DOI: 10.1002/chem.

201402277 Minireview

& Materials Science

Semiconductor and Metallic Core–Shell Nanostructures:

Synthesis and Applications in Solar Cells and Catalysis
Mee Rahn Kim, Zhenhe Xu,* Guozhu Chen, and Dongling Ma*[a]

Chem. Eur. J. 2014, 20, 11256 – 11275 11256  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Abstract: Nano-heterostructures have attracted great atten-
tion due to their extraordinary properties beyond those of
their single-component counterparts. This review focuses on
a specific type of hybrid structures: core–shell structures. In
particular, we present and discuss the recent wet-chemical
Introduction
Recent advances in the fundamental understanding of and
synthetic methodologies for nano-heterostructures have pro-
vided a wealth of research and technological opportunities for
the rational development of new materials, devices and appli-
cations, as they exhibit improved physical and chemical prop-
erties over their single-component counterparts.[1–5] Two
classes of promising nanoscale building blocks for complex
nanomaterials are colloidal semiconductor nanocrystals and
metallic nanoparticles (NPs). Mainly due to the quantum con-
finement effect and large surface-to-volume ratios, these build-
ing blocks show unique or largely improved properties, such
as size-tuneable band gaps and remarkable catalytic behaviour,
which are distinctly different from those observed in bulk ma-
terials.[6, 7] These properties are highly affected by their size,
shape, and surface characteristics, allowing them to be readily
manipulated.[8, 9] The further integration of these nanomaterials
into nano-heterostructures offers even greater flexibility in
tuning their properties through adjusting various structural
and morphological factors and by exploiting synergistic ef-
fects.
Colloidal semiconductor quantum dots (QDs) are nanocrys-
tals containing a few hundred or a few thousand atoms. They
have been extensively explored in the past two decades, since
they show interesting size-dependent optical absorption and
emission properties, which are tuneable over a wide spectral
range from visible to near-infrared (NIR).[6, 10–12] This specific fea-
ture arises from the quantum confinement effect, as the size of
QDs is smaller than their exciton Bohr radius. Following initial
efforts in the 1990’s, mainly on the development of single-
component QDs, hybrid nanostructures (such as alloy, core–
shell, doped and hetero-branched structures) have recently
been actively investigated to overcome the limits of single-
component QDs.[13–21] In particular, semiconductor-core/semi-
conductor-shell QDs are considered to be extremely promising
materials among diverse semiconductor hybrid nanostructures
in view of their greatly enhanced chemical, thermal, and pho-
tochemical stability compared with corresponding organic-
ligand-surrounded single-component QDs. The inorganic shell
of a second semiconductor is ideally grown epitaxially on the
[a] Dr. M. R. Kim, Dr. Z. Xu, Dr. G. Chen, Prof. Dr. D. Ma
Centre-nergie, Matriaux et Tlcommunications
Institut National de la Recherche Scientifique
1650 Boulevard Lionel-Boulet, Varennes, QC J3X 1S2 (Canada)
Fax: (+ 1) 450-929-8102
E-mail: zhenhe-xu@emt.inrs.ca
ma@emt.inrs.ca
Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org
Minireview
synthesis approaches for semiconductor and metallic core–
shell nanostructures, and their relevant properties and po-
tential applications in photovoltaics and catalysis, respective-
ly.
surface of a core QD to improve the surface passivation of the
core QD by removing the dangling bonds on the core QD.[4]
Moreover, such an inorganic shell is expected to serve as
a physical barrier to provide a more robust protection to the
core QD. Furthermore, depending on the band alignment of
the semiconductor core and shell, both optical and electronic
properties can be engineered. With all these advantages, core–
shell QDs have been broadly investigated by various research
groups in the past decade and applied to a wide variety of
fields, such as renewable energy, electronics, photonics, cataly-
sis and biology.[22–25]
Metallic NPs or clusters have also been emerging as a new
type of important functional materials for optical, electronic,
magnetic and catalytic applications.[26–29] They can exhibit inter-
esting properties, such as band gap opening (responsible for
metal-to-semiconductor transitions), size-dependent band
gaps, strong surface plasmon resonance, and unusual catalytic
behaviour. All of these properties are quite different from
those of individual metal atoms and/or their bulk counterparts,
due to the quantum-size and surface effects. However, for
many applications, simple single-metal NPs do not satisfy the
requirements and complex heterostructures, such as a bimetal-
lic core–shell structure, are desired instead. The combination
of two different metal elements into metallic core–shell NPs
allows not only significant improvements in their properties
over those of their monometallic analogues,[3, 29, 30] but also
makes it possible to obtain unique properties that cannot be
achieved with simple NPs. This improvement is largely attribut-
ed to the so-called “synergistic” effect between component
metals, as they can be selected and their structural details can
be designed in such a way that they positively interact with
each other.[31, 32] This metallic core–shell strategy is also a feasi-
ble way to combine multiple, quite different functionalities on
the nanoscale as desired. In this case, the shell metal mainly
determines surface-related properties, such as catalytic proper-
ties, of the core–shell NPs, whereas the core may bear another
beneficial function, such as luminescence or superparamagnet-
ism. One of the most-studied applications of metallic core–
shell NPs is perhaps catalysis. As a matter of fact, great prog-
ress has been made and a number of metallic core–shell NP
catalysts have been reported for a range of reactions, including
hydrogen activation,[33] oxygen reduction reaction,[34] acetylene
hydrogenation,[35] H2O2 synthesis,[36] vinyl acetate synthesis,[37]
oxidation of alcohols to aldehydes,[38] and so on, in which the
core–shell NPs exhibit enhanced resistance to catalyst poison-
ing and/or increased catalytic activity. In addition to improving
catalytic performance, the realization of core–shell NPs has sig-
nificant economic advantages for the field of catalysis. By re-
11257  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

