell nanocomposite, AgNPs@BM,
As shown in Fig. 30b, the reaction did not occur over an Au as it forms both polar and nonpolar hydrogen species on respec-
(I20) catalyst and proceeded only sluggishly with an ‘‘induction tive Ag and BM, in a protocol that precludes the use of traditional
period’’ over a Ag (II02) catalyst.295 However, the catalytic activity bases such as NaOH and KOH. The Pd@MPSO/SiO2 core–shell
was significantly improved by applying the Au–Ag core–shell catalyst, deployed for semihydrogenation of terminal alkynes,
catalysts. Among all these synthesized catalysts,295 I22 displayed uses expensive Pd, which could be replaced by other transition
the highest activity with a rate constant estimated to be 4.97 metal such as Ni, Cu, etc.; core–shell recyclable catalysts Ag@Ni,
103 s1, suggesting that it is the most promising candidate employed for nitro and carbonyl group reduction reactions, is a
among Au- and Ag-based catalysts.326–329 Au–Ag core–shell cata- good example of cost-effective and sustainable process. Catalysts
lysts have also been shown to be highly reusable and stable,330 such as Cp*RhTsDPEN-CSSDMSS and Au–Rh core–shell provide
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ideal examples for asymmetric reduction of ketones and vapor- (H2O2); the concentration of H2O2 in the reaction medium is
phase cyclohexene hydrogenation, respectively. almost independent of the catalysts used (Fig. 31b). The catalytic
activity of the nanomaterials were then evaluated for the one-pot
4.2. Oxidation reactions oxidation of methyl phenyl sulfide into methyl phenyl sulfoxide
(A) (Fig. 31c) using in situ generated H2O2, where Pd/SiO2@
Catalytic oxidations of alcohols, aldehydes and sulfides are among
TiMSS was found to be the best catalyst.
the most important and common reactions in organic synthesis

4.2.2. Oxidation of alcohols on Fe3O4@MgAl–LDH@Au
as they can be used to produce a range of valuable raw materials
core–shell catalyst. Facile synthesis of hierarchical core–shell
for the fine chemical and pharmaceutical industry.36,331–333
Fe3O4@MgAl–LDH@Au (LDH = layered-double-hydroxides)
Various CSNs have been employed as catalysts for oxidative
nanomaterials as magnetically recyclable catalysts for catalytic
transformations,334,335 as shown below.
oxidation of alcohols was reported by Zhang and co-workers.341
4.2.1. One-pot oxidation of sulfides by Pd/SiO2@TiMS core–
Briefly, the nanomaterials were synthesized by making Fe3O4@
shell nanocatalyst. Yamashita and co-workers synthesized Pd NPs
MgAl–LDH nanospheres and then supporting Au NPs on the
supported on SiO2 nanosphere core coated with a Ti-containing
surfaces of the MgAl–LDH of Fe3O4@MgAl–LDH342,343 (Fig. 32A).
mesoporous silica shell (Pd/SiO2@TiMSS)336 for one-pot oxidation
Fig. 32B(b) shows SEM/TEM images of Fe3O4@MgAl–LDH@Au
of sulfide to sulfoxide. To make the nanocatalysts, colloidal SiO2
nanocatalyst and its precursors. The images show that the Fe3O4
nanospheres, prepared via Stöber method were first functionalized
NPs had a smooth surface and mean diameter of 450 nm with
with Pd NPs337–339 followed by a coating of Ti-containing meso-
a narrow size distribution. After coating the nanospheres with
porous silica shell (Fig. 31a).340
carbonate–MgAl–LDH, the materials showed honeycomb like
For catalytic studies, SiO2@Pd(R)/TiMSS and SiO2@Pd(S)/
morphology with many voids of about 100–200 nm in size.
TiMSS (where (R) denotes random and (S) designates the surface)
The catalytic oxidation of 1-phenylethanol was then performed
were investigated for one-pot generation of hydrogen peroxide
by using the magnetic Fe3O4@MgAl–LDH@Au (7.0 nm Au) NPs
as catalyst, affording acetophenone (99%) with excellent yield
and high turnover frequency (TOF) of 66 h1; the catalytic
activity was comparable to the value previously reported for
Au/MgAl–LDH (TOF, 74 h1) containing Au NPs with average
size of 2.7 nm at 40 1C.344 The magnetic property of the
Fe3O4@MgAl–LDH@Au nanospheres was successfully utilized
to easily separate the nanocatalysts from the reaction mixture
after the reactions (Fig. 32C).
4.2.3. Oxidation of benzyl alcohol by gold–palladium core–shell
nanocrystals. Tilley and co-workers developed Au–Pd core–shell NCs
with optimized size, shape and facets for catalytic applica-
tions.345 In their study, icosahedral Au–Pd core–shell NCs were
synthesized by a seed-mediated approach, in which nucleation
and growth stages were independently controlled. To grow the
Pd shell around the Au seeds, palladium acetylacetonate and
hexadecylamine in toluene in a 2 : 1 molar ratio of Pd to Au were
added into the solution (Fig. 33). The CSN catalysts were then
supported on activated carbon with a loading of 1 wt% metal
NPs. The catalytic activity of the resulting series of Au–Pd core–
shell NCs with varied shell thickness (0.4, 0.8, 1.5, 2.2, and
3.2 nm) was evaluated toward the oxidation of benzyl alcohol
to benzaldehyde. Typically, in the presence of 25 mg of these
Au–Pd/C NPs, benzyl alcohol (40 mL) was converted into benz-
aldehyde in an autoclave under 10 bar oxygen at 140 1C under
solvent-free conditions. The NCs with shell thickness of 2.2 nm
(ca. 12 atomic layers of Pd) were found to give the highest (TOF)
and selectivity in the reaction.
4.2.4. Lab-in-a-shell approach for selective catalysis. Dai and
co-workers have reported a ‘‘lab-in-a-shell’’ approach for the
synthesis of multifunctional CSNs with metal clusters as a core
Fig. 31 (a) Schematic of the procedure used to prepare Pd/SiO2@TiMSS,
and microporous silica as shell.334 Noble metals such as Pd and
SiO2/@Pd(R)/TiMSS and SiO2/@Pd(S)/TiMSS. (b) Effect of the catalysts on
the concentration of H2O2. (c) Oxidation of methyl phenyl sulfide using
Pt were incorporated in the void space mediated by the capture
in situ generated H2O2. Reprinted with permission from ref. 336. Copyright of polymer dots inside the silica shell (Fig. 34). TEM images of
2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. the Pd cluster@silica core–shell nanospheres revealed that the
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Fig. 32 (A) Synthesis of core–shell Fe3O4@MgAl–LDH@Au NPs. (B) SEM (a–c), TEM (d and e), and HRTEM (f) images of Fe3O4 (a), Fe3O4@MgAl–LDH
(b and d), and Fe3O4@MgAl–LDH@Au (c, e, and f). (C) Catalytic oxidation of 1-phenylethanol. Reprinted with permission from ref. 341. Copyright 2013
Royal Society of Chemistry.
Fig. 33 Micrograph images of Au–Pd core–shell NCs: (a) bright-field TEM, (b) high-resolution TEM, (c) STEM-EDX map shown as an overlay of gold and
palladium signals, and (d) HAADF-STEM image showing a contrast difference between the gold core (bright) and palladium shell (dark). Dotted blue line
represents the EDX line scan shown in (e) with Pd shown in red, Au in green and Cu in black. Reprinted with permission from ref. 345. Copyright 2013
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Fig. 34 (a) Schematic of the synthesis of metal cluster@silica core–shell nanospheres. (b) TEM image of Pd cluster@silica core–shell nanospheres.
(c) Size-selective catalysis of Pd cluster@silica core–shell nanospheres. Reprinted with permission from ref. 334. Copyright 2011 American Chemical Society.
Pd NPs were implanted inside the silica hollow shell and most 4.2.5. CO oxidation with core–shell nanoparticles. Chen et al.
of the core clusters were attached to the interior wall of the have reported a simple synthetic strategy for making core–shell
silica shell (Fig. 34b). microspheres consisting of CuO NPs dispersed on the surface of
The Pd-cluster embedded in the hybrid core–shell nano- Al2O3 for CO oxidation.347 The obtained Al2O3@CuO core–shell
catalysts displayed excellent size-selective catalysis for the submicrospheres displayed uniform core–shell structures, with
allylic oxidation of cyclohexene moieties with different mole- shells composed of small CuO NPs (without the formation of
cular size (e.g., 0.5 nm cyclohexene, 1.91 nm cholesteryl acetate CuAl2O4 passivation layer between CuO and Al2O3). Notably, when
(CA)). Whereas a Pd/silica nanocatalyst successively oxidized these Al2O3@CuO submicrospheres were used as a catalyst for CO
cyclohexene and CA to the corresponding 2-cyclohexene-1-one, oxidation, a significantly improved activity was observed compared
2-cyclohexenol, cyclohexene oxide and 7-ketochlolesteryl acetate to conventional supported CuO/Al2O3348 (prepared by impregna-
as main products with conversions of 23.1% (cyclohexene) and tion and calcination processes) catalysts in a continuous-flow
9.8% (CA), a 4 times higher than cyclohexene conversion (93.7%) fixed-bed reactor with feed gas containing 1.0 vol% CO, 1.6 vol%
was achieved with high selectivity for the dehydrogenation product O2, and 97.4% He (balance gas) at a total flow rate of 50 mL min1,
over the same catalyst (97.7%) (Fig. 34c). The selective oxidation which corresponds to a gas hourly space velocity (GHSV) of
of organic compounds such as hydrocarbons or alcohols is an 30 000 mL h1 gcat1. A maximum conversion was obtained at
important reaction in industrial organic synthesis.346 Further- 160 1C for the reaction.
more, Pd/silica (Pd loading 0.9%) CSNs have been employed Bao and co-workers developed a synthetic method for gen-
for the solvent-free oxidation of hydrocarbons and alcohols erating FeO-on-Cu@Pt-oxide-on-NM (noble metal) type nano-
in an O2 atmosphere to give corresponding products with materials349 for catalytic CO oxidation (Fig. 35). The Cu@Pt CSNs
excellent conversions. were synthesized by a sequential polyol process. In the synthesis,
Fig. 35 Various structural configurations of supported NPs catalysts: (A) noble metal NPs, (B) ‘‘TMO-on-NM’’ (transition metal oxide = TMO) NPs
consisting of a noble metal NPs decorated with surface TM oxide, and (C) ‘‘TMO-on-NM Shell’’ NPs with TM oxide decorating the surface of a core–shell
NP. Reprinted with permission from ref. 349. Copyright 2012 American Chemical Society.
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PtCl2 was first added to a ‘‘freshly prepared’’ colloidal solution of

