REVIEW

Layered Double Hydroxides www.afm-journal.de

Layered Double Hydroxide-Based Catalysts: Recent

Advances in Preparation, Structure, and Applications
Ming Xu and Min Wei*

performance. Many studies have shown

Layered double hydroxides (LDHs) are a class of functional anionic clays, that active sites can be efficiently modu-
which consist of positively charged host layers (brucite-like M(OH)6 octa- lated by controlling the particle size, com-
hedra) and interlayer anions. By virtue of their unique combination of struc- position, and morphology of catalysts,
regulating their surface/interface defect
tural features (including the tunability of both host layers and interlayer guest
structure (e.g., type and concentration),
anion, exfoliation property, structure topological transformation, confinement and modulating their electronic structures
effect), LDHs have many potential applications in heterogeneous catalysis— or metal–support interactions.[7,8] Thus, in
as catalysts themselves, catalyst supports, or catalyst precursors. In addition, order to substantially improve the activity,
the properties of LDH-based catalysts can be tailored for specific purposes selectivity, and stability of catalysts, it is
by facile modulation of their surface/interface defect structure (e.g., oxygen desirable to develop nanocatalysts with
tailored geometric, electronic, and sur-
vacancy defects or metal defects), controlling the concentration/strength
face/interface defect structures, which
of surface acid/base sites, tuning the geometric/electronic structure of also have a high exposure of active sites.
active sites, or by taking advantage of the confinement effect intrinsic to 2D However, using the traditional methods
materials. In addition, by utilizing the topological structural transformation of for the preparation of heterogeneous cata-
LDH precursors, supported metal catalysts can be obtained (as single metals, lysts, it is difficult to rationally design and
bimetallic alloys or heterostructures, and intermetallic compounds) with tun- precisely modulate active centers at the
atomic scale, and thus attaining simul-
able particle size/morphology and intriguing electronic properties. The main taneously enhanced activity and stability
focus of this review is on recent advances in structure design, preparation, remains a big challenge.
and catalytic applications of LDH-based heterogeneous catalysts. In addition, Layered double hydroxides (LDHs)[9,10]
future challenges and development strategies are discussed from the view- are a class of 2D anionic compounds
points of modulation of intrinsic active sites and establishment of scalable made up of positively charged brucite-like
host layers containing M(OH)6 octahedra,
fabrication processes.
with intercalated anions and water mol-
ecules confined in the interlayer gallery.
LDHs can be represented by the general
1. Introduction formula [M2+1−xM3+x(OH)2]z+An−z/n⋅mH2O, where M2+ and
M3+ are divalent and trivalent metal cations located in the host
Recent advances in the rational design and preparation of high- layers and An− are exchangeable anions in the interlayer region
performance catalysts with excellent stability have attracted compensating for the positive charge on the layers. By virtue
considerable attention in the heterogeneous catalysis field, of the wide range of possible physical and chemical proper-
owing to the extensive applications of the resulting materials in ties, LDH materials have found many applications in the het-
the energy and chemical industries.[1–3] Great efforts have been erogeneous catalysis field,[11,12] including as photocatalysts,
devoted to modulating fine structure of active catalytic sites, electrocatalysts, and thermocatalysts. The composition, particle
since this determines the activity and selectivity of catalysts.[4–6] size, morphology, and surface defect structure, as well as the
In particular, the simultaneous enhancement of activity and electronic properties of LDHs can be modulated by various
stability/lifetime is a key criterion in the evaluation of catalytic synthetic strategies and exfoliation approaches, affording the
coordinatively unsaturated active sites (e.g., low-coordinated
steps, edges, and/or corner atoms) which facilitate heteroge-
Dr. M. Xu, Prof. M. Wei
State Key Laboratory of Chemical Resource Engineering
neous catalysis.[10,13] Moreover, the construction of nanocom-
Beijing Advanced Innovation Center for Soft Matter Science and posites with other materials can also substantially enhance the
Engineering catalytic performance of LDHs, by modulating their geometric
Beijing University of Chemical Technology structure or coupling the electronic properties of the two mate-
Beijing 100029, P. R. China rials.[14,15] In particular, taking advantage of the topological
E-mail: weimin@mail.buct.edu.cn
structural transformation of LDH precursors, a series of high-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.201802943.
performance layered mixed metal oxide (MMO) catalysts and
supported metal catalysts (monometallic or bimetallic catalysts)
DOI: 10.1002/adfm.201802943 can be fabricated; many of these materials have high catalytic

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activity, selectivity, and stability.[8,11,12] Therefore, by virtue of
their unique combination of structural features (layered struc-
ture, compositional flexibility, tunable interlayer anions, and
exfoliation properties) and their topological transformation,
LDH materials have been widely studied as catalysts, catalyst
precursors, and catalyst supports.