placing the core of solid monometallic precious metal NPs
with a less expensive metal, the consumption of the precious
metal and thus material cost can be greatly reduced.
In this review, we focus on core–shell nanostructures with
the core and shell both made of semiconductor or metal mate-
rials. We start by introducing the recent progress in the design
and wet-chemical synthesis of semiconductor core–shell QDs
(e.g., type-I CdSe/ZnS and type-II CdS/ZnSe) and metallic core–
shell NPs (e.g., Au/Pd, Ni/Ru and Pt/Pd). Then, their properties
specifically related to the formation of the core–shell structure
and their potential applications in photovoltaics and catalysis
are discussed. In the last section, we conclude this minireview
with a brief summary as well as perspectives and challenges
for core–shell nanostructures.
Semiconductor Core–Shell Nanostructures
A number of colloidal semiconductor QDs, such as II–VI (e.g.,
CdS, CdSe, CdTe, ZnS, ZnSe and HgS), III–V (e.g., InP and InAs),
and IV–VI (e.g., PbS, PbSe and PbTe) QDs, have been synthe-
sized and studied during the past two decades.[6, 10–12, 39–41]
These QDs can also be classified by their emission wavelength
range into ultraviolet (UV)-emitting QDs, visible-emitting QDs,
and NIR-emitting QDs. In these QDs, as a large portion of
atoms are located at the surface. The realization of surface
control by, for example, forming a core–shell structure, has
been recognized as one of the most intriguing methods to
achieve tailored nanomaterials. Over the last decade or so, the
investigation of core–shell semiconductor QDs has exploded
all over the world.[4, 15–17, 22] Capping semiconductor QDs by in-
organic materials not only alters the charge, functionality and
reactivity of the surface of QDs, but also improves their optical
properties and enhances their thermal, mechanical and chemi-
cal stability as compared to QDs only capped by organic li-
gands. The stability improves because the inorganic shells can
provide stronger protection to the core QDs, in addition to
yielding better surface passivation by eliminating both anionic
and cationic dangling bonds at the surface (Figure 1).[17] More-
over, depending on the valence band and the conduction
band offset between the core and shell semiconductors, both
the electronic and optical properties can be tuned. In order to
gain the full advantages of the core–shell QDs, it is thus impor-
tant to coat a core semiconductor through epitaxial over-
growth of a shell semiconductor with a very small lattice mis-
Figure 1. Schematic synthesis of CdSe/CdS core–shell nanocrystals. Reprint-
ed with permission from reference [17]. Copyright 1997 American Chemical
Society.
Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org
Minireview
match, as well as appropriate band alignment for the targeted
applications.
Core–shell semiconductor QDs can be identified as type-I,
reverse type-I, type-II and quasi-type-II, depending on the rela-
Guozhu Chen is currently an associate pro-
fessor at University of Jinan, China. He received
his Ph.D. degree in Inorganic Chemistry in 2009
from Shandong University, China. After gra-
duation, he joined Prof. Ma’s group at the
Institut National de la Recherche Scientifique,
Canada, as a postdoctoral fellow. His main
research interest is the rational synthesis of
functional nanomaterials, including bimetallic
nanoparticles, hollow structured metal oxides
and metal nanoparticle/metal oxide nanocom-
posites, for heterogeneous catalysis (e.g., CO
oxidation and dehydrogenation).
Dongling Ma is currently a professor at Institut
National de la Recherche Scientifique, Canada.
Her main research interest consists in the
development of various nanomaterials (e.g.,
semiconductor quantum dots, transition metal
nanoparticles, plasmonic nanostructures and
nanohybrids) for applications in energy, cata-
lysis and biomedical sectors. She was awarded
Natural Sciences and Engineering Research
Council Visiting Fellowships and worked at
National Research Council of Canada during
2004–2006. She received her Ph.D. in Materials
Science & Engineering from Rensselaer Poly-
technic Institute, USA in May 2004.
Mee Rahn Kim graduated from Pukyong
National University with B.S. in Chemistry in
2004 and received her Ph.D. in Physical
Chemistry at Seoul National University, Korea,
in 2010. She worked as a postdoctoral fellow in
Nanochemistry Faculty of Istituto Italiano di
Tecnologia (2010–2012), Italy. She then moved
to Institut National de la Recherche Scientifi-
que (2013) where she is working in Professor
Dongling Ma’s group as a postdoctoral fellow.
Her research is focused on the synthesis of
colloidal nanocrystals and their solar cell
applications.
Zhenhe Xu was born in Shenyang, China, in
1981. He received his Ph.D. degree (inorganic
chemistry) from the Changchun Institute of
Applied Chemistry (CIAC), Chinese Academy of
Sciences in 2011. Then, he joined the Depart-
ment of College of Applied Chemistry, She-
nyang University of Chemical Technology as
an Assistant Professor. In 2011, he was
awarded the “ZhuLiYueHua Scholarship” by
Chinese Academy of Sciences. He became a
postdoctoral fellow in Prof. Ma’s group at the
center of nergie, Matriaux et Tlcommuni-
cations, Institut national de la Recherche
Scientifique, University of Quebec (Canada) in
2013. His current research interests include the development of nanostructured
materials and multifunctional composite materials mainly for catalytic
applications.
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Figure 2. Core–shell QDs can be divided in different types, depending on
the localization of the electron and hole wave function. In type-I, electrons
and holes are confined in the same region (either core or shell), in type-II,
they are spatially separated. In the quasi-type-II, one carrier is fully delocal-
ized over the entire volume and one is localized in one region. Adapted
with permission from reference [42]. Copyright 2011 American Chemical So-
ciety.
tive alignment of the conduction band and the valence band
of core and shell semiconductors. As shown in Figure 2, for the
type-I core–shell QDs, the shell material with a wider band gap
is overgrown onto core QDs, in which both photogenerated
electrons and holes are confined, leading to the significant re-
duction of their non-radiative recombination and considerably
enhanced optical emission. In contrast, reverse type-I core–
shell QDs have exactly the opposite band alignment of type-I
QDs, and their holes and electrons are partially or completely
confined in the shell depending on the shell thickness. There-
fore, reverse type-I core–shell QDs have demonstrated im-
proved charge extraction and injection behaviour, highly rele-
vant to solar cell applications. Concerning the type-II core–
shell QDs, either the conduction band edge or the valence
band edge of the core is located in the band gap of the shell,
causing the spatial separation of the electrons and holes into
different regions of the core and the shell (Figure 2). This gives
rise to the important broadening of the spectral range, which
could be difficult to achieve with single-component semicon-
ductor QDs. Furthermore, there is a special case of QDs, so
called quasi-type-II core–shell QDs, in which electrons (or
holes) are delocalized over the entire core–shell QDs, whereas
the other type of charge carriers are confined in the core
region.
Synthesis of core–shell semiconductor QDs
Initial attempts to synthesize semiconductor nanocrystals in so-
lution were focused on obtaining uniform and homogeneous
QDs with high quantum yields (QYs) with a hot-injection
method.[43, 44] In general, Cd(CH3)2, which is extremely toxic, py-
rophoric, expensive and explosive at elevated temperatures,
was utilized initially as the cadmium precursor. This situation
rapidly changed after Peng et al. reported the new preparation
method for synthesizing homogeneous CdE (E = S, Se, Te) QDs
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Minireview
by using relatively safe CdO as the precursor.[45] Since then, the
research on semiconductor QDs has boosted rapidly. In partic-
ular, core–shell QDs have attracted broad interest due to their
enhanced optical and other properties. Many efforts have
been made towards obtaining high-quality core–shell semicon-
ductor QDs and diverse strategies have been reported. In the
following, the most common synthesis methods to produce
high-quality core–shell QDs are discussed.
Precursor co-precipitation
In this method, the precursors of all shell elements are co-pres-
ent in the reaction solution containing core QDs, leading to
the simultaneous synthesis and deposition of the shell on the
pre-synthesized core QDs. For the introduction of the precur-
sors of shell materials, there are two ways, the so-called one-
pot and two-step approaches.[46–48] The major advantage of the
one-pot approach is a simple preparation route without any in-
termediate size selection and/or purification step. However,
since unreacted precursors or by-products are not eliminated,
they may affect the shell growth on cores and lower the level
of control of the shell growth in certain cases. In 1996, Hines
and Guyot-Sinnest successfully pioneered the synthesis of
type-I CdSe/ZnS QDs, the most studied system to date, by de-
veloping this method.[49] Monodisperse CdSe/ZnS core–shell
QDs with a high QY of 50 % were synthesized by injecting the
mixture of dimethylzinc and bis(trimethylsilyl) sulfide in tri-n-
octylphosphine (TOP) into the as-prepared CdSe dot solution
at a high temperature of 300 8C. Although most efforts have
been placed on the core–shell QDs involving II–VI cores, later
on, a few have been reported for IV–VI QDs. For example,
Sashchiuk et al. synthesized PbSe/PbS core–shell QDs by rapid-
ly adding tributylphosphine sulfur (TBP:S) precursor solution
into the reaction solution of pre-synthesized colloidal PbSe
QDs under inert gas.[46] The authors demonstrated that the
thickness of the PbS shell can be controlled by varying the
sulfur precursor concentration in the reacting solution.
In contrast, the two-step approach involves the size selection
or purification, and re-dispersion of the core QDs following
their synthesis. It was developed with the purpose of gaining
more control over the shell overgrowth. Immediately following
the one-pot synthesis work of Hines and Guyot-Sinnest in 1996,
Bawendi’s group described a two-step method for the synthe-
sis of a size series of monodisperse CdSe/ZnS QDs in 1997.[50]
They also performed in-depth structural characterization with
a combination of tools and further correlated optical proper-
ties with the shell structure. In addition to including the core-
size selection step, another major difference of this work from
the previous one is lowering the injection temperature to 140–
220 8C, depending on the size of core dots. Afterwards, Alivisa-
tos’s group reported the epitaxial growth of CdSe/CdS core–
shell QDs by the two-step synthesis route, showing photolumi-
nescence (PL) QYs at least 50 %, which are 15–20 times higher
than those of the cores, and the large increase of photostabili-
ty (Figure 3).[17] By displacing tri-n-octylphosphine oxide (TOPO)
with pyridine, known to be a weak binding molecule, and by
using a low shell-growth temperature of 100 8C, such modified
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Figure 3. Left: High resolution transmission electron micrographs (HRTEMs)
taken under black atom-contrast conditions near Scherzer defocus. Dark
areas in the nanocrystal correspond to atomic positions, whereas bright
spots indicate channels in the crystal structure. The length bar at the lower
left corner indicates 50 . CdSe cores viewed along the a) [001] zone axis
(the wurtzite c axis) and b) [100] zone axis (with the c axis in the image
plane, pointing up). The random speckled background is due to the amor-
phous carbon substrate. c) and d) are core–shell nanocrystals with thin
shells; e) and f) have thick shells. Right: Absorption (dashed) and PL (solid)
spectra of a 30  CdSe core diameter series of core–shell QDs. Spectra were
taken after successive injections of CdS stock solution. The increase in quan-
tum yield and of coverage of CdS with each injection is also shown. Q.Y.:
quantum yield of photoluminescence. q: number of monolayers of shell
growth. All spectra were taken at a concentration corresponding to an opti-
cal density (OD) of roughly 0.2 at the peak of the lowest energy feature in
the absorption spectrum. Adapted with permission from reference [17].
Copyright 1997 American Chemical Society.
synthetic conditions not only allowed for control of the shell
thickness on varying core sizes but also prevented CdSe core
dissolution and homogeneous CdS nucleation in solution,
which tends to occur during shell growth. Even though syn-
thesis parameters may be modified depending on specific core
and shell materials, the basic principle is that the reaction tem-
perature for the shell growth is generally lower than that for
the core synthesis to prevent separate and homogenous nucle-
ation of the shell material in the reaction solution and uncon-
trolled ripening of the core QDs. Progress has also been made
toward synthesizing type-II core–shell QDs. Klimov’s group syn-
thesized CdS/ZnSe type-II QDs with an emission QY up to 10–
15 % with a similar two-step approach, including the purifica-
tion of core dots with pyridine and the subsequent shell
growth on the cores.[51] They employed the TOPO-free environ-
ment by using a non-coordinating solvent, such as octadecene,
during the overcoating procedure, and annealed the reaction
solution at a low temperature of 150–170 8C for 24–48 h in
order to increase the PL QY of formed CdS/ZnSe core–shell
QDs. In the same report, the authors further increased the
emission efficiency of CdS/ZnSe core–shell QDs by alloying the
core–shell interface with small amounts of CdSe, resulting in
QYs up to 50 %. The formation of the intermediate ZnCdSe
layer with a graded composition can improve the lattice
matching at the core–shell interface and, hence, reducing the
Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org
Minireview
number of interfacial defects that consequently gives rise to
the high emission efficiency of CdS/ZnSe type-II QDs.
In addition to cadmium chalcogenide semiconductor QDs,
other types of semiconductors are also employed as cores for
the synthesis of core–shell QDs with the two-step approach.
For example, Banin’s group successfully synthesized novel
core–shell nanocrystals of InAs/InP and InAs/CdSe involving III–
V InAs as cores and further studied their properties.[52] The
band gap and luminescence of these QDs were size tuneable
through the NIR spectral range, where the choice of lumines-
cent dyes is very limited, not to mention their poor stability.
Therefore, these NIR-emitting core–shell QDs open up new op-
portunities for applications specifically related to or preferred
in the NIR range. Since then, multiple materials have been in-
troduced for synthesizing core–shell semiconductor nanostruc-
tures using this method, and the study on their physical prop-
erties, mainly optical and electronic, have also been carried out
deeply.
Successive ionic layer adsorption and reaction (SILAR)
To absolutely overcome the separate nucleation and growth of
shell materials in solution and to avoid inhomogeneous shell
growth on seed QDs, which often occur in the one-pot and the
two-step processes mentioned above, the SILAR method has
been employed for synthesizing core–shell QDs.[53–56] Originally
developed for the deposition of thin films on solid substrates
from solution baths, the SILAR method is uniquely based on
the formation of one monolayer shell at one time by alternat-
ing the injections of cationic and anionic precursors. It is
aimed at reducing the coexistence of cations and anions of the
shell materials in solution, thereby suppressing homogeneous
nucleation and non-uniform shell growth. The most attractive
advantage of this technique is that the shell thickness can be
precisely controlled, as compared to other approaches for syn-
thesizing core–shell QDs. Peng’s group first introduced the
SILAR technique to fabricate CdSe/CdS core–shell QDs
(Figure 4).[53] They demonstrated that the core–shell QDs with
20–40 % PL QY could be readily synthesized on a multigram
scale and their size distribution was able to be maintained
with five monolayers of CdS shells on 3.5 nm CdSe QDs. This
method has subsequently been extended to other types of
core QDs.[56–58] For example, Xu et al. reported PbSe/PbS core–
shell QDs prepared by the alternate syringe injection of the
predetermined dosages of lead- and sulfur-solutions into the
preheated PbSe core QD solution using the standard air-free
procedure.[56] For the growth of the first shell, the amounts of
lead and sulfur precursors required were determined by the
size and the lattice structure of the plain PbSe cores employed
in the synthesis.
Partial cation-exchange reaction
In this method, only the precursor of the cationic constituent
of a shell material is introduced during the shell formation pro-
cess, and the shell growth proceeds through the gradual re-
placement of core cations by newly introduced cations in solu-
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Figure 4. TEM images of CdSe plain core nanocrystals and the correspond-
ing core–shell QDs with different shell thickness from the same SILAR
method. Reprinted with permission from reference [53]. Copyright 2003
American Chemical Society.
tion and the anion sublattice remains basically undisturbed.
Generally speaking, the reports on NIR-emitting IV–VI lead
chalcogenide-based core–shell QDs are rather limited, in con-
trast to a large number of literature articles on the UV–visible
emitting core–shell QDs involving II–IV cadmium chalcogenide
cores. In these limited publications, almost exclusively high-
quality lead chalcogenide-based core–shell QDs have been
synthesized by this cation exchange method, which has only
been applied to the core–shell QD synthesis recently. Specifi-
cally, PbS/CdS, PbSe/CdSe and PbTe/CdTe QDs have been de-
veloped by partial replacement of lead ions with cadmium
ions.[59–61] For instance, for PbS/CdS core–shell QD synthesis, an
excess of cadmium oleate was added to a PbS QD suspension
in toluene heated to 100–150 8C and the reaction was allowed
to continue for certain time to get different shell thicknesses.[62]
As a result of the sacrifice of the core for shell growth, a de-
crease of the lead chalcogenide core size occurs during the
cation exchange. Therefore, the PL peak position of the core–
shell QDs was blue-shifted depending on the shell thick-
ness,[62–64] as shown in Figure 5. In addition, the increase in life-
time was consistent with the increase in QY and due to better
surface passivation. This synthetic approach of cation ex-
change to fabricate core–shell QDs using IV–VI semiconductor
QD cores is reliable and highly reproducible. Although the
SILAR technique is quite popular for synthesizing high-quality
core–shell QDs containing Cd and Zn, this cation exchange ap-
proach has also been used for their synthesis. For instance,
Groeneveld et al. reported the cation exchange between Cd2 +
and colloidal ZnSe QDs to form reverse type-I core–shell or
alloy structures.[65] The cation exchange efficiency was found to
depend on the reaction temperature and the Cd/Zn ratio.
ZnSe/CdSe core–shell QDs were formed at 150 8C, while
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Figure 5. a) Wavelength-tuneable spectra of PbS/CdS core–shell QDs and b)
PL decay profiles for bare PbS QDs (lmon = 1460 nm) and PbS/CdS core–shell
QDs (lmon = 1320 nm) shown on logarithmic scale. lmon : monitored lumines-
cence wavelength. Reproduced from reference [66] with permission of The
Royal Society of Chemistry.
(Zn1 xCdx)Se gradient alloy QDs were produced at 200–220 8C.
The systematically temperature-controlled experiment reveals
that fast cation exchange takes place at the surface of ZnSe
QDs to form core–shell QDs and is followed by relatively slow
and thermally activated solid-state cation diffusion to form
alloy QDs.
Microwave-assisted method
In contrast to conventional oil-bath heating, which is the case
for all the above-mentioned examples, the microwave-assisted
method uses microwave radiation as a heating source to syn-
thesize core–shell semiconductor QDs at elevated tempera-
tures. The main benefit of using microwave radiation is that it
offers rapid and uniform heating of the entire reaction solu-
tion, and thus leads to an improvement in reaction reproduci-
bility and product uniformity as well as a shortening of reac-
tion time in comparison with the conventional synthesis routes
using oil-bath heating.[67] This method has recently been dem-
onstrated to facilitate the formation of core–shell QDs. For ex-
ample, water-dispersed CdTe/CdS core–shell QDs with en-
hanced PL QY as high as 75 % were synthesized by He et al. by
microwave heating.[68] As-prepared CdTe core QDs were added
into a solution containing Cd and sulfur precursors. A given
amount of the mixture solution was loaded into an exclusive
vitreous vessel and the reaction underwent under microwave
irradiation. A CdS shell with a high degree of crystallinity was
successfully obtained through steady epitaxial growth at
100 8C, whereas at 120 8C the core–shell QDs’ size distribution
degenerated, due to the Ostwald ripening of the CdTe seeds
during the shell-growth process. This result implies that the re-
action temperature was extraordinarily critical during this spe-
cific shell-formation process. Similarly, Roy et al. described that
water-soluble CdSe/ZnS core–shell QDs with PL QY ranging
from 11 to 28 % (PL maxima from 511 to 596 nm) were pro-
duced using a commercially available microwave reactor under
ambient atmospheric conditions.[69] We have also succeeded in
synthesizing high-quality PbS/CdS core–shell QDs through a mi-
crowave-assisted method (Figure 6).[63] The uniform core–shell
QDs exhibited NIR PL with narrower band width and signifi-
cantly enhanced QYs as compared with core–shell QDs ach-
ieved by using conventional heating in a silicone oil both,
thanks to the uniform heating from microwave irradiation. This
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 Minireview