Cu/EG (EG = Ethylene glycol) at 130 1C under an Ar atmosphere.
The resulting Cu@Pt and Pt NPs were further decorated
with FeO through a reductive deposition–precipitation (RDP)
process and their catalytic activity was evaluated for PROX
(PReferential OXidation). The particles showed significantly
improved catalytic activity for the catalytic oxidation of CO,

especially after the Cu@Pt NPs had been decorated with FeO
patches. Moreover, even though they contained much less Pt,
these CSNs exhibited a similar catalytic activity to that of Pt NPs
covered with surface FeO patches.
4.2.6. CO oxidation on sinter-resistant Au–mesoporous-silica
core–shell nanoparticles. Yin and co-workers and Kresge et al.
synthesized sub-5 nm nanosized Au NPs@mesoporous-silica
(m-SiO2) nanospheres via a soft-templating method and investigated
Fig. 37 (A) (a) Transmission electron microscopy (TEM) image of 16 nm
their catalytic activity for CO oxidation (Fig. 36).350,351 The BET Au@Pd NPs with two monolayers of Pd. (b) Plot of yield vs. Pd shell
surface area and total pore volume of the resulting material, thickness as a function of reaction time for the cross-coupling between
as analyzed by the nitrogen physisorption, were found to 4-bromoanisole with phenylboronic acid. (B) Suzuki–Miyaura cross-coupling
be 736 m2 g1 and 0.92 cm3 g1, respectively. Besides their reaction. Reprinted with permission from ref. 357. Copyright 2011 Wiley-VCH
excellent catalytic activity for CO oxidation, the Au@m-SiO2
core–shell nanospheres displayed robustness, showing good
sinter-resistant properties even at 750 1C. The SiO2 shell not countless synthetic processes.356 The following section describes
only prohibited Au NPs from migrating but also restricted its examples of these reactions that can be effectively catalyzed by a
growth. Such silica-based catalytic systems could possibly be variety of CSNs containing metals.
extended to other important metals and high temperature and 4.3.1. Au–Pd core–shell catalyzed Suzuki–Miyaura reaction.
pressure organic reactions. Amatore and co-workers have reported the synthesis and
The significance of the catalytic reactions is exemplified by catalytic activity of Au–Pd CSNs toward the Suzuki–Miyaura
the selective oxidation of methyl phenyl sulfide to methyl phenyl cross-coupling reaction between 4-bromoanisole and phenyl
sulfoxide using SiO2/@Pd(R)/TiMSS and SiO2/@Pd(S)/TiMSS boronic acid in aqueous medium with base K2CO3 at room
catalysts, wherein in situ generated H2O2, avoids external addi- temperature (Fig. 37).357 The coupling products were obtained
tion of an oxidant. in excellent yield (95%) and also at a faster rate than other reported
catalysts.358,359 The Au@Pd CSNs were found to have unique
4.3. Coupling reactions structural features, in which a shell of one or several Pd(0) mono-
Coupling reactions are an integral part of the synthesis of layer(s) (MLs) was precisely wrapped around a Au(0) nanocore
many drug intermediates and pharmaceutical precursors.352–355 (Fig. 37A(a)). Two to five monolayers of Pd were found to be respon-
The most important coupling reactions include Heck reaction, sible for the NPs’ optimum catalytic conversion rate (Fig. 37A(b)).
Suzuki–Miyaura reaction and Sonogashira reaction, which often 4.3.2. Suzuki–Miyaura reaction catalyzed by Ni/Pd core–shell
involve precious metals, such as Pd, Au, etc., and are deployed in nanoparticles. Metin and co-workers synthesized Ni–Pd CSNs
Fig. 36 Schematic of the formation procedures used for mesoporous silica nanospheres with or without Au NPs. Adapted from ref. 344.
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Fig. 38 Suzuki–Miyura coupling reaction catalyzed by G–Ni/Pd CSNs.
supported on graphene (G) by a sequential reduction method for

the Suzuki–Miyaura reaction.360 The catalyst showed a narrow
size distribution with a mean particle size of B10 nm and a
standard deviation of 5% with respect to the particle diameter.
Phenyl boronic acid and 4-chloro-4-flurophenylboronic acid were
successfully coupled with aryl iodides, bromides, and even
Fig. 39 (a) Schematic of the synthesis of Fe3O4@mSiO2-NHC(x), (b) Suzuki–
chlorides, in a mixture of dimethylformamide (DMF)/water in Miyaura coupling products between various arylboronic acids with chloro-
the presence of base at 110 1C. To compare the effect of the NPs’ benzene over Pd-coordinated Fe3O4@mSiO2-NHC. (c) C–C coupling products
structural features on the catalytic activity, three different Ni/Pd between benzylic chloride and various arylboronic acids over Pd-coordinated
NPs with different Ni/Pd molar ratio, namely 2/3, 7/3 and 3/2, were Fe3O4@mSiO2-NHC. Adapted from ref. 361.
synthesized. The resulting Ni/Pd CSNs supported on graphene
were then employed as catalysts for the Suzuki–Miyaura cross-
coupling reactions, all delivering excellent yields of the corre- Using phenylboronic acid and benzylic chlorides as substrates, the
sponding products (Fig. 38). Among the three Ni/Pd NPs Pd-coordinated Fe3O4@mSiO2-NHC gave diphenylmethane in a yield
investigated, the one with Ni/Pd ratio of 3/2 was found to be the up to 79% (Fig. 39c). Both electron-rich and electron-poor aryl-
most active catalyst for the reaction. Moreover, the G–Ni/Pd boronic acids afforded various diarylmethanes in 71–89% yields.
nanocatalysts remained stable under the reaction condition and 4.3.3. Sonogashira coupling reaction catalyzed by inside-out
were easily recyclable, affording 98% conversion after five catalytic type core–shell nanoparticles. The Sonogashira reaction is typically
cycles without any noticeable Ni/Pd compositional change. a C–C bond forming reaction, which enables the coupling of a
Yang et al. have reported the synthesis of nanoporous terminal sp hybridized carbon from an alkyne with a sp2 carbon of
organosilica microspheres consisting of a magnetic Fe3O4 core an aryl or vinyl halide (or triflate).362 There are many examples in
and an organosilica shell with built-in N-heterocyclic carbene the literatures of this class of reaction, catalyzed by various metal-
(NHC) moiety attached to Pd (Pd-coordinated Fe3O4@mSiO2- containing nanomaterials, including CSNs.363,364
NHC) (Fig. 39a).361 The Fe3O4 microspheres were coated with a Recently, Varma and co-workers reported the use of inside-
thin layer of SiO2 on which a NHC-functionalized nanoporous out core–shell architectures (Cu2O@Cu) with a Cu2O core and
organosilica shell was created surrounding silica-coated Fe3O4 Cu shell as catalyst for the Sonogashira coupling reaction.365
cores via a sol–gel process in the presence of CTAB templates. Their facile solution-phase synthetic strategy generated Cu on
After removing the CTAB templates, magnetic core–shell nano- the outside, producing Cu2O@Cu type CSNs (cf., the more
porous organosilica microspheres with built-in NHC moieties commonly reported material is Cu@Cu2O) (Fig. 40).365
were formed. By gradually reducing the amount of siliceous The Cu2O@Cu CSNs were found to successfully catalyze
precursors added in the third step, three different materials Sonogashira coupling reactions between aryl iodides and phenyl-
could be obtained with decreasing shell thickness. The corres- acetylenes to afford the corresponding biarylacetylenes in excellent
ponding Pd-coordinated Fe3O4@mSiO2-NHC was finally obtained yields (85–94%) (Fig. 40b). Notably, the reaction does not proceed
by dispersing the nanospheres in dry 1,4-dioxane containing with either Cu2O or Cu alone but only with the porous core–shell
Pd(acac)2 (acac = acetylacetonate) and mixing the dispersion at catalyst. Thus, Cu2O@Cu offers a good substitute for expensive
100 1C for 30 h under N2 atmosphere. Pd in this type of coupling. The recovered Cu2O@Cu CSNs after
The catalytic activity of the resulting Pd-coordinated Fe3O4@ the catalytic reactions retained their core–shell nanostructures
mSiO2-NHC was evaluated for Suzuki–Miyaura coupling of and remained stable without significantly losing their catalytic
chlorobenzene and phenylboronic acid in isopropyl alcohol at activity even after multiple runs.
80 1C under N2 atmosphere (Fig. 39b). Many other substrates, Common coupling reactions such as Suzuki–Miyaura, Heck
including moderately sterically demanding arylboronic acids, reaction, and Sonogashira reaction are well studied using various
were found to be smoothly converted to the corresponding types of heterogeneous catalysts. A variety of core–shell NPs
coupling products in 70–86% yields with the aid of NPs as catalyst. namely Au–Pd, Ni/Pd and Pd-coordinated Fe3O4@mSiO2-NHC
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Fig. 40 (a) SEM images of inside-out core–shell architectures (Cu2O@Cu).