This Review highlights recent developments in the design
and preparation of LDH-based nanocatalysts (Figure 1) and their
potential applications in heterogeneous catalysis. New synthetic
approaches and exfoliation techniques for the preparation of
LDH-based catalysts are first reviewed, with a strong emphasis
on the ways in which the structure of the active sites (e.g., surface
defect structure, interface structure, geometric/electronic struc-
ture, and preferential exposure of highly active facets) of LDH-
based nanocatalysts can be precisely tailored. The identification
and characterization of active sites as well as structure–property
correlations are discussed in detail, since these provide helpful
guidelines for the rational design and preparation of future high-
performance heterogeneous catalysts. In the final section, future
opportunities and challenges in the fabrication of LDH-derived
catalysts are discussed in terms of structural design and control
over intrinsic active sites, and some strategies to resolve these
critical issues are proposed. It is hoped that this review will focus
attention on new LDH-based catalysts and encourage future
work in this exciting and rapidly developing area.
2. Catalysts Involving Pristine LDHs or LDH
Nanohybrids
In the past three decades, LDHs prepared by conventional
methods have attracted considerable interest in fields such as
solid base catalysis,[16–19] selective catalytic oxidation,[20,21] and elec-
trocatalysis.[22–27] In order to improve the catalytic performance
of traditional bulk LDHs, an efficient strategy is to decrease the
particle size to the nanoscale level or to exfoliate them to give
ultrathin nanosheets; this can be achieved by both reverse micro-
emulsion methods (bottom-up) and delamination approaches
(top-down).[10] The fabrication of nanocomposites, which can lead
to synergistic effects between LDHs and other nanomaterials, is
another strategy to enhance the catalytic activity of LDHs.[14,15]
2.1. Bulk LDH Materials as Catalysts
In view of the environmental pollution and equipment cor-
rosion caused by soluble alkali catalysts, their substitution by
solid base catalysts offers the advantages of environmental
friendliness and facile manipulation.[28,29] LDHs have many
potential applications in the solid base catalysis area,[30,31] due
to their abundant surface hydroxyl groups (Brønsted type basic
sites located in the brucite-like layers). By taking advantage of
the versatile elemental composition and structural architecture
of LDHs, the structure of the base sites can be tailored. In addi-
tion, the number and strength of basic sites can be effectively
modulated by preparing the materials via calcination of LDHs
to afford MMOs in a topotactic transformation, followed by
rehydration of the MMOs to regenerate an LDH material,[32–35]
often referred to as an “activated LDH;” this so-called “memory
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Ming Xu received his
Bachelor’s degree in 2012
from the Hebei University
of Technology. He joined
Professor Wei Min’s group
as a Ph.D. candidate at
Beijing University of Chemical
Technology (BUCT) in 2013.
His research interests cur-
rently focus on the design
and preparation of LDH-
based catalysts with new-
type Strong Metal–Support Interactions (SMSI) and their
applications in the heterogeneous catalytic water gas shift
(WGS) reaction.
Min Wei received her PhD
from Peking University in
2001, after which she joined
the staff of Beijing University
of Chemical Technology.
She was promoted as full
professor in 2006. She has
been a visiting scholar in
the Georgia Institute of
Technology (in 2008). Her
main research interests focus
on: (1) 2D intercalation
chemistry and functional materials and (2) new catalytic
materials for energy storage and conversion.
effect” of LDH materials can substantially increase the perfor-
mance of the original LDH in base catalysis. Base-catalyzed
reactions (e.g., aldol,[18,30,36] Knoevenagel,[16] and Claisen–
Schmidt condensations[37,38]) have considerable commercial
applications in the production of high value-added chemicals.
It is recognized that the catalytic performance of an LDH is
mainly determined by the geometric structure and electronic
properties of the basic sites. However, methods for identifica-
tion and characterization of solid base sites are rather limited,
and finding ways to enhance catalytic activity by modulating the
microstructure of these basic sites remains a great challenge.
Bing et al. recently reported that activated CaxAl-LDHs show
excellent activity as solid base catalysts for the aldol condensa-
tion reaction (Figure 2).[39] The catalysts were prepared by a facile
two-step process: CaxAl-mixed metal oxides (CaxAl-MMOs) were
obtained by calcination of CaxAl-LDH precursors, followed by a
subsequent rehydration process in basic solution. The optimal
rehydrated re-CaxAl-LDH catalyst showed excellent catalytic
activity for the aldol condensation of isobutyraldehyde and for-
maldehyde. The maximum yield of hydroxypivaldehyde was
≈61.5%, which is superior to that obtained with conventional
solid base catalysts and close to that afforded by soluble alkali
catalysts. The basic catalyst possesses sevenfold CaOH
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Figure 1.  General overview of the ways in which LDHs can be employed in the heterogeneous catalysis field.
coordination, and a combination of advanced characterization
techniques (X-ray photoelectron spectroscopy (XPS), extended
X-ray absorption fine structure (EXAFS), and deuterated chlo-
roform–Fourier-transform infrared spectroscopy (FTIR) spectra)
and density functional theory (DFT) calculations confirmed that
the sevenfold CaOH coordination site provides a weak Brøn-
sted type basic site. Structure–activity correlation studies demon-
strated that such a weak basic site provides an active center for
the aldol condensation reaction, which also accelerates desorp-
tion of the initial aldol product (i.e., inhibits further polyconden-
sation), accounting for the significantly enhanced selectivity com-
pared with other solid base catalysts.