ed electrons are injected into

and transported by a wide-band-
gap semiconductor, typically
TiO2, and dye molecules are sub-
sequently regenerated by solid
or liquid electrolytes.[76, 77] De-
spite great efforts, the efficiency
of these cells is still much lower
than that of Si solar cells and
must be improved for practical
applications. One of the promis-
ing solutions toward achieving
low-cost and high-efficiency
solar cells consists of enhancing
the absorption of light-absorb-
ing materials in these cells by
enhancing their absorption in
the visible range or by extending
their sensitization into the NIR
range by introducing new solu-
tion-processable nanomaterials,
Figure 6. a) The proposed growth path of PbS/CdS QDs during the cation exchange: (i) heating by microwave such as QDs. Both dyes and or-
and (ii) heating by oil at different reaction times. d0 is the “critical” shell thickness below which no obvious defects
are induced and overall the QDs largely benefit from better passivation from the CdS shell. b) TEM image of PbS/ ganic semiconductors mainly
CdS core–shell QDs synthesized by microwave heating with reaction time of 30 s at 100 8C. c) PL spectra of the absorb in the visible range,
bare PbS QDs and of the PbS/CdS QDs synthesized by microwave-assisted cation exchange at different reaction while leaving approximately
times and d) QY and full-width-at-half-maximum for PbS/CdS QDs synthesized using the microwave-assisted 50 % of photons in the NIR un-
method. Reproduced from reference [63] with permission of The Royal Society of Chemistry.
touched. In addition to using
nanomaterials as new sensitizers
to improve the performance of
well-controlled and highly reproducible microwave-assisted re- existing solar cells, it is also highly attractive to develop new
action has been successfully scaled up by almost five times configuration devices completely based on new nanomaterials.
through increasing the initial PbS QD concentration or through Among various nanostructured materials, QDs are one of
amplifying the reaction volume in very short reaction time, the most promising types for solar cell applications. They have
while maintaining the high-quality of the core–shell QDs. We several obvious advantages. First, they can be synthesized
would like to point out that one limitation of this method is through a wet-chemical method and processed from solution,
that, to be efficient, the synthesis has to be carried out in mi- consistent with the goal of developing low-cost solar cells. In
crowave-absorbing solvents, that is, polar solvents. addition, their band gaps can be easily adjusted by their size.
Such great flexibility in band gap engineering gives promise to
construct the so-called panchromatic solar cells, in which semi-
Solar cell applications of core–shell QDs
conductor QDs of different band gaps are integrated and each
For photovoltaic applications, more than 90 % of commercially size group is optimized to strongly absorb a particular portion
available solar cells are presently made of crystalline Si, with of visible light; together they lead to impressive photovoltaic
typical power conversion efficiencies of 15–20 %.[70–72] Although performance. Beyond enabling better matching of the cell ab-
they have shown sufficiently high and robust efficiencies, they sorption to the visible part of the solar spectrum, the use of
suffer from high manufacturing costs and long energy payback QDs makes it possible to harvest a good portion of NIR pho-
time, which have limited their large spread for photovoltaic tons as certain types of QDs can be tuned to efficiently absorb
power generation. Organic solar cells and dye-sensitized solar far in the NIR range, which corresponds to about 45 % of ter-
cells are two types of promising, new-generation alternatives restrial solar radiation.[78–80] Last but not least, QDs open up op-
that could potentially lead to low-cost and high-efficiency solar portunities to the efficient extraction of hot carriers and the
cells. The former involves the use of solution-processable small generation of multiple charge carriers from a single
organic semiconductor compounds and/or conjugated poly- photon.[81, 82] Up to now, solution-processed plain and core–
mers. One typical example is the bulk heterojunction solar cell shell semiconductor QDs have been utilized in different types
formed by blending hole-transporting poly(3-hexylthiophene) of solar cells, such as hybrid polymer-QD solar cells, QD-sensi-
(P3HT) and electron-transporting fullerene derivative of [6,6]- tized solar cells and depleted heterojunction solar cells
phenyl C-61-butyric acid methyl ester fullerene (PCBM).[73–75] In (Figure 7). QD-based Schottky junction solar cells have also
dye-sensitized solar cells, another type of cost-effective cells, been reported.[83–85] As this device configuration has not been
dye molecules solely serve as sensitizers and their photoexcit-

Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org 11262  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 7. Different types of QD-based solar cells: a) hybrid polymer-QD solar
cell, b) QD-sensitized solar cell, and c) depleted heterojunction solar cell.
extended to core–shell QDs, it is not covered in the current
review.
Hybrid polymer-QD solar cells
The exploration on the use of wet-chemically synthesized QDs
in solar cells started in the field of organic solar cells.[86] A typi-
cal way to integrate QDs is to blend them with a hole-conduct-
ing conjugated polymer to make bulk heterojunction polymer-
ic solar cells. QDs have also been incorporated as an additional
element to traditional polymeric solar cells containing both
hole- and electron-conducting materials, such as P3HT and
PCBM. One of critical factors to directly affect the photovoltaic
performance of hybrid polymer-QD solar cells is the charge
separation at the interface of the polymer and QDs. Alivisatos’s
group studied the charge separation and transport in compo-
site materials of CdSe (or CdS QDs), synthesized by wet-chemi-
cal methods, with the conjugated polymer poly(2-methoxy-5-
(2’-ethylhexyloxy-p-phenylenevinylene) (MEH-PPV).[86] After sur-
face treatment to remove surrounding ligands, the photolumi-
nescence of the polymer was dramatically quenched, indicat-
ing rapid charge separation at the polymer and QD interface.
As a result, the thin-film photovoltaic devices using the com-
posite materials showed significantly improved efficiency over
the control devices containing only MEH-PPV. At a high con-
centration of QDs, where both the networks of the QDs and
polymer provided charge carriers continuous pathways to-
wards respective electrodes, the quantum efficiency could
reach 12 %. By utilizing core–shell QDs with appropriate band
alignment, interfacial charge dissociation and transfer could be
further improved. As reported by Kim et al.,[87] photovoltaic de-
vices incorporating ZnTe/ZnSe type-II QD showed 11 times
higher power conversion efficiency, when compared with the
control devices involving ZnSe QDs. This interesting observa-
tion resulted from the type-II characteristic of broad QD ab-
sorption up to extended wavelengths and the spatially sepa-
rated electrons and holes in the QDs, both of which can en-
hance the carrier extraction in solar cells.
Although type-II core–shell QDs can help extend the absorp-
tion of photoactive materials to longer wavelengths, the level
of extension can be limited in many cases. In contrast, the ab-
sorption can be extended far into the NIR range by using NIR-
absorbing QDs, such as PbS QDs. We incorporated a hybrid of
PbS QDs and multiwall carbon nanotubes (MWCNTs) into P3HT
Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org
Minireview
Figure 8. a) TEM image of PbS-QD/MWCNT nanohybrids, b) HRTEM image of
PbS QD-MWCNT hybrid, and c) current density–voltage characteristics of the
nanohybrid-based photovoltaic cell and the standard cell under solar simula-
tor irradiation. Adapted with permission from reference [88]. Copyright 2011
John Wiley and Sons.
polymer, and fabricated P3HT:PbS-QD/MWCNT nanohybrid-
based solar cells (Figure 8).[88] In this system, PbS QDs acted as
NIR photon harvesters and MWCNTs as charge carrier transport
highways. Compared with the control devices made with P3HT
and PCBM mixtures, the power conversion efficiency of the
hybrid cells increased by approximately 18 %, due to the en-
hanced absorption and transportation of photoexcited charges
related to the QDs and MWCNTs, respectively. Considering the
stability issue of plain PbS QDs and significantly improved
photo- and thermal-stability of the PbS/CdS core–shell
QDs,[66, 89–91] it is interesting to explore the use of these core–
shell QDs in solar cells. One negative factor, however, could be
the inefficient charge transfer in these seemingly type-I QDs,
where, unlike in type-II QDs, the shell may serve as a barrier
for charge transfer. To evaluate whether these PbS/CdS core–
shell QDs are suitable for solar cell applications, we have inves-
tigated the charge transfer of the hybrid system consisting of
PbS/CdS core–shell QDs and MWCNTs as the first step.[89] The
results of PL quenching and PL lifetime shortening demonstrat-
ed that the electrons excited in the PbS cores could still be
transferred into the MWCNTs efficiently when shell thickness
was  0.7 nm, although the CdS shell played a role of an elec-
tron transfer barrier. Further considering their higher stability,
these core–shell QDs are very promising for the development
of highly efficient QD-based photovoltaic devices. It is worth-
while to mention that based on the systematic study of Hens
et al., PbSe/CdSe core–shell QDs, a very similar system to the
PbS/CdS core–shell QDs, are indeed at the boundary between
the type-I and quasi-type-II regimes.[42]
As mentioned above, since charge separation takes place at
the interface, the maximization of the interfacial area between
the core–shell QDs and polymer is important. Ren et al.
showed power conversion efficiency of 4.1 % under AM 1.5
solar illumination by controlling the morphology and interface
structure of P3HT-CdS hybrids.[92] CdS QDs were bound to crys-
talline P3HT nanowires through solvent-assisted grafting and
ligand exchange. The chemically grafted CdS QDs increased
the P3HT-QD interaction and maximized the interfacial area by
the formation of P3HT-CdS coaxial nanowire hybrids. This ar-
11263  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