(b) Sonogashira coupling reactions of aryl iodides with phenyl acetylenes
catalyzed by Cu2O@Cu NPs. Reprinted with permission from ref. 365.
Copyright 2012 Royal Society of Chemistry.
Fig. 41 (A) Schematic pathway for the synthesis and application of
high temperature-stable NH3 decomposition catalysts based on hematite
core–shell NPs are used for Suzuki–Miyaura coupling reactions in NPs in a porous silica shell. (B) TEM images of (a) a-Fe2O3-35@pSiO2,
(b) a-Fe2O3-75@pSiO2, (c) @pSiO2, and (d) a-Fe2O3-50 + @pSiO2 after
benign media. The noble and rare metals, Pd, and Au could be calcination, respectively. Reprinted with permission from ref. 369. Copyright
replaced by other inexpensive base metals such as copper. Chiral 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
NHC could be incorporated in core–shell NPs synthesis for applica-
tion in asymmetric reactions. The inside-out core–shell architectures
4.5. Tandem deprotection-Knoevenagel and Henry reaction
(Cu2O@Cu) used for the Sonogashira reaction is an example of a
by core–shell nanocatalysts
benign protocol where coinage metal replaces a noble metal.
In addition to stabilizing catalytic groups and increasing catalyst
shelf-life, some CSNs can serve as multifunctional catalyst
4.4. Ammonia decomposition reaction with iron-based
for tandem reactions. Catalytically active organofunctional
core–shell nanoparticles
groups can be grafted onto CSNs, as exemplified by Song and
Ammonia synthesis, which was invented by Fritz Haber almost co-workers,370 who designed a core–shell structured meso-
one-hundred years ago, is a key reaction in various industrial porous silica nanospheres with acid and basic groups in isola-
processes.366,367 In recent years, the reverse protocol that entails tion from one other (Fig. 42).
the decomposition of ammonia into hydrogen and nitrogen has The detailed synthetic method is illustrated in Fig. 42.
come into the limelight, particularly in the context of alternative Tetraethylorthosilicate (TEOS) and 3-mercaptopropyltrimethoxy-
fuel-resources. This approach has enabled the development of silane (MPTMS) were self-assembled with surfactant (CTAB)
ammonia-based hydrogen production, in addition to ammonia templates, followed by oxidation of the thiol groups to sulfonic
fuel cells (as sources of ‘clean’ energy).368 acid functionalities to produce acid-functionalized mesostruc-
In the hydrogen production process, ammonia decomposi- tured silica (MS-A). The resulting material was further coated
tion requires temperatures above 400 1C for thermodynamic with an amino functionalized mesoporous silica shell using
reasons, and therefore most direct ammonia fuel cells typically TEOS and APTMS. Final removal of surfactant by an extraction
function at temperatures between 500 and 700 1C. In this procedure delivered the desired acid–base bifunctional core–
context, high temperature stability coupled with long lifetime shell catalyst (MS-A@MS-B) (Fig. 42A). In two cascade reaction
is the most important requirement for potential catalysts. sequences, this catalyst was expected to show high activity and
Core–shell nanocatalysts address this problem, as exemplified selectivity towards the desired product with no intermediate
by Lu and co-workers, who synthesized high-temperature stable species (Fig. 42B). In fact, the bifunctional MS-A@MS-B catalyst
iron-based core–shell nanocatalysts for ammonia decomposi- was successfully used for performing one-pot tandem deprotection-
tion (Fig. 41).369 The catalysts were found to be highly stable at Knoevenagel and Henry reactions (Fig. 42C).
750 1C with a space velocity of 120 000 cm3 gcat1 h1 and
maintained conversions of around 80% for the test period of 33 h.
Furthermore, the particle size had only a limited effect on the 4.6. CO adsorption on Pd- and Pt-based core–shell
catalytic activity for the diameter range 35–75 nm (Fig. 41). More- nanocatalysts
over, it was noted that the cooling rate after reaction has a strong Remarkable advances in the field of CSNs have enabled nano-
influence on the observed iron and iron nitride phases. catalysts to be designed with unique properties because of their
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Fig. 43 (a) Schematic of the procedure used for synthesizing M@oxide

nanostructures. (b) Representative TEM image of dodecylamine-protected
Pt NPs (left), along with a histogram indicating particle size distribution
(right). Reprinted with permission from ref. 375. Copyright 2012 Wiley-VCH
Fig. 42 (A) Synthesis procedure for acid–base bifunctional core–shell struc- Verlag GmbH & Co. KGaA, Weinheim.
tured catalyst (yellow helix = –SO3H, white helix = –NH2). (B) Schematic reaction
flow of the two-step cascade reaction sequences on the core–shell structured
bifunctional catalyst MS-A@MS-B. (C) One-pot tandem deprotection-
Table 3 CO chemisorption promoted by CSNs containing Pd/Pt NPs
Knoevenagel and Henry reaction successfully catalyzed by acid–base
containing MS-A@MS-B core–shell type nanocatalyst. Reprinted with Sample Pd/Pt dispersion (%)
permission from ref. 370. Copyright 2012 Royal Society of Chemistry.
1 wt% Pd/Al2O3 32
1 wt% Pd@9 wt% CeO2/Al2O3 10
1 wt% Pd@9 wt% TiO2/Al2O3 16
varied nanoarchitecture, composition and particle size, which 1 wt% Pd@9 wt% ZrO2/Al2O3 17
can be easily adjusted in a controllable way to tune their 1 wt% Pt@9 wt% CeO2/Al2O3 6
1 wt% Pt@9 wt% TiO2/Al2O3 17
optical, electrical, magnetic and catalytic properties.288,371,372 1 wt% Pt@9 wt% ZrO2/Al2O3 18
All-metal core–shell colloids, especially Au-, Pd-, and Pt-based
core–shell colloids, with controlled shapes are attractive due to
under conditions identical to those employed in the diffuse
their excellent optical and catalytic activities. Among these,
reflectance infrared Fourier transform spectroscopy (DRIFTS)
Au@Pd, Au@Pt, Pt@Pd, and Pd@Pt CSNs have been shown to
experiments (Table 3).
exhibit superior catalytic properties generally not attainable by
The CO uptake was measured on Pt@CeO2/Al2O3 and
their monometallic counterparts.122,373,374
Pd@CeO2/Al2O3 CSNs after raising the reduction temperature
Gorte and co-workers have reported a synthetic procedure
to 673 K prior to chemisorption of CO at room temperature.
involving self-assembly to generate novel CSN catalysts with
After raising the reduction temperature from 423 to 673 K, disper-
optimized Pt and Pd cores and CeO2, ZrO2, and TiO2 shells for
sion of the Pd@CeO2/Al2O3 core–shell nanocatalysts decreased
CO chemisorption, which also show excellent dispersity in
considerably from 12 to 5% (Table 4). Re-oxidation of the
organic solvent (Fig. 43a).375 Previously, the same group prepared
Pd@CeO2/Al2O3 CSNs and subsequent reduction at 423 K, again
dispersible Pd@CeO2 NPs, from the reaction between cerium
decreased the dispersion only to 10%, signifying that the oxidizing
alkoxide and Pd NPs stabilized by 11-mercaptoundecanoic
acid, in which Ce species self-assembled on the surface of the
particles.376 Table 4 Metal dispersion based on CO uptake at RT
TEM study revealed that the core of the NPs was approxi-
mately 2 nm in diameter and decorated by amorphous oxide 1st reduction 2nd reduction 3rd reduction
Sample at 423 K at 423 K at 423 K
shells (Fig. 43b).375 These particles adsorbed onto inert sup-
ports and served as heterogeneous nanocatalysts. The inter- 1 wt% Pd@9 wt% 12 5 10
CeO2/Al2O3
action between the different metals and the reducible shells 1 wt% Pt@9 wt% 6 8 6
was undoubtedly the key factor affecting the activity as well as CeO2/Al2O3
stability of the core–shell catalysts. The uptake of CO was 1 wt% Pd@9 wt% 18 11 17
ZrO2/Al2O3
quantitatively determined by volumetric adsorption measure- 1 wt% Pt@9 wt% 18 14 19
ments on samples after they had been oxidized and reduced ZrO2/Al2O3
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treatment partially restored the initial dispersion. In contrast, for 4.7. Aerobic oxidative esterification by AuNiOx/SiO2–Al2O3–
Pt@CeO2/Al2O3, there was no loss in CO uptake upon increasing MgO catalysts
the reduction temperature. Rather, the calculated dispersion Esterification is one of the most common transformations in
actually increased slightly from 6 to 8%. Oxidizing the Pt@CeO2/ organic synthesis.377 The oxidative esterification of aldehydes
Al2O3 core–shell nanocatalysts, followed by subsequent reduction with alcohols is a useful route for the synthesis of esters
at 423 K, restored the initial metal dispersion, suggesting that
because aldehydes as raw materials are readily available on a