By virtue of the synergistic effects between the surface hydroxyl
groups and the surface defect structure (e.g., oxygen vacancies),
LDHs also show excellent catalytic performance in the heteroge-
neous selective oxidation of alcohols. Recently, Li and co-workers
reported that MgMnTi-LDH catalysts displayed good catalytic
performance in the aerobic oxidation of benzyl alcohol (under
solvent-free conditions).[20] The optimum Mg4Mn2Ti1.0-LDH cata-
lyst was investigated in detail by XPS and the diffuse reflectance
infrared Fourier-transform spectroscopy (DRIFTS) combined
with kinetic analysis, and the results showed that the excellent
catalytic performance can be attributed to cooperative catalysis
by Ti4+OH species, Mn4+OH species, and Ti3+O vacancy
sites. The synergistic effect of Ti4+OH and Mn4+OH species
via π-electron induction promotes the adsorption and activation
of the benzyl alcohol molecule, while the oxygen vacancies asso-
ciated with Ti3+ species located in the host layers significantly
accelerate the adsorption of O2 molecules. The calculated acti-
vation energy value for the Mg4Mn2Ti1.0LDH catalyst is lower
than that of other nonprecious metal catalysts, and is comparable
to the values reported for noble metal catalysts.
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Modulation of the electronic structure of LDH materials
can also influence their performance in other heterogeneous
catalytic reactions. The use of LDH-based nanocatalysts for
the splitting of water to give hydrogen and oxygen by photo-
catalysis[40–43] or electrocatalysis[23–27] has attracted considerable
interest, in view of its ability to reduce our dependence on fossil
energy resources. The oxygen evolution reaction (OER)[44–48] is
an important step in electrocatalytic water splitting. Since OER
is a multistep reaction involving a four proton/electron-cou-
pled process with sluggish kinetics, the development of OER
electrocatalysts[49,50] which can decrease the overpotential and
accelerate the reaction rate is necessary. Numerous studies of
high-performance OER catalysts have focused on tailoring the
chemical composition and the electronic structure of active
sites. However, identification of the active sites and under-
standing the catalytic mechanism are necessary in order to
design improved OER electrocatalysts.
NiFe-LDH catalysts have been shown to exhibit excellent
electrocatalytic activity for OER,[46,48] although the identity
of the active sites remains controversial. Some studies have
reported that Ni serves as the active sites, while others have
claimed that Fe provides the active centers. For instance, evi-
dence from in situ Mössbauer spectra, in situ X-ray absorption,
and in situ XPS strongly suggested the importance of Ni spe-
cies in LDH catalysts for OER. Upon anodization under basic
conditions, abundant discrete Ni4+ domains become located in
regular NiIVO6 octahedra (as a result of charge transfer from
NiO6 to FeO6 octahedra),[24,27] which serve as the optimal
active sites. Moreover, γ-NiOOH was shown to be the active
phase, since it is more active than β-NiOOH and dominates
the OER behavior. Recently, operando Mössbauer spectros-
copy studies were performed to gain an insight into changes
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Figure 2.  Schematic illustration of the structure of re-MgxAl-LDH and re-CaxAl-LDH. A) Normalized XANES spectra at Ca K-edge for (a) re-Ca2Al-LDH,
(b) re-Ca3Al-LDH, (c) re-Ca4Al-LDH, and calcium hydroxide. B) Fourier-transform EXAFS spectra at Ca K-edge for (a) re-Ca2Al-LDH, (b) re-Ca3Al-LDH,
(c) re-Ca4Al-LDH, and calcium hydroxide (solid line, experimental data; dashed line, fitting curve. Reproduced with permission.[39] Copyright 2017,
American Chemical Society.

in the electronic structure of Fe centers in NiFe-LDH catalysts
under actual reaction conditions.[25] The formation of Fe4+ spe-
cies (probably located at an edge, a corner, or a defect site) was
observed during the steady-state water oxidation; in contrast, no
Fe4+ species were detected in the reference catalyst (Fe oxide).
In addition, the Fe4+ species were surrounded by second-coor-
dination-sphere of Ni ions within a NiOOH lattice. This clearly
indicates the advantage of LDHs as a precursor for mixed metal
oxide catalysts, namely, the uniform atomic scale distribution
of the metal cations in the LDH layer; this is much harder to
achieve when using mixed precursors.
DFT calculations have been carried out to explore the active
sites and the mechanism of OER over the NiFe-LDH-based
catalysts.[51,52] Shin et al.[52] found that both Ni4+ and Fe4+ spe-
cies play an important role in the enhancement of OER per-
formance: the high spin d4 Fe sites facilitate the formation of
O⋅ intermediates, while the low spin d6 Ni centers provide the
active site for OO bond formation. In addition, the calcula-
tions also suggested the formation of O2− species, as a result
of deprotonation of the OOH species adsorbed on Ni4+ sites.
Therefore, the presence of both Ni4+ and Fe4+ species contrib-
utes to the excellent OER performance of the NiFe-LDH-based
material.