chitecture had advantages over a randomly mixed system, be-
cause isolated phase segregation was minimized and the
P3HT-CdS interface was maximized, improving dissociation of
photogenerated excitons between the P3HT and QDs phases.
Although this work is focused on plain and inorganic-shell-free
CdS QDs, it can provide important guides to the rational
design and realization of solar cells incorporating core–shell
QDs.
QD-sensitized solar cells
QD-sensitized solar cells can be regarded as an analogue of
dye-sensitized solar cells. A typical configuration of cells con-
sists of QDs as light absorbers and large-band-gap nanocrystal-
line semiconductors (e.g., TiO2 and ZnO) on a fluorine-doped
tin oxide (FTO) or indium-doped tin oxide (ITO) glass as a work-
ing electrode, solid or liquid electrolytes to regenerate QDs,
and a counter electrode.[93] Photogenerated excitons in the
QDs dissociate at the interface between TiO2 (or ZnO) and
QDs, and electrons are injected into and transported by TiO2
(or ZnO). A polysulfide liquid electrolyte is commonly used to
transport the holes to the counter electrode. Kamat’s group re-
ported QDs-sensitized solar cells made with different-sized
CdSe QDs and in another case two types of different semicon-
ductor QDs, CdSe and CdTe.[94–96] The photo-electrochemical re-
sponse and photoconversion efficiency could be tuned
through the size control of CdSe QDs, and in addition, the
photoconversion efficiency was improved by using tubular
TiO2 rather than particulate TiO2.[94, 95] In addition, they showed
the scavenging of photogenerated holes by a sulfide redox
couple in photoirradiated CdSe system, but not in CdTe, be-
cause the charge transfer with sulfide at the CdSe interface do-
minated over the anodic corrosion and substitution reactions
which occurred favourably in the CdTe system.[96] The research
interest has recently been extended to core–shell QDs. As
mentioned above, two of the major beneficial features of the
type-II core–shell QDs relevant to solar cell applications are the
extended absorption and reduced charge recombination
(therefore enhanced charge extraction) due to the spatial sepa-
ration of electrons and holes. Itzhakov et al. explored type-II
CdTe/CdSe core–shell QDs as a sensitizer in QD-sensitized pho-
toelectrochemical solar cells (Figure 9).[97] CdTe/CdSe QDs com-
prise a hole-localizing core and an electron-localizing shell and,
similar to other type-II QDs, they show improved absorption
characteristics and intraparticle exciton dissociation upon pho-
toexcitation. As a result, the solar cells made with these type-II
core–shell QDs together with porous TiO2 and a polysulfide
electrolyte exhibited efficient charge separation and high inter-
nal quantum efficiency despite the hole localization in the
CdTe core. Moreover, this specific type of QD has the advant-
age of containing a relatively small content of the less abun-
dant tellurium element, which has economic benefits.
Another important driving force for the incorporation of
core–shell QDs into solar cell devices is enhanced stability. As
successfully demonstrated by Zhu et al., core–shell QD-sensi-
tized solar cells showed improved stability, in addition to the
increase of power conversion efficiency, as compared with the
Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org 11264
Minireview
Figure 9. a) Schematic representation of the system consisting of a type-II
CdTe/CdSe core–shell QD adsorbed on nanocrystalline TiO2 and overcoated
by a ZnS shell. The assumed band diagram of the system is also shown.
Arrows show the charge directions after exciton generation. b) Current den-
sity versus voltage and c) incident photon-to-current conversion efficiency
(IPCE) curves for four different TiO2 thicknesses and two SILAR cycles of ZnS
coating as was measured under 1 sun of simulated irradiation (AM 1.5G,
100 mW cm 2) and a 1 cm2 cell area). Note that the peaks around 850 nm in
the IPCE spectra are an artifact of the measurement system. Adapted with
permission from reference [97]. Copyright 2013 American Chemical Society.
solar cells sensitized by plain QDs.[98] Shell thickness is an im-
portant factor to consider in designing and optimizing core–
shell QD solar cells. To understand how the shell thickness af-
fects the solar cell performance, they investigated charge sepa-
ration and recombination kinetics of type-I CdSe/ZnS core–
shell QDs of different shell thicknesses. The charge separation
and recombination rates decreased exponentially with the
shell thickness. Model calculations helped understand these re-
sults, which yielded a similar exponentially decreasing trend of
the 1S electron and hole densities at the QD surface with in-
creasing shell thickness. The sharp decrease in charge recombi-
nation rate with shell thickness can be attributed to the signifi-
cant decrease in the surface hole density, which results from
larger hole effective mass in the ZnS shell. This finding sug-
gests the importance of optimizing and balancing the charge
separation and stability (in principle stability improves with in-
creasing shell thickness) by controlling the shell thickness and
the nature of shell materials. Lai et al. investigated the per-
formance of PbS/CdS QD-sensitized solar cells and particularly
studied the shell thickness effect.[99] The power conversion effi-
ciency of the core–shell QD-sensitized solar cell was four times
higher than that of the plain PbS QD-sensitized solar cell. Sig-
nificantly enhanced mean electron lifetimes and electron diffu-
sion lengths contributed to the higher efficiency of the cell.
Furthermore, it was found that the average electron lifetime in-
creased with the thickness of the CdS shell, suggesting that
the CdS shell plays an important role in preventing carrier re-
combination. They also concluded that the CdS shell prevent-
ed photo-corrosion of PbS, although simultaneously it had
a negative effect of hindering carrier injection from PbS to
TiO2. Similarly increased corrosion resistance has also been re-
 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ported by Benehkohal et al.[100] They employed electrophoretic
deposition to deposit a CdS coating to protect colloidal PbS
and PbSeS QDs from corrosive electrolytes. Efficiencies as high
as 2.1  0.2 % were obtained. There have also been attempts to
fabricate other types of core–shell QD-sensitized solar cell devi-
ces. Zhong et al. showed that a high-quality reverse type-I
CdS/CdSe core–shell QD-sensitized solar cell exhibited conver-
sion efficiency of 5.32 % under simulated AM 1.5 illumina-
tion.[101] Lai et al. recently reported the enhanced power con-
version performance of PbS/CdS QD-sensitized solar cells with
four times higher efficiency with respect to plain PbS QD-sensi-
tized solar cells.[99] Although the maximal power conversion ef-
ficiency of QD-sensitized solar cells that can be achieved so far
is still lower than that of dye-sensitized solar cells, the usage of
QDs is highly encouraged in view of largely tuneable absorp-
tion and relatively higher stability. More systematic optimiza-
tion work is required to make significant improvements.
Depleted heterojunction solar cells
In general, this type of solar cell utilizes the depleted hetero-
junction region between a p-type colloidal semiconductor QD
film and a n-type ZnO (or TiO2) layer to separate charge carriers
photogenerated mainly in the QD layer.[102–107] As illustrated in
Figure 10,[105] such a heterojunction device has a favourable
device configuration for light utilization and charge transporta-
tion as compared with a Schottky QD solar cell, because the
depleted region is formed on the front side of the QD layer de-
posited on a TiO2/ZnO film formed using a ZnO NP film on
FTO as a template for TiO2 deposition. Sargent’s group has per-
Figure 10. a) Schematic of the depleted heterojunction device, b) cross-sec-
tional SEM image of the same device, and c) measured current–voltage char-
acteristics under solar illumination for representative devices employing or-
ganic (red), inorganic (green) and hybrid (blue) passivation schemes. Adapt-
ed with permission from reference [105]. Copyright 2012 Nature Publishing
Group.
Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org
Minireview
formed a series of experiments that has dramatically improved
the performance of depleted heterojunction solar cells from
their first report by using a heterojunction of plain PbS QDs
and TiO2.[106–109] Specifically, they have improved the power
conversion efficiency from 3.6 to 7.0 % over the last few years.
Bawendi and co-workers demonstrated the importance of opti-
mizing interfacial energy offsets in photovoltaic devices by in-
vestigating the improvement of ZnO-PbS heterojunction devi-
ces through the incorporation of a MoO3 interlayer between
the PbS QD layer and the top-contact anode.[110] The improve-
ment in the power conversion efficiency is largely attributed to
the PbS/anode interface by introducing the high-work-function
MoO3 film. Even though core–shell QDs are expected to have
a higher elimination of a reverse-bias Schottky diode present
at the potential for solar cell applications, to date, few groups
have reported their integration into depleted heterojunction
solar cell devices. Very recently, our group introduced PbS/CdS
core–shell QDs to the depleted heterojunction solar cells. A
power conversion efficiency of > 2 % was attained, which rep-
resents a > 40 % increase in the efficiency that can be achieved
by similar devices involving plain PbS QDs processed under an
inert atmosphere.[111]
Metallic Core–Shell Nanostructures
Metallic core–shell NPs are composed of two or more metallic
elements. Depending on the way they combine into a complex
architecture, they can be divided into four classes
(Figure 11):[29] a) single-core/single-shell NPs, in which a core is
completely coated by a shell of a different metal; b) multiple-
core/single-shell NPs, in which multiple cores are encapsulated
within a matrix; c) single-core/multiple-shell NPs, in which
a core is coated by different metals layer-by-layer; and d) the
so-called yolk-shell NPs, in which a movable core is situated
within a hollow single-shell NP. In this review article, we mainly
focus on the most common single-core/single-shell NPs. Unless
otherwise specified, core–shell NPs refers to single-core/single-
shell NPs.
Figure 11. Different types of metallic core–shell NPs: a) single-core/single-
shell NPs, b) multiple-core/single-shell NPs, c) single-core/multiple-shell NPs
and d) yolk–shell NPs.
Metallic core–shell NPs display many intriguing properties,
such as tuneable electronic, optical and other properties.[112, 113]
Specifically for catalysis, the synergistic effect between the
core and shell was found to play a very important role in ach-
ieving greatly enhanced catalytic activity, stability and/or selec-
tivity. This beneficial contribution stems from mainly ligand,
strain and/or ensemble effects, with the first two being funda-
mentally related to the variation of the electronic structure
due to the core–shell interaction.[31] As all these effects can be
11265  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

entangled in real cases, and because it is complex to model
and carry out calculations for tiny bimetallic nanoparticles, the
contribution from each single factor is usually not clearly discri-
minated in most published work.
Synthesis of metallic core–shell NPs
Preparation strategies for core–shell structured bimetallic NPs
are diverse and can be complicated for certain systems. Al-
though nano-hybrid fabrication capabilities have been greatly
enhanced during the last two decades due to the develop-
ment of advanced experimental techniques, theoretical studies
are still important to provide guides in selecting core and shell
materials and in rationally designing bimetallic systems with
desired properties. Johnson et al. investigated 132 bimetallic
systems (groups 8 to 11 in the periodic table) using density
functional theory (DFT) and systematically explored segrega-
tion energies to determine the preference of two different
metals in forming a core–shell structure.[114] They found that
the core–shell preference estimated from segregation energies
could be largely described by two independent key factors: 1)
the cohesive energy and 2) the Wigner-Seitz radius (atomic
size), and the interplay between them. Based on their predic-
tions, some metal pairs, such as Pd/Pt and Ag/Au, tend to
form the core–shell structure, while others do not. This work
may shed some light on the formation of bimetallic core–shell
NPs. In addition, regarding the growth of core–shell NPs, the
concept of three different types of growth modes, originally
developed for film growth, has been borrowed to predict the
growth or explain the final morphology of the core–shell NPs
that have different level of lattice mismatch partially arising
from atomic size differences.[115] These three basic growth
modes are referred to as layer-by-layer mode (Frank–van der
Merwe, FM mode), island-on-wetting-layer growth mode
(Stranski–Krastanow, SK mode), and island growth mode
(Volmer–Weber, VW mode) and are shown in Figure 12. Basical-
ly, for heterostructures with a high degree of lattice mismatch,
the resulting interface is often non-coherent with a large den-
sity of defects. The larger the mismatch is, the more positive
this strain energy becomes, and the more difficult it tends to
be to form the epitaxial core–shell structure or even the non-
epitaxial core–shell structure. Moreover, for the same pair of
core and shell metals, the positive strain energy also is not
constant; it increases rapidly with the growth of second metal
nuclei. The morphology therefore could change during the
particle growth process.[115]
In this review article, we summarize several mostly accepted
approaches for the fabrication of core–shell NPs.
Seed-mediated growth
Successive seed-mediated growth is the most universal way to
prepare core–shell bimetallic NPs. In this method, the core is
prepared first, and then the shell is deposited onto the surface
of the core. Even as the most popular method, it suffers from
separate self-nucleation of the shell material in solution, which
however can be overcome by introducing a large number of
Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org
Minireview
Figure 12. Schematic illustration of three different growth modes. Adapted
with permission from reference [115]. Copyright 2009 Elsevier Ltd.
seeds (core NPs) and performing slow shell deposition by low-
ering the concentration of precursors and/or choosing mild re-
ducing agents. As mentioned above, the lattice mismatch is
expected to be an important factor in determining whether
two metals can form a core–shell structure and what the final
morphology looks like. Yang’s group’s experimental work has
clearly demonstrated the importance of this factor.[116] They
used highly faceted cubic Pt seeds to direct the growth of dif-
ferent secondary metals, yielding quite different bimetallic
structures. With the small lattice mismatch (0.77 %) between Pt
and Pd, they could produce the epitaxial overgrowth and gen-
erate Pt/Pd core–shell NPs of various shapes, such as nano-
cubes, cuboctahedra, and octahedra, by using NO2 to control
the relative growth rates along different crystallographic direc-
tions during the shell-precursor reduction process (Figure 13).
Such epitaxial growth (or FM mode growth), nonetheless, did
not take place for the Pt/Au system with the lattice mismatch
of 4.08 %. It is worthwhile to point out that other factors can
also influence the growth mode in addition to the lattice mis-
match. Huang’s group successfully synthesized Au/Pd core–
shell NPs with various shapes, including octahedral, cubic, and
truncated octahedral structures, by a two-step reduction
method.[117, 118] In this case, the shape control was interestingly
and relatively easily realized by varying the number of Au
seeds in solution. Although the lattice mismatch is 4.65 %, they
could get the core–shell structure. Similarly, Yan et al. demon-
strated the hetero-epitaxial growth of the core–shell and
single-core/multiple-shell nanocrystals that were composed of
Au and Pd.[119, 120] The Pd nanocubes (or Au nanooctahedrons)
were employed as the cores, then the Au (or Pd) shells were al-
ternately grown step-by-step to form Pd/Au/Pd/Au (or Au/Pd/
Au/Pd) core–trishell nanocrystals. Tian et al. used a two-step
11266  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Minireview