Pt@CeO2/Al2O3 is considerably less susceptible towards deactiva- commercial scale.
tion following the reduction–oxidation process. The interaction Suzuki et al. have investigated AuNiOx core–shell nanostruc-
between the reducible shells and different metals certainly tures for oxidative esterification, in which the surface of a Au
appears to be an overbearing factor affecting the stability of NP core was covered by NiOx.378 The oxidative esterification of
these core–shell nanocatalysts. methacrolein with methanol to form methyl methacrylate was
performed on supported gold-nickel oxide (AuNiOx) NPs as the
catalyst and molecular oxygen as the terminal oxidant. Various types
Table 5 AuNiOx-catalyzed aerobic oxidative esterification of aldehydes of supports, such as SiO2–Al2O3 and SiO2–TiO2, were explored for
with alcohols with AuNiOx/SiO2–Al2O3–MgO catalystsa the esterification of aldehydes by alcohols, and the best yield was
obtained for AuNiOx/SiO2–Al2O3–MgO catalysts.378 The reaction
Conversion/
Entry Aldehyde Alcohol Product selectivityb (%) scope was studied using different aldehydes and alcohols under
optimized conditions (Table 5).
The distribution of AuNiOx NPs was precisely controlled to
1 Methanol 62/98
avoid any loss of metal during these reactions. The AuNiOx
layer was sharply localized to a region 10 mm deep from the
catalyst surface layer (Fig. 44).
2 Ethanol 11/97
4.8. Catalytic applications of Al2O3@Fe2O3 CSNs for the

synthesis of adipic acid
3 n-Butanol 15/97
Adipic acid is one of the most widely used dicarboxylic acids in
the chemical industry.379 The most common industrial process
for its synthesis involves nitric acid oxidation of cyclohexanol
4 Methanol 61/97 or cyclohexanol–cyclohexanone mixtures.380 However, in this
process, production of nitrous oxide (N2O) as an unavoidable
chemical waste contributes significantly to global warming.
5 Ethanol 10/97 Bhaumik and co-workers have reported mesoporous, crystalline
Al2O3@Fe2O3 CSNs via a new synthetic approach in aqueous
a medium381 utilizing the negative charges on the surface of
Reaction conditions: aldehyde (15 mmol), AuNiOx/SiO2–Al2O3–MgO
(Au: 0.1 mol%) in alcohol (10 mL), O2/N2 (7 : 93 (v/v), 3 MPa) at 80 1C g-Al2O3 for the formation of the CSNs. TEM images and
for 1 h. b Determined by GC. the BET surface area analysis support the mesoporosity in the
Fig. 44 Electron-probe microanalysis spectra of a single particle of AuNiOx/SiO2–Al2O3–MgO. (a) Secondary electron image and line analysis. (b) Color
mapping display corresponding to the concentration of the element distribution. Reprinted with permission from ref. 378. Copyright 2013 American
Chemical Society.
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Fig. 45 TEM images of (a) self-assembled Al2O3@Fe2O3 CSNs, and (b and c)

single particles. In (b), a peripheral a-Fe2O3 layer and (012) lattice fringes are
Fig. 46 Schematic of the synthesis of heterogeneous exposed core–shell
clearly seen. The FFT pattern of (c) is shown in (d). Reprinted with permission
catalysts using space specificity. The inset diagram shows the principle of
from ref. 381. Copyright 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
space specificity. Reprinted with permission from ref. 382. Copyright 2013
Royal Society of Chemistry.
materials (Fig. 45). These Al2O3@Fe2O3 CSNs acted as a Fenton
catalyst in the presence of hydrogen peroxide, and it displayed technologies such as water electrolysers, fuel cells and metal–air
high catalytic activity for the one-step conversion of cyclohexa- batteries to be developed.387,388 As mentioned earlier, some of
none to adipic acid in an environmentally greener aqueous the main synthetic methodologies employed for the synthesis of
reaction medium. core–shell materials include dendrimer encapsulation,389 sol–gel
synthesis,390 as well as colloidal and reverse micelle methods.391
4.9. Heterogeneously exposed core–shell Pt@TiO2 catalysts Energy conversion using electrocatalysts plays an important role
A simple method for the synthesis of exposed core–shell hetero- in the design and improvement of cost-effective benign technol-
geneous catalyst array has been reported using the space specificity ogies that have the potential to alleviate global warming and
of an embodied micelle.382 The particular chemical sources for the over-dependence on fossil fuels. In this regard, fuel cells (elec-
core and shell were deposited selectively at specific regions on the trochemical energy-conversion devices) with polymer electrolyte
embodied micelles with the help of chemical treatment (Fig. 46). membranes can act as convenient power sources in the trans-
The catalyst was prepared by spin coating 0.5% micelle solution portation sector, one of the principal consumers of fossil fuels
(polystyrene-block-poly(4-vinylpyridine)) (PS-b-P4VP) in toluene on a and emitters of greenhouse gases.
silicon wafer, followed by immersing the silicon wafer in methanol The optimum catalytic activity of these materials can be
at room temperature for 10 h, which generated micelles with tuned by controlling their size, structure, and composition for a
distinct core and shell regions. This arrangement allowed the specific catalytic reaction.392,393 The electrocatalytic activity of
catalyst to act as photocatalyst for water splitting, and such micelles such catalyst depends on its synergistic interactions between
are also commonly used materials for thin film processes,383 the core and shell, primarily involving (a) ligand effects, which
allowing NPs to be produced with varied compositions384,385 that affect charge transfer between the components, (b) ensemble
can be deposited on various substrates.386 Additionally, a hetero- effects, which govern the material’s adsorption due to the
geneous Pt–TiO2 catalyst array was also developed to permit presence of distinct atomic groups, and finally (c) geometric
facile fabrication of a catalyst for efficient hydrogen generation effects, which depend on three dimensional structural charac-
through photocatalytic water decomposition. teristics.394 Based on the type, core–shell catalysts have been
used in many areas of electrocatalysis, such as ORR (oxygen
reduction reaction), OER (oxygen evolution reactions), alcohol
5. Electrocatalysis by core–shell oxidation, etc.;287,395–416 some recent examples of core–shell based
nanocatalysts catalysts are discussed below.
Platinum metal is the single best metal catalyst for the ORR
Noble metal-based catalysts are widely employed for various at low temperature in polymer electrolyte membrane (PEM) fuel
electrochemical transformations and energy conversion, enabling cells in both, alkaline and acid electrolytes.417–419 To increase
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Fig. 48 Schematic of the inner Pt diffusion process to the defective sites at