2.2. Ultrathin Nanosheets of LDHs as Catalysts
Bulk LDH materials can be delaminated into ultrathin or even
monolayer nanosheets by two general approaches, bottom-up
or top-down.[10,53–55] Li et al. developed a facile electrosynthesis
approach[56] to fabricate ultrathin Fe based LDH nanosheets
(lateral length: ≈200–300 nm; mean thickness: ≈8–12 nm)
within 300 s. These ultrathin nanosheet catalysts showed excel-
lent catalytic performance in OER (overpotential: ≈224 mV at
10.0 mA cm−2) and stability, as a result of the high exposure
of active sites and the formation of nanoplatelet arrays. Mono­
layer MgAl-LDH catalysts[57] have also been prepared by a
delamination approach. Recently, Song and Hu reported that

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exfoliated single-layer nanosheets of NiFe and NiCo-LDHs[58]
exhibited significantly better OER performance than the cor-
responding bulk LDH counterparts, with the catalytic activity
even exceeding that of a state-of-the-art IrO2 catalyst. The
enhancement of activity of the bulk LDHs after delamination is
related to the increased electrochemical surface area and better
electron transport properties. Similarly, ultrathin nanosheets of
molybdate-intercalated NiFe-LDHs prepared by an exfoliation-
free hydrothermal approach exhibited OER current densities
about three times higher than those of the corresponding bulk
materials, resulting from the larger density of electrochemically
active sites associated with the ultrathin sheets.[59] In order to
further improve the exposure of active sites, Zhang et al. devel-
oped a one-step in situ growth approach to prepare NiFe-LDH
hollow microspheres,[60] which showed high electrocatalytic
performance for OER. Electrochemical studies demonstrated
that the ultrathin hollow structure can also enhance the ion
transport kinetics. More recently, Lou and co-workers reported
a facile self-templated approach for the preparation of hollow
nanoprisms composed of ultrathin NiFe LDH nanosheets,[61]
which showed high electrocatalytic performance in OER, with
a relatively low overpotential and excellent stability: this was
attributed due to the very large surface area and tailored com-
position. These studies show that the construction of ultrathin
or single-layer nanosheets is an efficient way to substantially
enhance the catalytic performance of LDHs in OER; this is due
to simultaneous increases in the degree exposure of active sites,
the electrochemical surface area, and the ion transport kinetics.
In addition, the electrosynthesis approach offers a new path
to prepare ultrathin LDH materials amenable to large-scale
production.
Precise modulation of the electronic structure of LDHs can
significantly influence their catalytic performance. This can be
achieved by introducing surface defect structures (especially
oxygen vacancies) into the host brucite-like layers. Coordina-
tively unsaturated metal cations (located in the edge-sharing
MO6 octahedra) can be obtained by reducing the layer thick-
ness to atomic length scales of about 1 nm. Recently, Jin and
co-workers reported that ultrathin NiCo-LDH nanosheets pre-
pared by chemical exfoliation exhibited a high catalytic activity
for OER.[62] The enhancement of catalytic activity obtained
by chemically exfoliating LDH nanoplates to afford ultrathin
nanosheets was attributed to a change in electronic structure
resulting from the introduction of surface defects. Ultrathin
ZnAl-LDH nanosheets have been synthesized by a facile
bottom-up approach (an inverse microemulsion technique).[63]
The resulting materials possess abundant coordinatively
unsaturated Zn ions due to the high density of oxygen-vacancy
defects confined in the host brucite-like layers, resulting in sig-
nificantly enhanced photocatalytic activity for the conversion
of CO2 to CO in the presence of water vapor. EXAFS spectra
and positron annihilation measurements, combined with DFT
calculations, conclusively demonstrated the formation of coor-
dinatively unsaturated Zn (Zn+–Vo complexes) after decreasing
the layer thickness. The defect structure serves as the active site
for the adsorption and activation of CO2 and H2O molecules
and simultaneously promotes photoinduced charge separa-
tion, which significantly enhances the rate of photocatalytic
CO2 reduction. Song and Hu prepared ultrathin nanosheets of
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CoMn-LDHs by a facile coprecipitation method,[64] and showed
they behaved as a highly active and robust OER catalyst in an
alkaline medium (with the turnover frequency (TOF) being
nine times higher than that of an IrO2 catalyst). The good per-
formance was attributed to the formation of amorphous layers
at the surface, with an accumulation of active Co(IV) species.
These results show that the precise modulation of the elec-
tronic properties of OER catalysts, either by introducing a sur-
face defect structure or simply by decreasing the layer thickness
of the LDH precursors, can play an important role in improving
the catalytic performance.
The preparation of single-layer nanosheets of NiCo-LDHs by
a liquid phase exfoliation method has been reported recently.
The materials showed significantly higher OER activity than
the corresponding bulk LDHs, resulting from increased
number of active edge sites and improved electronic conduc-
tivity.[62] However, the liquid exfoliation method shows dis-
advantages of long reaction times, low efficiency, and solvent
pollution. Therefore, it is necessary to develop facile, clean,
and efficient approaches to synthesize monolayer nanosheets
LDHs for use as OER catalysts. For example, Wang et al.