Figure 13. Well-defined cubic Pt seeds were used to direct the epitaxial overgrowth of Pd to form Pt/Pd core–shell nanocubes. a) The overall morphology is
shown by SEM. b) TEM indicates the presence of a cubic Pt seed at the core of each particle. c) Analysis by high-angle annular dark-field scanning transmis-
sion electron microscopy (HAADF-STEM) gives the orientation of the cubic Pt seed within the Pd shell. The Pt core stands out sharply in relation to the Pd
shell owing to the enhanced contrast from the difference in atomic numbers between the two elements. d) The orientation of the core and shell are mod-
elled with the axes projecting along the < 100 > directions through the faces of the central Pt cube. e–l) Control over the directed growth of Pd on Pt nano-
cubes was achieved by the addition of increasing amounts of NO2, which altered the growth rates along the < 100 > and < 111 > directions to give Pt/Pd
core–shell cuboctahedra (e–h) and octahedra (i–l). The SEM images (e,i) are provided for clarification of the three-dimensional morphology, and TEM images
(f,j) to show the presence of a Pt seed at the core of each particle. HAADF-STEM images give the orientation of the cubic Pt seed within a Pd cuboctahedron
(g) and octahedron (k). The Pt/Pd octahedron (k) is oriented along the < 111 > zone axis with the Pt seed on a three-fold axis giving a hexagonal projection.
The corresponding models are provided (h,l). Adapted from reference [116] with permission from Nature Publishing Group.

seed-mediated growth method for synthesizing Au/Pd nano-
cubes.[121] They proposed that the atomic radius, bond dissoci-
ation energy, and electronegativity of the core and shell metals
could play key roles in determining the growth mode.
High-quality metallic core–shell NPs can also be synthesized
efficiently in non-aqueous media by a thermal decomposition
process, which involves dissolving organic metallic complexes
in high-boiling point organic solvents with the assistance of
surfactants, and subsequently decomposing these precursors
at elevated temperature.[122] Our group reported the prepara-
tion of bifunctional (catalytic and magnetic) Ni/Ru core–shell
NPs through this thermal decomposition method.[123] TEM
images of Ni seeds and Ni/Ru core–shell NPs are shown in
Figure 14. As we can see from Figure 14 a and b, after Ru depo-
sition, most Ni/Ru core–shell NPs do not inherit the initial
spherical shape of the Ni NPs. In the high-resolution TEM
images (Figure 14 c), the measured d spacing of the centre and
outer regions correspond to the lattice spacing of Ni and Ru,
respectively, which further demonstrates the formation of the
core–shell structure. Accordingly, the selected area electron dif-
fraction (SAED) pattern for Ni/Ru NPs (Figure 14 d) exhibits two
sets of diffraction rings, one set corresponding to the fcc struc-
ture of Ni, the other corresponding to the hcp structure of Ru
in the Ni/Ru core–shell NPs. These core–shell NPs were likely
formed following the VW growth mode based on the observed
morphology. There is a relatively large lattice mismatch be-
tween Ni (111) and Ru (100) (about 6.4 %). In synthesizing
these uniform core–shell NPs with a jagged Ru shell, which are
difficult to achieve in principle, oleylamine was found to be
a key factor. It acts as both a solvent for the Ru3(CO)12 and
a capping ligand that binds Ru with the surface of Ni NPs after
the thermal decomposition of the Ru precursor.
Co-reduction
Compared to the seed-mediated growth method, the co-re-
duction approach appears to be a simpler method for the syn-
thesis of core–shell NPs. The fundamental idea of this method
is to take advantage of the different reduction potentials of
different metal salts. Typically, the metal with the higher stan-
dard redox potential is reduced first and then acts as the core,
followed by the reduction of secondary metal ions on the sur-

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Figure 14. TEM images of a) oleic acid-capped Ni and b, c) Ni/Ru core–shell
NPs: b) low resolution and c) high resolution. d) SAED patterns of Ni (left)
and Ni/Ru (right) core–shell NPs, respectively. The indexes of crystal planes
in the upper left refer to Ru and those in the lower right to Ni. Reproduced
from reference [123] with permission from the Royal Society of Chemistry.
face of the core. The shell is typically composed of a noble
metal, whereas the core can be either a noble or non-noble
metal, leading to combinations such as Fe/Ag, Co/Au, Co/Pd
and Co/Pt.[124–126] Although thermodynamically governed by
the redox potential difference, the formation of uniform core–
shell NPs with this method is also largely affected by kinetic
factors, such as precursor concentration, the type of reducing
agents and reduction rate. In particular, it is important to
choose an appropriate reducing agent, which can directly in-
fluence the reduction rate of core and shell precursors. Xu’s
group reported a rational and general strategy for the fabrica-
tion of magnetically recyclable Au/Co core–shell NPs through
the one-step route at room temperature under ambient at-
mosphere within a few minutes.[127] The synthesis was achieved
by exposing a mixture of Au3 + and Co2 + precursors to a rela-
tively weak reducing agent, ammonia borane (AB), at the same
time. Due to the much higher redox potential of Au3 + /Au (Eo
Au3 + /Au = 0.39 eV vs. standard hydrogen electrode (SHE)) than
that of Co2 + /Co (Eo Co2 + /Co = 0.28 eV vs. SHE), Au NPs were
formed first. Thanks to the active Au–H species produced in
the reaction as well as the reducing power of AB, Co2 + ions
were efficiently reduced on the surface of Au NPs and the dep-
osition of this first Co layer further promoted the successive
shell growth of Co. Following this similar strategy, other core–
shell NPs have also been prepared, demonstrating the general-
ity of this method. For example, Han and co-workers reported
a one-step aqueous synthesis of Au/Pd core–shell NPs with
a well-defined octahedral shape (Figure 15).[128] Figure 15 a
shows a representative SEM image of the prepared sample,
which demonstrates that the sample was composed of octahe-
dral NPs. A high-resolution TEM image (Figure 15 b) clearly con-
firms the core–shell structure of the octahedral NPs. They fur-
Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org
Minireview
Figure 15. a) SEM and b) HRTEM images of the Au/Pd nanooctahedra. c)
High-magnification HRTEM image of the square region in (b). d) HAADF-
STEM image and cross-sectional compositional line profiles of a Au/Pd nano-
octahedron. e) HAADF-STEM-EDS mapping images of the Au/Pd nanoocta-
hedra. Adapted from reference [128] with permission from the American
Chemical Society.
ther used HAADF-TEM and HAADF-STEM-EDS mapping tech-
nologies to reveal the Au/Pd core–shell structure. In short, the
co-reduction method is an effective approach to fabricate bi-
metallic core–shell NPs. Its major limitation consists in that
only the core–shell NPs with a higher core reduction potential
can be potentially synthesized by this approach. In addition, if
the reducing agent fails to introduce the relatively large differ-
ence in the reduction rate of core and shell metals, it is possi-
ble to simultaneously form homogeneously nucleated NPs
made of completely shell metals, alloy NPs or non-uniform
core–shell NPs in solution.
Galvanic replacement reaction
Galvanic replacement is an electrochemical process that in-
volves the oxidation of one metal (which is often referred to as
a sacrificial template) by the ions of another metal having
a higher reduction potential.[129] The template metal will be
oxidized and dissolve into the solution while the ions of the
second metal will be simultaneously reduced by the core and
therefore, the secondary metal will only be allowed to grow
onto the outer surface of the template. The galvanic replace-
ment reaction, also widely referred to as redox transmetalation,
is the most straightforward method to prepare the core–shell
NPs since no additional reducing agents are required, which
ideally avoids any homogeneous nucleation events. In this
field, Prof. Xia has made a great contribution and has synthe-
sized various core–shell NPs, such as Au/Ag, Pd/Au, Pd/Ag, Pt/
Ag, and Pd/Pt.[130–133] Very recently they further used Pd/Cu
core–shell nanocubes as sacrificial templates for the galvanic
reaction with HAuCl4 in ethylene glycol at room temperature
to prepare a Pd/MxCu1 x (M = Au, Pd, and Pt) yolk–shell struc-
11268  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ture.[134] As shown in Figure 16 a and b, a Pd cube is clearly
present in the interior of each Au–Cu alloyed nanocage. The
HRTEM image (Figure 16 c) of an individual Pd/AuxCu1 x yolk-
shell nanocage reveals that the walls of the nanocage were
made of a random assembly of small crystallites. The elemental
distributions of a single Pd/AuxCu1 x yolk-shell nanocage were
resolved by EDX mapping and line scan profiles (Figure 16 e
and f). Distinct Cu and Au signals were detected from the
walls, while the Pd signal was only observed from the core.
These nanostructures had much larger reactive surface areas
compared with corresponding solid particles of the same size
owing to the presence of the inner surface, which was also ac-
cessible for reactants. As a consequence, their catalytic activity
could be largely increased. Additionally, it is anticipated that
rationally choosing different core and shell metallic materials
will allow for the optimization of the catalytic activity and se-
lectivity for specific reactions. The disadvantage of this ap-
proach can be incomplete redox transmetalation, resulting in
the incomplete shell or the shell of non-uniform shell thick-
ness.
Figure 16. Morphological, structural, and compositional characterizations of
the Pd/AuxCu1 x yolk–shell nanocages obtained by reacting the Pd/Cu core–
shell nanocubes with a solution of HAuCl4 (1.0 mL, 1.0 mm) in ethylene
glycol: a) TEM image, b) HAADF-STEM image, c) and d) HRTEM images, e)
EDX mapping, and f) line scan profiles of a single Pd/AuxCu1 x yolk–shell
nanocage along the dashed line. Adapted from reference [134] with permis-
sion from John Wiley and Sons.
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Adsorbate-induced surface segregation
It is well known that core–shell NPs can transform into alloy
NPs under high-temperature annealing or by a process of gas
absorption/desorption as a trigger.[135] However, there are only
a few reports about the opposite process, where the alloy NPs
eventually developed into core–shell NPs under certain condi-
tions. One procedure is based on the adsorbate-induced sur-
face segregation effect, in which the difference in the gas ad-
sorption energy on different metals can induce surface segre-
gation of bimetallic NPs.[136] In most cases, such formed core–
shell NPs contain alloyed cores. For example, Mayrhofer et al.
have synthesized NPs consisting of a Pt shell around a PtxCoy
core by utilizing the adsorbate-induced surface segregation
effect.[136] More specifically, these NPs were obtained from
Pt3Co alloy upon CO annealing, where the adsorption enthalpy
of CO on Pt is higher than that on Co. As a result, Pt segregat-
ed to the surface of the NPs, and correspondingly displaced
Co to the core. AbruÇa et al. also reported a simple method
for the preparation of PdCo/Pd core–shell NPs supported on
carbon through an adsorbate-induced surface-segregation
effect.[137] Figure 17 a and b shows a pair of HAADF-STEM and
bright-field (BF)-STEM images simultaneously acquired prior
electron energy loss spectroscopy (EELS) map acquisition.
These images reveal the internal crystal structure of the NP.
Figure 17 c and d show projected Co and Pd distributions. The
Pd (red) and Co (green) composite image (Figure 17 e) demon-
strates that a Pd-rich shell was formed on the surface. Accord-
ing to the line profiles of Pd and Co across the Pd-rich shell
(Figure 17 f), the thickness of the shell was estimated to be
Figure 17. a) HAADF-STEM and b) BF-STEM images of a PdCo/Pd core–shell
NP; EELS maps of c) Pd and d) Co along with e) an overlay of those two
maps; and f) EELS line profiles of Pd and Co showing the Pd shell. Adapted
from reference [137] with permission from the American Chemical Society.
11269  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