the vertex during cycling in electrolyte. For clarity, the inner Pt atoms involved
in diffusion are shown in green, whereas defects are in yellow. Reprinted with
permission from ref. 426. Copyright 2012 American Chemical Society.
Table 6 Mass activities (MA) and specific activities (SA) for PtML samples
synthesized by either ethanol-based approach or by Cu underpotential
deposition (UPD), derived from the ORR kinetic currents at 0.9 V vs.
reversible hydrogen electrode (RHE)427
Fig. 47 (a) HAADF-STEM image of a PtNiN CSN with corresponding two- Pd@PtML Pd@PtML Pd@Pt2ML
dimensional EELS mapping of Pt M and Ni L signals (dotted lines for Samples Cu UPD ethanol ethanol
visualization purposes only). (b) STEM image of PtNiN CSNs. (c) EELS
linescan profiles of Pt and Ni and schematic of a single PtNiN NP (blue, Pt/(Pt + Pd) (at%) 26.9 27.3 33.3
Pt (wt%) 16.5 17.1 18.1
Pt; gray, Ni; purple, N). Reprinted with permission from ref. 426. Copyright
Pd (wt%) 24.5 24.9 19.7
2012 American Chemical Society. MAPta (A mg1) 0.62 0.64 0.62
MAPGMb (A mg1) 0.25 0.26 0.30
SAc (mA cm2) 0.25 0.58 0.70
ECSAd (m2 g1) 191 110 89
the reaction rate, several bimetallic electrocatalysts composed of Pt a
MAPt, mass activity normalized by the mass of Pt. b MAPGM, mass
and 3d-transition metals (Fe, Co, Ni,) have been examined.401,420–425 activity normalized by the mass of Pt-group metals (PGM). c SA, specific
Adzic and co-workers have investigated PtNiN core–shell catalysts activity normalized by the ECSA. d ECSA, electrochemical surface area.
with a low Pt content shell and inexpensive NiN core and showed
that they displayed excellent electrocatalytic activity and stability
for the ORR.426 The catalysts were synthesized by chemical the temperature, H2O, and pH. Table 6 summarizes the ORR
reduction and subsequent thermal annealing in N2, wherein activities for Pd@PtML and Pd@Pt2ML samples fabricated
NH3 was used as a nitrogen precursor at ambient pressure. via the ethanol-based approach as compared with those for
High angle annular dark-field (HAADF) images of the materials Pd@PtML fabricated via Cu under potential deposition. The smooth
revealed the core–shell structure of the NPs (Fig. 47). By over- Pt surface obtained at 70 1C was responsible for a smaller electro-
lapping the two-dimensional mapping of Pt and Ni in EELS chemical surface area (ECSA) than that obtained at room tempera-
signals from a single NP, as shown in Fig. 47a (dotted lines), ture owing to high coordination sites on smooth terraces (less
the core–shell structure of the materials was confirmed. The reactive to H adsorption/desorption) rather than low coordination
EELS line scan profile defined the distribution of Pt and Ni sites on a roughened surface with edges and defects.
components in a representative single NP, enabling the Pt shell Ge et al. have synthesized composition-controlled bimetallic
thickness to be directly measured (Fig. 47c). The presence of catalysts containing Pt as a shell and Cu as a core by electro-
N atoms in the core allowed facile diffusion of interacted Pt chemically dealloying a bulk Pt15–Cu85 (atom %) binary alloy
from the inner shells to the surface, filling the vacancy sites using a potential-controlled approach.428 Dealloying at 0.4, 0.5,
(geometric effect), resulting in augmented durability of the 0.6 and 0.7 V yielded bimetallic Pt–Cu catalysts with chemical
catalysts (Fig. 48). compositions of Pt48Cu52, Pt55Cu45, Pt67Cu33 and Pt100Cu0, respec-
Electrochemistry and DFT methods revealed that the high ORR tively. The Pt/Cu ratio of the dealloyed nanoporous catalyst could
activity and durability of the PtNiN catalyst can be attributed to the readily be adjusted over a wide composition range by simply
Ni nitride core, which influences the behavior of the Pt shell by controlling the dealloying potential. The thickness of the Pt shell
inducing both geometric and electronic effects, thus controlling was dependent on the potential cycles. The prepared catalyst was
the catalytic activity.426 The same group used a surfactant-free, well characterized by aberration corrected scanning transmission
ethanol-aided, wet chemical synthetic approach to coat Pd NPs electron microscopy (STEM) equipped with electron energy-loss
with uniform Pt atomic layers on a carbon support.427 The spectroscopy (EELS), the results of which are shown in Fig. 49.
monolayer deposition was carried out during the oxidation of The resulting material was used as an electrocatalyst for the
ethanol catalyzed by the core NPs. Subsequent reduction of electrochemical oxidation of formic acid and its catalytic activity
[PtCl6]2 ions to Pt atoms allowed the formation of atomic Pt was compared with a commercial Pt/C catalyst in 0.1 M HClO4
layers; the reducing power of ethanol was tunable by adjusting solution media. The dealloyed Pt–Cu sample containing E67.2% Pt
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Fig. 49 STEM image and EDS elemental maps of the dealloyed Pt–Cu ligament: (a) HAADF-STEM image of the nanoporous structure; (b) mixed STEM-EDS
elemental mappings of Pt-L & Cu-K; (c) elemental mapping of Pt-L; and (d) elemental mapping of Cu-K. The composition intensity profile of (e) Pt and (f) Cu
were taken from the labeled region in (a). Reprinted with permission from ref. 428. Copyright 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Fig. 50 (a) Scheme showing the synthetic route for Au@Co3O4 core–shell NCs. (b) TEM image of Au NCs (inset: histogram of the size distribution).
(c) TEM image of Au@Co NCs (inset: histogram of the size distribution). (d) TEM image of a two-layer array of the Au@Co NCs (inset: modeled projection
of the two-layer NC assembly). (e) HRTEM image of a single Au@Co NC. (f) TEM image of Au@Co3O4 NCs supported on carbon. (g) HRTEM image of a
single Au@Co3O4 NC. Reprinted with permission from ref. 430. Copyright 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
exhibited voltammetric behavior very similar to that of the Pt/C relatively Ir-rich shell. Partial removal of the surface Cu by
catalyst, i.e., hydrogen adsorption/desorption at 0.03–0.4 V, the dealloying greatly increased the mass activity and specific
electrochemical double layer at 0.4–0.6 V and the formation of activity of the catalyst. It was suggested that these IrCu particles
Pt oxides and their reduction at 0.6–1.2 V vs. RHE. may have a controlled Pt monolayer, leading to a downshift
Bimetallic IrCu NPs have been synthesized and used as of the d-band center with respect to the Fermi level. The
a core for a Pt monolayer electrocatalyst.429 The CSNs were altered electronic and geometric effects due to the IrCu core
prepared by dissolving IrCu alloy, which ultimately resulted in a were compared to pure Ir enhanced ORR activities and an
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Fig. 51 (a) iR-corrected polarization curves of Au@Co3O4/C (64 mgAu@Co3O4 cm2, in which the Au loading was 24 mgAu cm2 and Co3O4 loading was
40 mgCo3O4 cm2), (Au + Co3O4)/C (24 mgAu cm2 and 40 mgCo3O4 cm2), Co3O4/C (40 mgCo3O4 cm2), and Au/C (24 mgAu cm2) catalysts recorded in
O2-saturated 0.1 M KOH at a scan rate of 5 mV s1 and continuous electrode rotating speed of 2500 rpm. (b) Activity of the catalysts at an overpotential of
0.35 V. (c) Tafel plots of catalysts. (d) Chronopotentiometry curves of Au@Co3O4/C and Ir/C (40 mgIr cm2) under a current density of 10 A gAu@Co3O41
or 10 A gIr1 in O2-saturated 0.1 M KOH. Reprinted with permission from ref. 430. Copyright 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
augmented stability for the PtMLIrCu core–shell electrocatalyst only 0.31 V was needed for Au@Co3O4 to achieve a current
was obtained. density of 10 A gcatalyst1.430
IrNi@IrOx NPs were also prepared in an analogous manner, Wang et al. have investigated the effect of synthetic para-
using IrNix as precursor alloy by selective surface dealloying of meters on a Pd–Pt core–shell catalyst by STEM analysis and
Ni and controlled surface oxidation of Ir. These metal-oxide their electrocatalytic activity for the ORR;431 effects of the
hybrid (M1M2@M1Ox) core@shell NPs were used as electro- thickness of the Pt shell, lattice mismatch and particle size
catalysts for the OER; a 3-fold higher catalytic activity was on the specific and mass activities originating from changes in the
observed for the electrochemical OER over benchmark catalysts effective surface area were discussed. The prepared core–shell
(IrNi@IrOx metal oxide core–shell). Furthermore, the noble- structure was characterized at an atomic level using Z-contrast
metal content of the catalysts could be lowered without com- scanning transmission electron microscopy coupled with element-
promising the catalytic activity of the materials411 and the sensitive electron energy loss spectroscopy (Fig. 52a–f). The total
general synthetic approach could be adapted to make a range number of atoms in the column, the square of their average
of other noble metal NPs for catalysis. atomic number (Z2), was determined based on brightness
In another recent report, a Au@Co3O4 core–shell nanocata- reflecting into enhanced HAADF intensity. Coupling element-
lyst with uniform overall particle size and shell thickness was sensitive EELS with HAADF images offered an alternate means
synthesized by adjusting the amount of oleylamine (OAm) and for determining the thickness and uniformity of the Pt shells
oleic acid (OA) ligands (Fig. 50). The resulting material showed (Fig. 52g and h). The enhanced catalytic activity was attributed to
a very strong synergistic effect between the core and shell. the effect of nanosize-induced surface contraction on the facet-
Specifically, the Co3O4 shell in Au@Co3O4 displayed strong dependent oxygen binding energy.
binding to oxygen due to its Co atoms, which are known active Sun et al. have reported a facile synthetic method for making
centers for the OER. The nanocatalyst was shown to catalyze the monodisperse, sub-5 nm core/shell Au/PtCu NPs by reducing
OER, giving an overpotential value of 0.35 V. The Au@Co3O4 platinum- and copper–acetylacetonate in the presence of 5 nm
NCs gave a 7 times higher current density in the OER than a Au NP seeds and 1,2-hexadecanediol (HDD), OAm and OA as
Au and Co3O4 NC mixture or Co3O4 NCs alone and 55 times capping agent at 200 1C (Fig. 53a–d).432 The Au core provided
higher than Au NCs alone (Fig. 51). A stable overpotential of suitable nucleation sites for CuPt alloy formation. The interaction
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Fig. 52 (a and b) HAADF-STEM images of the Pd(core)–Pt(shell) NPs obtained for the PdCPt1 and PdCPt4 samples, respectively. NPs overlap on the left
side in (a) and at the top in (b). (c and d) Intensity profiles (O) from the scan lines (the left ends are defined to be zero on the x-axes and the intensity at the
nearby vacuum set the zero for y-axes) in (a) and (b), and the best fits (black lines), based on the structure models shown in (e) and (f) for Pd particles with
1 and 3–4 Pt surface layers, respectively. (f) Projection of the structure model with 4 Pt layers on the STEM image plane (left) and the arrangements of
atoms in the vertical columns along the scan line (right); HAADF and Pd EELS intensity profiles for a PdCPt2 sample. (g) Comparison of HAADF (black) and
Pd EELS (red) intensity profiles in a line scan. (h) Two-dimensional mapping of HAADF intensity (left) and Pd EELS signal (right) obtained with 0.27 nm per
pixel resolution. Reprinted with permission from ref. 431. Copyright 2009 American Chemical Society.
Fig. 53 TEM images of (a) 5 nm Au NPs and (b) 7.5 nm Au/Cu35Pt65 NPs. (c and d) HRTEM images of a single Au/Cu35Pt65 NP acquired at a different focus
condition. Reprinted with permission from ref. 432. Copyright 2014 American Chemical Society.
between the core and shell made these Au/CuPt NPs useful for Their specific (mass) reduction and oxidation activities reached
ORR and methanol oxidation reaction in 0.1 M HClO4 solution. 2.72 mA cm2 (1500 mA mg1 Pt) at 0.9 V and 0.755 mA cm2
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Fig. 54 (A and B) TEM and (C) HRTEM images of hAg@Pt–RGO. The inset in image (A) shows the corresponding SAED pattern. Reprinted with permission
from ref. 433. Copyright 2014 Royal Society of Chemistry.
(441 mA mg1 Pt) at 0.8 V (vs. RHE), respectively (Fig. 53e and f). 0.9 V, respectively, which were found to be 3.1 and 3.7 times
The existence of the Au NPs at the core suppressing the Pt usage larger than values obtained for a commercial Pt/C catalyst,
as well as the stability of the Au/CuPt catalyst for fuel cell respectively.435 According to theoretical calculations, the elec-
reactions was demonstrated. The core/shell design was found tronic effect of the Cu substrate on the Pt monolayer was
to be effective for optimizing the catalysis. responsible for the higher activity of PtCu NWs compared to
A one-pot solvothermal method has been used for the the commercial Pt/C catalyst. Furthermore, the PtCu NWs
preparation of reduced graphene oxide (RGO) supported hollow showed much better durability and stability compared to the
Ag@Pt core–shell nanospheres (hAg@Pt), using ethylene glycol commercial Pt/C.
(EG) as a reducing agent and sodium dodecyl sulfate (SDS) Recently, Yung and co-workers have synthesized Pt nano-
as a soft template.433 Control experiments showed that the structures from submonolayer to monolayer by ion adsorption-
molar ratios of the Pt–Ag precursors, amount of SDS, presence in situ electrochemical reduction of Au NPs supported on
of RGO and reaction temperature were critical for achieving multiwall carbon nanotubes (MWCNTs).436 The coverage of Pt
the best catalytic activity (Fig. 54). The electrocatalytic activity on the Au surface was controlled by varying the concentration
and durability toward ethylene glycol oxidation was enhanced of Pt(II) or by repeating the ion adsorption and electrochemical
using hAg@Pt–RGO, which could offer a promising potential reduction process. The as-prepared Au@Pt/CNTs catalysts dis-
electrocatalyst for direct alcohol fuel cells. Certain defects in played coverage-specific electrocatalysis. Au@Pt/CNTs with low
RGO were suggested to be responsible for better adsorption Pt coverage were shown to be inactive towards methanol
of the OH(ads) species generated from water dissociation oxidation but oxidized formic acid effectively through a direct
during the electrochemical measurements. Compared to metallic pathway with mass specific activity 90 times higher than that of
nanostructures, hAg@Pt–RGO showed a higher catalytic activity a commercial Pt/C catalyst. Owing to the catalyst’s inertness to
for water dissociation as more OH(ads) could be adsorbed on methanol, it showed high performance in the ORR with high
the catalyst. Meanwhile, the well-dispersed hAg@Pt on the RGO methanol tolerance. However, simply increasing the Pt cover-
increased the surface area and improved the electrical conductivity age to above 40% caused the formic acid oxidation process to
of the nanocomposites, providing more active sites available for proceed by both direct and indirect catalytic pathways, resulting
EG molecules.433 in high methanol oxidation activity (Fig. 55). A strong relation-
In another study, monodispersed core/shell Ni/FePt NPs ship between the surface Pt coverage of the as-prepared Au@Pt/
were prepared by seed-mediated growth and subsequently CNTs material and its electrocatalytic activity towards formic
converted to Ni/Pt NPs. The aforementioned NPs were washed acid, methanol and oxygen was reported.
by acetic acid to obtain active Ni/Pt catalysts and employed in the Kim et al. have reported Pd@Pt core–shell NCs437 synthe-
ORR. The specific activity and mass activity of 4.2/0.8 nm core/ sized by an aqueous one-pot synthetic method comprising
shell Ni/FePt after an acetic acid wash reached 1.95 mA cm2 sequential formation of the Pd core followed by the Pt shell
and 490 mA mg1 Pt at 0.9 V (vs. RHE). These results were much as a result of the inherently slower reduction of Pt precursors
better than those obtained with a benchmark commercial Pt used in the synthesis. The Pt shell thickness of the Pd@Pt NCs
catalyst (0.34 mA cm2 and 92 mA mg1 of Pt at 0.9 V). Cu@CuPt could readily be manipulated by controlling the molar ratio of
core@shell NWs with 1D nanostructure were also synthesized Pt and Pd precursors in the growth solutions (Fig. 56). The
using Cu NWs as templates in organic solvent medium and electrocatalytic activity of the prepared Pd@Pt catalyst was
they were shown to have efficient electrocatalytic activity toward tested for MOR activity and shown to be highly dependent on
the ORR.434 the Pt shell thickness due to different interactions between the
Well-defined Pt–Pd@Pd core–shell nanospheres (PtPd@Pd Pt and Pd. The Pd1@Pt1 catalyst was found to exhibit the
NSs) have been synthesized for electrocatalytic oxidation using highest catalytic activity.
a simple one-pot solution approach, where N-methylimidazole Nogami and co-workers synthesized Pt–Pd core–shell nano-
and poly(vinyl pyrrolidone) (PVP) were used as directing and particles using a modified polyol method and have described
capping agents without application of any seed, template or the details of their formation and growth mechanism.70,438–440
organic solvent.435 The ORR mass activity and specific activity In their procedures, in order to control the morphology of the
over the PtCu NWs were 0.216 A mg1 and 0.404 mA cm2 at Pt-NP core, AgNO3 acts as a structure-modifying agent; ensuing
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Fig. 55 (a) Cyclic voltammograms (CVs) of Au@Pt/CNTs with 27.9% Pt coverage in 0.1 M H2SO4 + 0.025 M HCOOH (black line) and 0.1 M H2SO4 + 0.1 M
methanol (red line), both recorded at 50 mV s1. (b) CVs of Au@Pt/CNTs with 57.6% Pt coverage in 0.1 M H2SO4 + 0.025 M HCOOH (black line) and 0.1 M
H2SO4 + 0.1 M methanol (red line), both recorded at 50 mV s1. (c) LSVs (linear sweep voltammograms) of Au@Pt/CNTs with 27.9% Pt coverage in 0.5 M
H2SO4 with and without 0.1 M methanol, 10 mV s1, 1600 rpm. (d) Linear sweep voltammetry (LSV) results of Pt/C in 0.5 M H2SO4 with and without 0.1 M
methanol, 10 mV s1, 1600 rpm. Reprinted with permission from ref. 436. Copyright 2013 Springer.
Fig. 56 Low (a–c) and high magnification (d–f) HRTEM images of Pd3@Pt1
(a and d), Pd1@Pt1 (b and e), and Pd1@Pt3 (c and f) NCs. Scale bars indicate
5 nm. Reprinted with permission from ref. 437. Copyright 2014 American
Chemical Society.
Pt-NP core serve as seeds for Pd-shell materials. Well-