reported a dry exfoliation method for the synthesis of mono­
layer CoFe-LDH nanosheets involving Ar plasma etching
(Figure 3).[65] Compared with traditional liquid exfoliation
methods, this strategy is clean, creates no toxic waste, and
avoids the adsorption of solvent molecules. Moreover, the as-
synthesized monolayer CoFe-LDH nanosheets exhibited high
activity for electrocatalytic OER, requiring a lower overpotential
(266 mV) to reach a current density of 10 mV cm−2 than the
corresponding bulk CoFe-LDHs (321 mV). This high activity
was attributed to the large number of exposed surface multiple
vacancies (including O, Co, and Fe vacancies). Most impor-
tantly, the introduction of oxygen vacancies and metal vacan-
cies simultaneously into monolayer LDH nanosheets can mod-
ulate the electronic structure of the materials. The presence
of oxygen vacancies decreases the adsorption energy of inter-
mediates and improves their stability, while the Co vacancies
in the ultrathin nanosheets modulate the surface electronic
structure with change in valence state from Co2+ to Co3+. In
order to further improve the activity of OER, N-doped ultrathin
CoFe-LDH nanosheets with edge-rich sites have been pre-
pared by N2 plasma etching.[66] The material exhibited excellent
activity for OER (with an ultralow overpotential of 233 mV at
10 mA cm−2) attributed to the introduction of surface defects.
This dry exfoliation approach opens up a new path for the syn-
thesis of ultrathin LDH materials.
In summary, reducing the layer thickness of LDHs to afford
ultrathin nanosheets or single-layer nanosheets can substan-
tially improve their catalytic activity. The ultrathin or monolayer
nanosheets can be efficiently prepared by liquid phase exfolia-
tion methods, electrosynthesis or dry exfoliation methods. The
excellent catalytic performance of ultrathin LDHs can be attrib-
uted to the high exposure of active sites and/or defect structures
(oxygen vacancies and metal vacancies) in the brucite-like host
layers. Most importantly, the electronic properties resulting
from the introduction of a defect structure can significantly
enhance the adsorption of reactant molecules and improve the
stability of reaction intermediates, which results in substantial
enhancements in catalytic performance.
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Figure 3.  Schematic illustration of CoFe-LDH nanosheets prepared by Ar plasma exfoliation; AFM images of A) bulk CoFe-LDHs and B) ultrathin
CoFe-LDH-Ar nanosheets. C) The corresponding height curves; D) X-ray diffraction (XRD) patterns of bulk CoFe-LDHs and ultrathin CoFe-LDH-Ar
nanosheets. All panels reproduced with permission.[65] Copyright 2017, Wiley.

2.3. LDH-Based Nanohybrids as Catalysts
The combination of LDH materials and a variety of other
building blocks (e.g., carbon nanotubes (CNTs), graphene, gra-
phene oxide (GO), and metal oxides) can give rise to hierarchical
nanocomposites[14,15] with significantly enhanced catalytic perfor-
mance, due to the synergistic effects between the components.
Moreover, this approach offers an opportunity to engineer sophis-
ticated geometric structures with tunable electronic properties.
Great effort has been devoted to developing facile and cost-effective

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methods for the preparation of such nanocomposites. A series
of creative fabrication methods have been reported, including
grafting LDH nanosheets on nanocarbon,[67–72] forming
core–shell architecture structures,[73–78] and self-assembly of
ultrathin single-layer LDH nanosheets on 3D materials.[79]
Dai and co-workers were the first to report that ultrathin NiFe-
LDH nanoplatelets with good crystallinity can be grown on mildly
oxidized multiwalled CNTs.[67] The resulting NiFe-LDH/CNT
nanocomposite exhibited a high OER electrocatalytic activity with
a TOF of 0.56 s−1 at an overpotential of 300 mV in 1 m KOH, which
is superior to that of commercial precious metal Ir catalysts. More-
over, the catalytic performance was approximately three times
higher than that of previously reported mixed nickel and iron
oxide electrocatalysts. The catalyst also exhibited good durability in
alkaline solutions. The strong interaction between the LDH and
CNTs was verified by X-ray photoelectron spectroscopy, with the
substantial increase in the carbonyl π∗ peak intensity (located at
≈288.5 eV) indicating the formation of MOC bonding via the
carboxyl group, accompanied by large perturbations of the carbon
atom. This work provides a new approach to fabricate low-cost
and high-performance oxygen evolution electrocatalysts.
Subsequently, Yang and co-workers reported another strategy
to construct NiFe-GO LDH hybrids, by taking advantage of the
electrostatic attraction between positively charged exfoliated
NiFe-LDH nanosheets and negatively charged GO layers,[70]
resulting in the formation of hybrid sheets. The as-prepared
hierarchical NiFe-GO LDH catalyst shows an extraordinarily
high electrocatalytic activity for OER with an overpotential as
low as 210 mV and Tafel slope of 40 mV dec−1, which is supe-
rior to the values for NiFe-LDHs, NiFe-LDHs/GO (NiFe-LDHs
nucleated and grown on GO), and NiFe-LDHs+GO (a physical
mixture of NiFe-LDHs and GO). The enhanced electrocata-
lytic performance was attributed to the high exposure of active
sites and the synergistic catalysis between NiFe-LDHs and GO.
Furthermore, NiFe-rGO hybrids were obtained by reduction of
NiFe-GO LDH, and shown to exhibit even better electrocatalytic
activity for OER: the overpotential decreased to 195 mV, and the
TOF reached 0.98 s−1 at an overpotential of 300 mV. The catalytic
performance shows a significant enhancement compared with
earth-abundant metal hydroxide catalysts and is comparable to
that of noble-metal-based electrocatalysts. This was attributed to
the strong interaction between NiFe-LDHs and rGO giving rise
to a molecular level assembly, which facilitates charge transport.