about 1 nm. Eichhorn et al. reported the preparation of PtSn/
Pt core–shell NPs by similar CO-induced surface segregation of
PtSn intermetallic NPs.[138]
Applications of metallic core–shell NPs in catalysis
As far as metallic core–shell NPs are concerned, catalytic appli-
cations are attracting the most attention. In this section, we
will outline the use of certain typical bimetallic core–shell NPs
as catalysts in different types of catalytic reactions.
Dehydrogenation of AB
Hydrogen is an environmentally friendly fuel and is regarded
as one of the most promising future energy vectors.[123] Recent-
ly, AB has been identified as one of the leading molecular can-
didates for hydrogen storage because of its outstanding physi-
cochemical properties.[139, 140] Hydrogen can be released by the
hydrolysis of AB in the presence of a metal catalyst, such as Pt,
Rh and NiRh alloy NPs that have been demonstrated to be
among the most active ones.[141, 142] Very recently, core–shell
NPs have also been explored for this reaction and were found
to show higher activity than corresponding single-metal NPs.
For example, metallic Au/Co core–shell NPs with the core size
of about 2.5 nm and shell thickness of about 4.5 nm showed
markedly higher catalytic activity than pure Au, pure Co, and
AuCo alloy NPs (Figure 18).[127] The dehydrogenation reaction
of AB was complete within 12 min for the Au/Co core–shell
NPs; in contrast, it took about 1, 14 and 60 times longer to
complete in the presence of AuCo alloy, pure Co and pure Au
NPs, respectively. The authors attributed the better catalytic ac-
tivity of the Au/Co core–shell NPs than similarly bimetallic,
AuCo alloy NPs to the modification of the electronic structure
in the core–shell configuration. Chen and Tao also reported
a polyol reduction synthesis of Co1 x/Ptx and Ni1 x/Ptx core–
shell NPs and their catalytic behaviour for the hydrogen gener-
ation.[143, 144] Both types of core–shell NPs presented good cata-
lytic activities with rapid hydrolytic rate and high hydrogen
generation efficiency. Synergistic effects are considered to be
reasons for the enhanced catalytic activity in the dehydrogena-
tion of AB.[143, 144]
Figure 18. Hydrogen generation from AB aqueous solution (0.26 m, 10 mL)
catalyzed by a) Au/Co, b) AuCo, c) Co, and d) Au NPs under ambient atmos-
phere at room temperature. Catalyst/AB = 0.02 (molar ratio). Adapted from
reference [127] with permission from the American Chemical Society.
Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org 11270
Minireview
Reduction of nitro-aromatic compounds
Nitro-aromatic compounds are toxic organic compounds that
can be formed as by-products during the industrial manufac-
turing process of agrochemical, pigments and pharmaceuti-
cals.[145, 146] On the other hand, aromatic amine chemicals, a hy-
drogenation product of nitro-aromatic compounds, are useful
materials, which can be used as important intermediates in
pharmaceutical synthesis of analgesic and antipyretic drugs, or
as antioxidants in plastics fabrication.[147] Among the investigat-
ed catalysts to date, metal core–shell NPs have shown unusual
catalytic behaviour for the reduction of nitro-aromatic com-
pounds. For example, Xu and co-workers reported the prepara-
tion of Au/Ag core–shell NPs immobilized on a metal-organic
framework by a sequential deposition-reduction method and
their hydrogenation of 4-nitrophenol (4-NP) behaviour.[148]
These core–shell structured Au/Ag NPs showed strong syner-
gistic effect, yielding much higher catalytic activity than alloy
and monometallic NPs (Figure 19). Moreover, the core–shell
NPs also showed outstanding recyclable performance and high
stability. The authors proposed that the modification of the
electronic structure in the Au/Ag core–shell NPs led to the
prominent catalytic activity. Similarly, our recent work also
demonstrated that the synergistic effect between Pt and Au,
Figure 19. a) Catalytic conversion of 4-NP over metal-organic framework
(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 2Au-2Ag (I22). In the above denotation of Iab and IIab, a and
b represent the weight percentage of Au and Ag to ZIF-8, and I and II refer
to the core-shell structure of Au@Ag and Au@AuAg, respectively. b) Arrhe-
nius plots of the rate constants of the reduction of 4-NP over I22. Adapted
from reference [148] with permission from the American Chemical Society.
 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Minireview

although they are not in the core–shell configuration, enhan-

ces the catalytic activity of the reduction of 4-NP.[149] Very re-
cently, Huang et al. synthesized Au/Ag core–shell NPs with
tuneable shapes. They found that Au/Ag core–shell octahedra
were more catalytically active than cubes toward the reduction
of 2-amino-5-nitrophenol at 30 8C.[150]

Oxygen reduction reaction (ORR)

For both polymer electrolyte membrane fuel cells and metal-
air batteries, the cathode catalyst involving the ORR plays
a vital role in determining the performance of electrochemical
energy devices.[151–153] It is well-known that Pt NPs are the most
efficient catalyst for the ORR.[154] However, pure Pt NPs are
easily poisoned, which limits the ORR kinetics and long-term
stability.[155–157] Forming a core–shell structure is a promising
solution in addressing this poisoning issue. Moreover, pure Pt
catalysts are too expensive for commercial applications. There-
fore, it is generally accepted that core–shell type M/Pt NPs
with a very thin layer of Pt in the shell and a less-expensive
metal in the core are more desirable for the ORR. They can
maintain (or even improve) the activity of Pt, yet decrease the
cost of the catalysts. For example, Han et al. prepared hetero-
geneous bimetallic NPs consisting of Pt multibranch shells on
Au nanocrystal cores with well-defined morphologies (cubes,
rods, and octahedra).[156] In all cases, the Au/Pt nanostructures
exhibited higher electrochemically active surface areas than
Ptdendritic shape, indicating that the formation of heterostructures
can provide more catalytically active surface areas. The ORR ac-
tivities were highly dependent on the shape of the core and
the Auoctahedron/Pt showed the largest improvement of the ORR
activity. The authors attributed this large enhancement to the
presence of the (111)-orientation-rich Pt surface in the
Auoctahedron/Pt core–shell NPs. This structural characteristic was
largely determined by the facets of the Au seeds. Moreover,
the presence of Au underneath Pt introduced the compression
to the Pt (111) surface, which can lead to the increase of Pt ac-
tivity according to theoretical predictions (Figure 20). Very re-
cently, they further reported that well-defined Pd/Pt core–shell
NPs with controlled Pt shell thickness (0.4–1.2 nm) could be
synthesized and that their ORR performance strongly depend-
ed on the thickness of the Pt shell.[158] In particular, the carbon-
supported core–shell NPs with a shell thickness of 0.94 nm ex-
hibited enhanced specific activity and higher durability toward
Figure 20. a) Cyclic voltammograms of the Auoctahedron@Pt, Aurod@Pt,
ORR compared to other Pd/Pt-on-carbon NPs and commercial Aucube@Pt, and Ptden in 0.1 m HClO4 at a scan rate of 50 mV s 1. The current
Pt-on-carbon catalysts. The improved properties may be attrib- densities were normalized to the geometric surface area of the GC electrode
uted to the lower OHad bonding strength on their surface (0.071 cm2). b) Specific ECSA for each nanostructure. c) Polarization curves
atoms compared to pure Pt catalysts, due to the beneficial var- for the Auoctahedron@Pt, Aurod@Pt, Aucube@Pt, and Ptden nanocatalysts in O2-satu-
rated 0.1 m HClO4 at a scan rate of 10 mV s 1 and a rotation rate of
iation of the electronic structure in the core–shell NPs. 1600 rpm. d) Mass- and area-specific activity at 0.8 V vs. RHE for the various
nanocatalysts. Adapted from reference [156] with permission from John
Wiley and Sons.
CO preferential oxidation (PROX)
PROX is one of the most important processes for high-purity estingly, Eichhorn et al. reported that their newly developed
hydrogen production from hydrocarbons.[159] Pt-based catalysts Ru/Pt core–shell NPs exhibited predictable high catalytic prop-
have been used for the selective and deep removal of CO in erties, even superior to Pt1 xRux alloy NPs, not to mention
H2-rich stream. Recently, there are many studies regarding monometallic mixtures (Figure 21).[159] In the presence of the
PROX with monometallic and alloy catalysts.[160, 161] Very inter- core–shell catalyst, CO oxidation preceded H2 oxidation to

Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org 11271  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 21. a) Graphical representation of alloy, core–shell and linked mono-
metallic nanoparticles in the Pt–Ru bimetallic system. Pt is black and Ru is
red. Catalytic results for core–shell and alloy PtRu particles. b) Temperature-
programmed reaction (TPR) results for the different Pt–Ru catalysts showing
H2O formation versus temperature for H2 feeds contaminated by 0.1 % CO
by volume. The H2O yields are plotted as % maximum formation based on
the limiting reactant O2. With complete CO conversion in the 0.1 % CO feed,
the maximum formation of water is 90 %. The monometallic Pt remains in
the baseline in this temperature range and does not light off until 170 8C.
c) % Formation of H2O (open symbols) and % CO conversion (filled symbols)
plotted against temperature for the core–shell (black) and alloy (red) nano-
particles catalysts for H2 feeds contaminated by 0.2 % CO. In these feeds, the
maximum H2O yield is 80 % when CO is preferentially oxidized. CO is normal-
ized to its inlet concentration. Note that 70 % of the CO is already converted
to CO2 at 30 8C for the Ru/Pt catalyst. Adapted from reference [159] with
permission from Nature Publishing Group.
a greater extent and both occurred at much lower tempera-
tures. It suggests that the core–shell NPs are more active and
more selective PROX catalysts. Furthermore, in 1 % CO feeds
with 0.5 % O2, the Ru/Pt core–shell NPs showed 70 % oxygen
conversion with 80 % selectivity in clear contrast to < 10 %
conversion and approximately 50 % selectivity for the PtRu
alloy and mixed monometallic systems. These important find-
ings may open new possibilities for the realization of improved
PROX catalysts and possibly CO-tolerant anode catalysts for
low-temperature fuel-cell applications. The same group has
also systematically studied Rh/Pt core–shell NPs for PROX.[162]
The Rh/Pt core–shell NP catalyst had the best activity, showing
impressive, complete CO oxidation at 70 8C and very high
PROX selectivity at 40 8C with 50 % CO conversion, which was
much higher than that over Pt + Rh and PtRh alloy catalysts
(Figure 22). Following this highly interesting work, they further
reported on the first-principle-guided design, synthesis, and
characterization of core–shell NP catalysts made of a transition
metal core (M = Ru, Rh, Ir, Pd or Au) covered with an approxi-
mately 1–2 monolayer thick shell of Pt atoms (i.e., a M/Pt
core–shell NP).[163] Among these core–shell NPs, Ru/Pt core–
shell NPs exhibited the highest PROX activity, followed by Rh/
Pt, Ir/Pt, Pd/Pt, pure Pt, and Au/Pt NPs, in order of decreasing
activity.
Suzuki coupling reactions
Suzuki coupling reactions offer a powerful one-step method
for carbon-carbon bond formation, which plays an important
role in the synthesis of complex molecules to be used as phar-
Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org
Minireview
Figure 22. TPR plots showing a) H2O formation and b) CO2 formation for
monometallic Pt NPs, monometallic mixtures of Pt NPs and 2.7 nm Rh parti-
cles, 4.9 nm Pt50Rh50 alloy NPs, and 3.2 nm Rh/Pt NPs for H2 streams contami-
nated with 2000 ppm CO. Percent of maximum H2O formation was calculat-
ed from the limiting reactant, O2, and % of maximum CO2 formation is rela-
tive to the CO inlet concentration. Adapted from reference [162] with per-
mission from the American Chemical Society.
maceuticals and fine chemicals.[164–166] Recently, scientists found
that Pd-based nanocrystals are attractive as catalysts for Suzuki
reaction. Huang and co-workers found that Au/Pd core–shell
concave cubes had a much superior performance as compared
to other structures.[163] All the Suzuki coupling reactions were
finished in just 30 min with product yields of 89–91 %. They at-
tributed the excellent catalytic activity to the high-index sur-
face facets in the core–shell cubes. Additionally, they also dem-
onstrated that a broad range of Suzuki coupling reactions can
be efficiently catalyzed by the Au/Pd core–shell concave cubes.
Summary and Outlook
The concept of designing and realizing nano-heterostructures
provides great opportunities for the rational development of
new materials and devices. By combining different nano-com-
ponents into the same architecture, not only can the existing
physical and chemical properties be improved over those of
their single-component counterparts, but also new, unique
properties can be introduced. With a choice of diverse compo-
nents and different ways to combine them, nano-heterostruc-
tures have opened up opportunities to a broad range of appli-
cations. Among various types of nanohybrid structures, the
core–shell structure appears as one of the most attractive
ones. In this review, we focus on the discussion of the most
powerful wet-chemical synthesis approaches for achieving
semiconductor and metallic core–shell nanostructures and fur-
ther highlight their potential applications in solar cells and cat-
alysis, respectively.
Despite recent progress, many significant challenges are still
ahead. First, it is still difficult to fabricate high-quality core–
shell nanostructures with precise control over their size, shape
and other structural factors. Narrow core-size and shell-thick-
11272  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ness distributions and uniform, well-defined shapes are re-
quired for most applications. Certain applications may have
some specific requirements. For example, for catalytic reac-
tions, it is expected that the strongest synergistic effect takes
place when the shell is limited to a few monolayers of metal
atoms, which, nonetheless, is very challenging to achieve. As
for the structure of a shell, amorphous, single-crystalline, or
polycrystalline may be preferred, depending on targeted appli-
cations. In addition, some properties may only be offered by
a few, very specific materials. It is thus critical to broaden the
scope of materials that can be involved in the core–shell struc-
ture design and further increase our capability in controlled
synthesis in order to gain flexibility in obtaining the nanostruc-
ture as desired to meet specific requirements of different appli-
cations. Second, more fundamental understanding of core–
shell nanostructures and their properties is still needed. Ther-
modynamic and kinetic factors are important in the synthesis
of a core–shell structure. Their interplay during synthesis deter-
mines the quality of the final nanostructures. Understanding
these factors can help us understand the formation mecha-
nism of core–shell structures and provides a guide for future
designs. In addition, specifically for semiconductor core–shell
QDs, charge-transfer dynamics in different types of QDs
capped by different ligands with different inorganic shell thick-
ness are not well-understood, and neither are multiple exciton
generation and efficient carrier extraction from these excitons.
Moreover, exactly how the band structure is modified by form-
ing different core–shell structures with different shell thickness
and how such a modification affects photovoltaic performance
are among other important questions to answer. On the other
hand, for metallic core–shell NPs it is highly desired to study
their local structure with atomic resolution. Combined with ex-
tensive theoretical work, this can help to achieve in-depth un-
derstanding of the synergistic effect between the core and
shell, which has direct impact on the catalytic behaviour (in-
cluding, for example, activity, selectivity and stability). It is even
more challenging to simulate and monitor in situ the surface
dynamics of core–shell NPs during catalysis, which can play an
important role in unravelling complicated catalysis mecha-
nisms. Knowledge obtained through such fundamental studies
will be beneficial for designing and realizing high-performance
catalysts. Last but not least, considering practical applications,
the low-cost, large scale, high-yield synthesis of high-quality
core–shell NPs with a pre-set morphology is highly desired, al-
though hard to achieve at present. Microwave-assisted synthe-
sis recently emerged as a very promising approach. Moreover,
for the industrialization of metallic core–shell NPs, further ef-
forts are required to replace expensive noble metals, which are
the most common choice for current core–shell structures,
with less expensive metals. To sum up, the high potential of
core–shell nanostructures has served as a large driving force
for ever increasing research interest, even though some tough
challenges remain for these nanostructures. For them to be
broadly used in real-world applications, the combination of ex-
tensive experimental and theoretical work is important, which
holds the promise to overcome these challenges.
Chem. Eur. J. 2014, 20, 11256 – 11275 www.chemeurj.org
Minireview
Acknowledgements
We are grateful to NSERC, FQRNT and AEE for financial sup-
port.
Keywords: catalysis · core–shell structures · nanocrystals ·
nano-heterostructures · solar cells
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