characterized materials by HRTEM and EDS have revealed the
information regarding the morphology and the size of the core
and shell (Fig. 57), which have allowed them to provide the
possible growth mechanism. The materials were successfully
applied as electrocatalyst in proton exchange membrane fuel
cells (PEMFCs) and in direct methanol fuel cells (DMFCs). Their
Fig. 57 (a–e) HRTEM images of Pt–Pd core–shell nanoparticles. (f–h)
electrochemical study revealed that the Pt–Pd nanocatalysts Models of octahedral, cubic and tetrahedral Pt–Pd core–shell nano-
showed better electrocatalytic activity and stabilization than particles. Scale bars: (a–d) 5 nm and (e) 2 nm. Reprinted with permission
the parent Pt nanocatalysts and the activity is more dependent from ref. 439. Copyright 2011 Elsevier Ltd.
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Fig. 58 Size-dependent percentage of atoms on the (111) plane, edge

and vertex, represented by R(111), Re and Rv, respectively. Rshell denotes the
percentage of atoms on the shell, where Rshell = R(111) + Re + Rv. Atoms in
yellow, blue and orange denote Ptv, Pte and Pt(111) atoms. Inset is the
structure of Pt561 where Re = R(111). Reprinted with permission from Fig. 59 (a) Surface metal migration of CSNs. (b) Thick shell Au–Pd
ref. 441. Copyright 2014 Nature Publishing Group. nanooctahedra, and (c) HR-TEM image of a thin shell octahedron’s Au–
Pd interface, showing epitaxial growth. Reprinted with permission from
ref. 443. Copyright 2014 American Chemical Society.
on the nanostructuring effect than the size of materials. This is