Hierarchical hybrid architectures involving a metal oxide core
and an LDH shell, which can be prepared via hydrothermal
Figure 4.  Schematic illustration of the fabrication of TiO2@CoAl-LDH core–shell nanospheres for oxygen evolution from water splitting. Reproduced
with permission.[76] Copyright 2015, Wiley.
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methods or electrosynthesis, have attracted considerable atten-
tion.[15] Recently, Dou et al. reported a facile two-step approach to
fabricate TiO2@CoAl-LDH core–shell nanospheres: preparation
of TiO2 hollow nanospheres via hydrothermal synthesis followed
by in situ growth of a CoAl-LDH shell (Figure 4). The hybrid
material exhibited an extraordinary high activity for photocata-
lytic water oxidation,[76] with the oxygen gas generation rates
being 2.34 and 2.24 mmol h−1 g−1 under full sunlight (>200 nm)
and visible light (>420 nm), respectively. The observed full utili-
zation of sunlight results from the combination of the visible-
light-responsive LDH shell and the UV-light-responsive TiO2
core. Electron transfer from the LDH shell to the TiO2 core
was observed by XPS, and was confirmed by Bader charge
analysis (with a charge transfer of 0.62 electrons). The photo­
luminescence (PL) signal almost disappeared for the TiO2@LDH
nanospheres, indicating that the recombination of photoinduced
electron–hole pairs in this heterostructure is significantly inhib-
ited. This gives rise to an enhanced carrier transfer efficiency,
which facilitates the photocatalytic performance. DFT calcula-
tions verified that the formation of the heterostructure leads to
an efficient spatial separation of electrons and holes: the strong
donor–acceptor coupling and suitable band matching between
the TiO2 core and LDH shell play an important role in the
enhancement of photocatalytic activity for O2 generation.
In summary, the fabrication of nanocomposites based on
LDHs and other 2D layered materials is an efficient way to
enhance the catalytic performance by taking advantage of
the interfacial synergistic effects between the two materials.
Moreover, the strong coupling between LDHs and nanocarbon
materials facilitates the charge transport at the interface (i.e.,
improves the conductivity), which contributes to the high cata-
lytic activity. However, finding ways of effectively inhibiting the
restacking of nanosheets and improving the contact between
the reactant and active sites are prerequisites if there are to be
further improvements in catalytic performance.
3. MMO Based Nanocatalysts
As discussed above, MMOs can be obtained by calcination of
LDHs in a topotactic transformation.[8,11] A series of studies
have demonstrated that the exposure of crystal facets and defect
structure (e.g., oxygen vacancies) of MMOs can be precisely con-
trolled by varying the conditions for the synthesis of the LDH
precursors and/or the calcination step. In addition to acting as
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
catalysts in their own right, MMOs offer many advantages as
catalyst supports, including a high specific surface area, control-
lable composition and defect structures (e.g., oxygen vacancies),
and tunable quantity and strength of acid/basic sites.
3.1. MMOs as Catalysts
Metal oxides are extensively employed in heterogeneous
catalysis.[80–85] It has been shown that modulation of crystal facets
and surface defect structures of metal oxides can have a signifi-
cant influence on their catalytic performance. In this respect,
MMOs[8,86] offer considerable advantages, since the exposure of
crystal facets and defect structure can be controlled by varying the
topotactic transformation parameters (e.g., heating rate, calcination
temperature, and calcination atmosphere) of the LDH precursors.
He et al. reported a facile in situ topotactic preparation of
ZnO nanocatalysts from ZnAl-LDH precursors. A ZnAl-LDH
flower-like shell was grafted onto amorphous Al2O3 micro-
spheres by an in situ growth method, followed by calcination
to afford ZnO hexagonal nanoplatelets (diameter: 10–50 nm;
thickness: 6–8 nm) immobilized on a hierarchical flower-
like Al2O3 matrix.[81] High resolution transmission electron
microscopy (HRTEM) and selected area electron diffraction
ZnO showed that ≈50% of the exposed facets are ZnO(0001).
The as-obtained ZnO-based MMOs exhibit excellent photo-
catalytic performance in the degradation of Rhodamine B
under visible light irradiation. This was attributed to the pref-
erential exposure of the highly active ZnO(0001) facets, which
have abundant oxygen vacancies and a relatively low bandgap
(≈3.0 eV) in the UV–visible diffuse reflectance spectrum. More-
over, the resulting ZnO hexagonal nanoplatelets exhibit a high
degree of dispersion on the substrate, and thus offer a larger
number of surface active sites than other ZnO catalysts. This
work provides a new approach to fabricate highly dispersed
oxide catalysts with preferential exposure of highly active facets.