one of the examples, where a direct synergistic effect of Pt–Pd Under electrochemical conditions, Au metal migrated from the
nanocatalysts was demonstrated, which aided the materials to core to shell, and the extent of migration was shown to depend
achieve higher catalytic activity than their individual components. on the type and pH of the electrolyte, as well as the potential
The size-dependent activity of Pt-based alloys consisting of range employed (Fig. 59). TEM images revealed Au seeds and
Pt and late transition metals (TM) elements in the 3d series, thin and thick shell Au–Pd octahedra (Fig. 59b). Additionally,
typically Pt3Fe, Pt3Co and Pt3Ni, were studied for the ORR continual lattice fringes from the Au core to Pd shell phases
in fuel cells. The electrocatalytic results were supported by were observed, indicating epitaxial growth (Fig. 59c). Both particle
DFT calculations. The activity of core–shell Al13@Pt42 catalyst types had well-defined structures and good monodispersity, which
was found to depend on the formation of alloy with Al with enabled a thorough electrochemical evaluation. The Au@Pd core–
the cluster; the covalent Pt–Al bonding effectively activated the shell nanocatalyst was employed for its electrocatalytic activity,
Pt atoms at the edge sites, which enabled a high utility to be including metal relocation by cyclic voltammetry and the ethanol
achieved of up to 70% (Fig. 58).441 oxidation reaction (EOR).443 In the EOR, it was observed that
Guo et al. used a seed-mediated growth method to prepare migration was more prevalent in the thin shell particles, at first
core/shell FePtM/FePt (M = Pd, Au) NWs.442 They adapted a promoting EOR activity by strain effects, but then inhibiting
method of controlled decomposition of Fe(CO)5 and reduction activity because of a combination of ligand and ensemble effects.
of Pt(acac)2 in the presence of 2.5 nm wide FePtM NW seeds and The thick octahedral shell prevented relocation but inhibited
were able to deposit B0.3–1.3 nm thick FePt shell on the FePtM Au-induced strain effects, resulting in overall low catalytic activity.
core. These FePtM/FePt NWs were used for the ORR and displayed Migration of metals during catalytic ethanol oxidation was found to
activity that was dependent on shell thickness and core composi- alter the particle’s surface composition and electronic structure,
tion as well as significant stability under the ORR conditions. thus improving the core–shell particles’ activity (Fig. 60).
Generally, bimetallic and multimetallic NPs display better Sun and Lu have reported444 the synthesis of monodispersed
catalytic activity compared to their monometallic counterparts. M/CuPd NPs using palladium- and copper–acetylacetonate
It is quite tricky to optimize activity on the basis of composition in the presence of Ag (or Au) NPs with well-ordered shell
and structure, as metal migration allows the geometric, electronic, thicknesses (0.4, 0.75, and 1.1 nm) and CuPd compositions
and ensemble effects to change over time. Bimetallic nano- for use in the ORR (Fig. 61). Catalysts with compositions of
particles endure metal migration under specific reaction condi- Ag/Cu37Pd63 and Au/Cu40Pd60 having 0.75 and 1.1 nm shells,
tions, caused by surface energy discrepancy and/or presence of respectively, were found to be more efficient compared to a com-
oxidizing or reducing agents in the system. This has gained mercial Pt catalyst, exhibiting their mass activity B0.20 A mg1 of
tremendous interest in nanocatalysis research.322 For instance, noble metal at 0.1 V vs. Ag/AgCl (4 M KCl). Additionally, DFT-based
in well-designed core–shell structure, the core metal could have calculations showed that Ag/CuPd and Au/CuPd NPs with 0.8
lower surface energy than the shell metal, so when sufficient and 1.2 nm thick CuPd2 shells have the optimal surface strain
energy provided, the core metal would migrate to the particle and composition to catalyze the ORR. The obtained catalysts
surface in order to lower the overall surface energy. exhibited higher stability than Pt-based catalysts, retaining
Brodsky et al. have synthesized Au@Pd core–shell octahedral 77.6% of their activity after 48 000 s i–t test (62.9% for the
NPs with tunable thicknesses for electrocatalytic applications.443 Pt catalyst). Thus, these Ag (Au)/CuPd NPs offer a promising
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Fig. 60 (a and b) EOR performed on thin and thick shell Au–Pd core–shell octahedra, respectively, in 1 M KOH and 1 M ethanol. (c and d) Plots of EOR
current density vs. cycle number for thin and thick shell octahedra, respectively, for peaks I–IV as labeled in (a). Reprinted with permission from ref. 443.
Copyright 2014 American Chemical Society.
valence charge donation from Pt to Ru, thereby increasing the