More recently, a single-layer NiTi-MMO with a high per-
centage exposure of (110) facets was successfully prepared via
topotactic transformation of single-layer NiTi-LDH nanosheets
(Figure 5).[85] The monolayer NiTi-LDH nanosheets with
mean platelet diameter of ≈20 nm and mean thickness
of ≈0.8 nm were synthesized by a reverse microemulsion
method. The ultrathin NiO nanosheet catalysts derived from
monolayer NiTi-LDH precursors show high electrocatalytic
activity for H2O oxidation. X-ray absorption near-edge struc-
ture (XANES) spectroscopy shows that the absorption edge
of the monolayer NiTi-MMO shifts to higher energies with
less oscillation compared with NiO and bulk NiTi-MMO,
resulting from a higher average Ni oxidation state. The pres-
ence of Ni3+ species were confirmed by electron spin reso-
nance (ESR) and XPS. Moreover, EXAFS demonstrates that
the first NiO shell of monolayer NiTi-MMO has a distance
of ≈2.05 Å and coordination number of ≈5.70, both of which
are smaller than those of bulk NiO (NiO distance: ≈2.08 Å;
coordination number: 12.00) and bulk NiTi-MMO (NiO
distance: ≈2.08 Å; coordination number: 7.70), due to the
presence of nickel vacancies (VNi) in the NiO nanosheets. Nor-
malized XANES spectra at the Ti K-edge further confirmed
that the TiO6 octahedra are disordered in the monolayer
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NiTi-MMO, which is closely related to the formation of oxygen
vacancies. Furthermore, the presence of Ti3+ species was revealed
by XPS (a 2p3/2 peak at 458.2 eV), consistent with the EXAFS
spectra. Therefore, the geometric/electronic structure of mono­
layer NiTi-MMO (the predominance of Ni3+ species, Ti3+ species,
and abundant oxygen vacancy defects) gives rise to a high elec-
trical conductivity and facilitates charge transfer, accounting for
its enhanced electrocatalytic activity for water splitting.
3.2. MMOs as Catalyst Supports
MMOs have been frequently used as supports for hetero-
geneous catalysts.[87–95] Recent studies have shown that the
acidity and basicity of MMO supports can be controlled by
tuning the composition of the brucite-like host layers in the
LDH precursor. Moreover, the synergistic interactions between
supported metal (single metal or alloy) particles or subnano
clusters and the acid/base sites of the MMO supports can lead
to remarkable enhancements of catalytic performance.
Li and co-workers reported that PdAg catalysts supported
on various reducible Mg–Ti mixed oxides with tunable acidity/
basicity exhibited high performance and selectivity for the
selective hydrogenation of acetylene.[88] The quantity and
strength of the acid and basic sites can be controlled by simply
changing the Mg/Ti ratio, which significantly influences the
catalytic activity of the resulting PdAg/MgxTi1−xOy catalysts.
The material with the optimal composition PdAg/Mg0.5Ti0.5Oy
exhibits excellent hydrogenation performance at relatively low
temperature (conversion: ≈99%; selectivity: ≈83.8%; 70 °C). In
situ DRIFTS (e.g., pyridine/CO2 DRIFTS) combined with
temperature-programmed desorption (TPD) experiments (e.g.,
CO2-TPD and NH3-TPD) showed that both the medium acid sites
and weak basic sites promote the hydrogenation of acetylene.
The selectivity was attributed to two factors: i) the high alloying
degree of PdAg increases the number of linearly coordinated Pd
sites, which facilitates desorption of ethylene and prevents further
hydrogenation to ethane; ii) the increased Pd electronic density
arising from the electron transfer from basic sites and Ti3+ spe-
cies also promotes the desorption of ethylene.
Recent studies have mainly focused on the fabrication of
highly dispersed metallic catalysts (e.g., single-atom, pseudo-
single-atom, or subnano clusters), since these materials often
show excellent catalytic performance in a series of industrially
important reactions.[96–99] Although some successful methods
have been developed to enhance the dispersion of active
metal sites (e.g., a mass-selected soft-loading technique,[100] a
wet-chemistry approach,[101–103] or a support surface induced
method[104]), the preparation of stable single-atom or pseudo-
single-atom catalysts remains a considerable challenge. He
and co-workers developed an efficient approach to fabricate
stable single-atom Pt, pseudo-single-atom Pt, and small Pt
cluster catalysts.[92,93] Their method involved the introduction
of Sn4+ cations into the brucite-like layers of an LDH with an
atomic-level dispersion. After calcination to form an MMO,
single-atom Pt precursors or small Pt clusters (fewer than
10 atoms) were immobilized via electrostatic attraction between
negatively charged surface sites and cationic Pt precursors. The
high degree of dispersion of Pt species (single atoms and small
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Figure 5. A) TEM image of monolayer NiTi-LDH nanosheets. B,C) TEM and HRTEM images of monolayer NiTi-MMO. D) FFT pattern of the
corresponding NiO area. E) Geometrical model of the hexagonal NiO nanocrystal. F) AFM image, and G) the corresponding height profiles of
monolayer NiTi-MMO. The numbers 1 to 3 in part (G) correspond to the line scan numbers in part (F). Reproduced with permission.[85] Copyright
2016, American Chemical Society.

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clusters with a Pt dispersion of 96%) was demonstrated by high-
angle annular dark-field scanning transmission electron micros-
copy (HAADF-STEM) combined with EXAFS. The optimal
0.3 wt% Pt/Mg(Sn)(Al)O@Al2O3 catalyst showed high selectivity
for cyclization during the n-heptane reforming reaction. By
contrast, a 2 wt% Pt/Al2O3 catalyst with large Pt particles gave
preferential selectivity for C1 products rather than C7. There-
fore, the size of the Pt particles clearly plays an important role
in determining the performance and selectivity of catalysts for
the n-heptane reforming reaction. This work shows that intro-
ducing high-valent metal ions such as Sn4+ into the brucite-like
host layers of LDH precursors provides a facile way to pre-
pare highly dispersed (even single-atom) noble metals with
promising catalytic behavior.