(binding energy) Eb by 0.44 eV and thus lowering the valence
band (VB) level by 0.31 eV. Such VB amendment increased the
surface activity for the electrooxidation of methanol and sub-
sequent chemisorption, initiated carbon monoxide oxidation and
enhanced the anodic reaction kinetics of the DMFC system. The
electrocatalytic results indicated that the Ptshell/Rucore NPs are
promising candidates for the development of high-performance,
inexpensive and environmentally benign DMFCs.
Fig. 61 Monodisperse M/CuPd NPs for the ORR. Reprinted with permis- The noble and the non-noble metals can be tuned in the alloy
sion from ref. 444. Copyright 2014 American Chemical Society. precursor, such that both expansive and compressive strain can
control the strengthening or weakening of surface bonds, per-
mitting continuous alteration of their catalytic activity. Strasser
non-Pt alternative for catalyzing the ORR. This investigation et al. have investigated the remarkable electrocatalytic activity
focused on tuning the surface strain and composition in the exhibited by dealloyed Pt–Cu NPs and demonstrated how lattice
core–shell structure to maximize its ORR performance, thereby strain can be employed practically to adjust the catalytic activity
identifying an advanced nanocatalyst that exhibited ORR activity of dealloyed bimetallic NPs for the ORR.95 The density of the
superior to that of Pt. shell changed the d-band structure of the Pt atoms, thereby
Lin and co-workers have reported near-monolayer thick weakening the adsorption energy of the reactive intermediates
shell atoms for application as ORR electrocatalysts in the direct compared to using unstrained Pt, resulting in increased catalytic
methanol fuel cell (DMFC).445 X-ray diffraction results con- performance, as confirmed by DFT-based calculations. Energy-
firmed that the crystal structure experienced compressive strain dispersive elemental color-map overlays for Pt and Cu were acquired
near the Pt shell region. The shell thickness of Ru@Pt CSNs was using a probe-corrected scanning transmission electron microscope
determined to be 1.5 atomic layers using a core–shell scattering (STEM) for the Pt25Cu75 alloy precursor annealed at 800 1C and
model in the small-angle X-ray scattering experiment. The power dealloyed catalyst separately (Fig. 63). A resultant EDS sketch across
density of a DMFC with Ru core–Pt shell NPs was B450% (from the diameter of characteristic (B4 nm) dealloyed NPs con-
17.1 to 92.8 mW cm2 mg1), which was far superior to compo- firmed the existence of a Pt-enriched layer (B0.6 nm) on the
nent Pt NPs, Overall, this proved to be one of the most inexpensive surface of the dealloyed particles, (Fig. 63c). Fig. 63d shows that
and environmentally benign DMFCs showing exceptional per- the dealloyed NP catalysts synthesized at higher annealing
formance (Fig. 62). The inherent strain promoted substantial temperature displayed reduced activity probably because of
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Fig. 62 Scheme for assembly of a DMFC full stack. (a) Devices of flow field, fluid components, frames and membrane electrolyte assembly (MEA).
(b) Assembled full stack. (c) Details of MEA component. Reprinted with permission from ref. 445. Copyright 2014 American Chemical Society.
Fig. 63 Elemental maps and line profiles of Pt–Cu bimetallic NP precursors and dealloyed active catalysts. High resolution energy dispersive
spectroscopy (HR-EDS) elemental maps of a Pt25Cu75 bimetallic NP alloy precursor (a) and the active electrocatalyst obtained after Cu dealloying from
the precursor (b). Pt is shown in blue, Cu in red and pink domains indicate well-alloyed Pt–Cu domains. (c) HR-EDS line profile across an individual 4 nm
diameter dealloyed Pt–Cu alloy active-catalyst particle. (d) Experimental and predicted relationships between electrocatalytic ORR activity and lattice
strain. Reprinted with permission from ref. 95. Copyright 2010 Nature Publishing Group.
alterations in the mean particle size. Overall, the strain-related that involve amendment of the adsorption energy of reactive
tuning for the ORR may offer a useful route for controlling the intermediates, including the electrooxidation of small organic
activity of other significant electrocatalytic chemical reactions molecules (viz. methanol, ethanol and related moieties).95
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The deployment of core–shell nanostructures as electro- study, the atomic arrangements of Fe/Cu and Fe/Au core–shell
catalyst in various applications including ORR, HER, EOR, nanomaterials, prepared via gas-phase deposition, have been
DMFC, etc. displayed many unique properties that are not investigated using EXAFS (extended absorption fine struc-
exhibited by several others catalysts. The design and develop- ture)456 which revealed the structural complexity of the core
ment of practical electrochemical processes using core–shell materials as a function of shell materials. The synergism
nanocatalysts is generally meant to overcome the overpotentials between the core and shell is an important factor for several
and low current density. Moreover, core–shell nanostructures catalytic and electrocatalytic applications; electrocatalytic activity
provide an exceptional way to increase the surface energy of active of Pd–Pt alloy and core–shell has been investigated for DMFCs as
sites on shell surface and decrease the reactions overpotential. a function of size, shape, and compositions of the nanocatalyst
The integration of various components into a hybrid nano- and the highest activity was discerned for core–shell nano-
system for the optimum and synergistic utilization offers an particles with monolayer shell when compared to their alloys
effective way to design effective electrocatalysts as exemplified and mixed NPs.457 Such continuing progress in this area will
by various hybrid strategies to enhance the electrocatalytic help attain the optimum conditions to develop core–shell nano-
property of core–shell nanostructures nanoparticles for different catalysts endowed with higher efficiency.
electrocatalytic applications. Another significant challenge for core–shell synthesis is
their bulk-scale preparation, as during the scaling up process,
they often lose their intrinsic chemical and physical properties,
6. Perspectives and future prospects which are fundamentally important for their catalytic behavior.
Additionally, most of these core–shells NPs, especially the ones
Over the last decade, CSNs have been actively employed in employed in electrocatalysts, are rather expensive, although they
various advanced applications, including solar cells, chemical are quite effective for the respective applications.458–463 Hence,
sensing, catalysis and electrocatalysis. Some of the biggest replacing such noble metal containing CSNs by inexpensive
challenges in this field include ensuring the compatibility materials for electrocatalysis and related applications is likely
between the core and shell and utilizing the unique properties to be an active area of future research.464–467
of core and shell individually. In addition, improvement of both Recently, ‘‘surface-protected etching’’ processes have been
core and shell materials for specific applications, particularly successfully employed for the fabrication of several nanostruc-
in the context of sustainable energy, has also been the focus of tured systems, including yolk–shell and core satellite nano-
recent research efforts. catalysts, in which mostly metal nanocatalysts are stabilized by
Various types of cores have been used, including oxides such porous shells.330,468–470 Although, the uniformity of the pores
as silica, ZrO2, iron oxides and also metals especially the noble can often be a concern and needs thorough investigation, the
ones (e.g., Ag, Cu, Pd). Among these options, earth-abundant porosity of the silica and titania shells, which affects the reaction
iron oxide (magnetite and maghemite) or iron supports are rates of catalytic processes, can be well controlled during such an
considered a superior class for decorating (or being decorated etching process. An advanced ‘‘surface-protected calcination’’
with) various catalytic active shells (Cu, Pt, Ni, etc.),293,434,446–451 method may also be ideal for the preparation of anatase titania
mainly because they (i) are inexpensive, (ii) can be prepared shells, in which added silica species can stop overgrowth of
easily, and, most importantly, (iii) can be separated magneti- the titania grains and help maintain its porous structure and
cally, which is undoubtedly a great advantage from sustainable structural reliability.
chemistry viewpoint. Recently, iron (Fe(0))-based CSNs have also A similar approach may also be used for materials with
been synthesized successfully in a variety of applications,452–454 effective photocatalytic activity. Additional important consid-
but maintaining a stable Fe(0) oxidation state has always been a erations for these types of core–shell nanostructures are the
topic of concern which needs to be resolved in a better and more availability of various metal combinations and prospects for
efficient way. studying the synergies between the different components of the
As explained in the review, core–shell nanomaterials are core–shell structures to boost structural stability and catalytic
often known to have better catalytic activity due to the presence activity/selectivity. This has allowed the development of highly
of different effects (ligand, ensemble and geometric). Hence, effective and stable photocatalysts featuring multilayer core–
it’s important to identify the experimental factors that can steer shell structures. The etching-based protocol mentioned above
the core–shell materials to have such desirable effects. The is easy to use, convenient in engineering the pore size and
understanding of the atomic arrangements and the interac- generally applicable to many oxide materials.
tions between core and shell at the interface has always been In terms of the synthesis, recent advances have led to the
considered crucial for designing efficient nanocatalysts. The design and preparation of more complicated structures including
availability of the state-of-the-art instrumental techniques and movable cores within hollow shells and hollow movable cores
powerful computational ability has allowed studying them within hollow shells and surface metal migration of CSNs.443
so closely. For instance, high aberration corrected STEM tech- The unique design and characteristics of these nanocatalysts
nique and theoretical-calculation-directed studies have eluci- offer advantages in different applications, including magnetic
dated the formation mechanism and explained the stability of photocatalysts, self-assembled photonic crystals with controlled
Pd–Pt and Pt–Pd bimetallic core–shell materials.455 In another bandgaps, and magnetic toners and inks. Additionally, since
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they are known to have good encapsulation ability, the targeted made from transition or non-transition metals, and their
release of biomolecules may also be possible. properties have been varied or tuned according to the elements
The emerging areas of flow chemistry, MW- and sonication- they are composed of and the synthetic protocols employed to
assisted techniques have also recently made inroads in the make them. Many of the synthetic methods used to make these
nanocatalysis and electrocatalysis arena.471,472 Use of a flow materials mainly involved wet chemical approaches, electrode-
reactor in conjunction with MW-assisted methods appears to position, electrochemical dealloying, solvothermal method,
be the best approach for preparing CSNs on a relatively large etc. By using one or a few of these synthetic methods, or in
scale. Also, the fact that the synthesis of CSNs by MW irradia- combination, and by varying the synthetic conditions, a wide
tion or sonochemical methods is relatively unexplored owing to variety of core–shell electrocatalysts with different structure
their inadequacy in controlling morphology, suggests the and properties has been prepared. While many of the materials
future paths based on the development of the novel CSNs reported and discussed above contain noble metals, making
involving such technologies.473 Additionally, mechanochemical materials entirely from non-noble metals and earth-abundant
techniques such as grinding, has not yet been explored for the elements is of increasing interest in order to address sustain-
synthesis of CSNs, probably due to inherent limitations of the ability challenges. Many of these materials and the electro-
technique. Recently, a trimetallic core–shell system, also known chemical transformations they catalyze would also be of great
as trimetallic NPs or integrated NPs, has been employed for interest for future renewable energy technologies, such as fuel
ORR, hydrolytic dehydrogenation, methanol electrooxidation, cells, water electrolysers and energy storage devices.
catalytic hydrolysis of amine borane and other applications.474–476 CSNs appear to offer great potential for vapor phase reac-
On this basis, optimal metallic cores or shells could be designed tions (e.g., hydrogenation, oxidation, and alkylation) involving
for specific applications. Considering the current state of core– gas phase reactors as well. Combination of two different metals
shell nanocatalysts, we are hopeful that better systems than (bimetallic) for the core and shell has led to the emergence of a
currently available ones will be found that are capable of perform- new generation of nanocatalyst that can be explored for a
ing more efficiently and selectively. number of important chemical reactions. Further, tuning the
composition of the two metals would allow selective organic
transformations with ease and provide additional tools for
7. Concluding remarks chemists to attain the goal of sustainability. These advance-
ments in core–shell nanocatalysis will be expected to provide a
CSNs have emerged as valuable and versatile nanomaterials for solid and stable platform for the development of heterogeneous
catalysis because of their additive or complementarily enhanced catalysis, green chemistry, and environmentally benign proto-
properties compared to their one-component counterparts. The cols in the near future.
strain and ligand effect between the core and surrounding shell
can be exploited for tailoring the catalytic activity and selectivity
of core–shell nanocatalysts. Recent developments in the prepara-
tion of CSNs and their catalytic and electrocatalytic applications, Disclaimer
including hydrogenation reactions, oxidation reactions, coupling
U.S. Environmental Protection Agency (EPA), through its Office of
reactions, cycloaddition reactions, ammonia decomposition,
Research and Development, partially funded and collaborated in,
ORR, AOR, etc. have been summarized in this review article.
the research described herein. It has been subjected to the
Advanced techniques used for the characterization of core–shell
Agency’s administrative review and has been approved for external
nanostructures have also been briefly illustrated. The key struc-
publication. Any opinions expressed in this paper are those of the
tural factors affecting catalytic activities of nanostructured mate-
author(s) and do not necessarily reflect the views of the Agency,
rials, namely surface charge, surface area, surface functionality,
therefore, no official endorsement should be inferred. Any
size distributions, structure, etc., have particularly been empha-
mention of trade names or commercial products does not
sized. In addition, ways to unravel their structure–catalytic
constitute endorsement or recommendation for use.
activity relationships and use the outcomes of studies as a guide
for further development of new and improved CSNs for catalytic
applications have been discussed.
In spite of their widespread application in catalysis, some Acknowledgements
aspects require further research; the interaction between the
core and shell is possibly the most important among them. As an The authors gratefully acknowledge support from the
example, there have been some disagreements as to whether the project LO1305 and the Operational Program Education for
ligand effect contributes to the d-band width or induces a direct Competitiveness – European Social Fund (project CZ.1.07/2.3.00/
charge transfer that affects d-band filling and how the thickness/ 30.0041) of the Ministry of Education, Youth and Sports of the
properties of the shell influences the overall catalytic process. Czech Republic. TA gratefully acknowledges financial support
Moreover, core–shell catalysts have become useful materials from the National Science Foundation in the USA (Grant Nos.
for electrocatalysis and have shown enhanced catalytic activity 1508611 and 1134289) for his group’s work on core–shell
in various electrocatalytic reactions. These catalysts have been nanocatalysis.
View Article Online
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Volume 44 Number 21 7 November 2015 Pages 7431–7920

Chem Soc Rev

Core–shell nanoparticles: synthesis and

1. Introduction in chemistry.30–33 Besides offering solutions to the traditional

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selective, robust, low-cost and environmentally benign catalytic catalytic efficiency).

Manoj B. Gawande received his Anandarup Goswami obtained his

Tewodros (Teddy) Asefa is a Ankush V. Biradar received his

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In addition to decreasing the amount of expensive material used

tailored structures and eﬃcient catalytic activity can often be

Radek Zboril received his PhD Rajender S. Varma was born in

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used to synthesize nanomaterials can generally be applied to

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employed to coat CeO2 outside the Pd-NP-grafted carbon spheres,

and aggregation of the Pd-NPs in the catalytic reaction. Following

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the cores), encapsulation (via a second polymerization to make

In addition to metal oxides, diﬀerent metal-based hollow

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employed to fabricate core–multishell NPs using Re–OA (rare-

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of styrene with good recyclable property and almost no leaching

Pd/SiO2 and Ca–Pd/SiO2 egg–porous-shell nanomaterials via an

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hydrophobic porous core and hydrophilic porous surface.285

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of dyes, biologically active compounds, pharmaceuticals, rubber

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Table 1 Semihydrogenation of internal alkynes using Pd@MPSO/SiO2-1a

Entry Alkyne Product (h) Alkenes Z : E Alkanes

Fig. 21 Schematic showing the principles behind the synthesis of

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one-pot process has been developed where oleylamine serves as

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the most important and common reactions in organic synthesis

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PtCl2 was first added to a ‘‘freshly prepared’’ colloidal solution of

improved catalytic activity for the catalytic oxidation of CO,

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Fig. 38 Suzuki–Miyura coupling reaction catalyzed by G–Ni/Pd CSNs.

supported on graphene (G) by a sequential reduction method for

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Fig. 40 (a) SEM images of inside-out core–shell architectures (Cu2O@Cu).

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Fig. 43 (a) Schematic of the procedure used for synthesizing M@oxide