4. Supported Metal Catalysts Derived from LDH
Precursors
Supported metal catalysts are extensively employed in many
industrial reactions including ammonia synthesis,[105] selec-
tive hydrogenation,[106–108] selective oxidation,[109] and steam
reforming.[110–113] Great effort has been focused on tailoring
the metal active sites so as to simultaneously enhance the cata-
lytic performance, selectivity, and stability. Previous studies
have verified that control over composition, particle size, mor-
phology, dispersion, electronic property, and defect structure of
supported metal nanoparticles can tune the adsorption and acti-
vation of reactant molecules, which improves catalytic activity
and selectivity.[8,11] Furthermore, the construction of supported
bimetallic catalysts is an efficient strategy for simultaneously
tailoring the geometric and electronic structure of catalytic sites.
In addition to control over the metal sites themselves, tuning
the metal–support interfacial structure also plays a crucial role
in improving catalytic performance, by virtue of the synergistic
interactions between metal particles and acid/base sites or
oxygen vacancies on the supports. In particular, the preparation
of supported metal catalysts with tunable strong metal–support
interactions (involving electron transfer) has been recognized
as an important way to enhance catalytic properties. The calci-
nation and subsequent reduction of LDH precursors has been
widely used to prepare metal oxide-supported monometallic
catalysts, bimetallic alloy catalysts, and intermetallic compound
catalysts with tunable particle size, morphology, and geometric/
electronic structure. In this section, we summarize methods for
the rational design and preparation of supported metal catalysts
using LDH precursors and review our current understanding
of structure–activity relationships.
4.1. LDH-Based Monometallic Catalysts
Employing the calcination of LDH precursors followed by
reduction (e.g., under a hydrogen atmosphere) to prepare sup-
ported monometallic catalysts offers three advantages:[7,8,11,12]
First, due to the atomic-level dispersion of divalent and trivalent
metal cations in the brucite-like layers, the reduction process
generally results in a high dispersion of metal nanoparticles.
Second, the cleavage of metal–oxygen bonds and formation of
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metal–metal bond during the transformation of LDH precur-
sors can lead to the production of metal nanoparticles with
selective exposure of specific facets and defects. Finally, using a
single precursor leads to the formation of strong metal–support
interactions which should increase catalyst stability. Recently,
He et al. developed a facile approach to prepare a surface defect-
promoted Ni-based nanocatalyst using a flowerlike NiAl-LDH
shell formed on an amorphous Al2O3 core via an in situ hydro-
thermal method, followed by reduction in hydrogen.[114] X-ray
diffraction (XRD) combined with STEM images reveals that the
supported Ni nanoparticles have a high exposure of (111) planes
with an average particle size of ≈5.0 nm and extremely high par-
ticle density (≈2.4 × 1016 particles m−2), but retain a high degree
of dispersion. When used as a catalyst for the CO2 methanation
reaction, the optimal Ni/HAl2O3(400) material exhibits excel-
lent performance at a relatively low temperature and pressure
(conversion: ≈99% at 300 °C, TOF value: 2.4 × 10−3 s−1 at 220 °C,
selectivity >99%) and the performance is superior to that of
supported noble metal (e.g., Ru or Pd) catalysts. An obvious
distortion of the lattice fringes of the Ni nanoparticles was
demonstrated by HAADF-STEM and HRTEM (e.g., bending
and dislocation), indicating the presence of abundant surface
defects. Positron annihilation spectroscopy (PAS) showed that
the optimal Ni/HAl2O3(400) catalyst had the highest relative
concentration of Ni vacancy clusters, consistent with its excel-
lent low-temperature performance. EXAFS spectroscopy was
carried out to reveal the structure–activity relationship between
Ni vacancy clusters and the catalytic performance, and the
results demonstrated that the Ni/HAl2O3(400) catalyst had
the lowest average NiNi coordination number, consistent with
the PAS results. In addition, the Ni/HAl2O3(400) catalyst shows
long-term catalytic stability: CO2 conversion remained constant
over 252 h and no obvious sintering or aggregation of Ni nano-
particles was observed. The high stability was attributed to the
strong anchoring of the Ni nanoparticles on the Al2O3 support.
Since the first report[118] by Tauster et al. in 1978, the strong
metal–support interaction (SMSI) has attracted considerable
interest and has been shown to play a crucial role in heteroge-
neous catalysis.[5,6,115–117] Tauster showed that supporting VIII
group metals on TiO2 markedly inhibited their ability to adsorb
hydrogen and carbon monoxide. The SMSI effect was attributed
to the migration of partially reduced titania on the surface of the
metal at an elevated reduction temperature.[119,120] Recent studies
have focused on new types of SMSI,[121–125] which differ from the
original. Rodriguez and co-workers reported a new type of SMSI
in Pt/CeOx/TiO2(110) catalysts, which involved electronic pertur-
bation of small Pt particles in contact with ceria, leading to a sig-
nificantly enhanced dissociation of the OH bonds in water.[122]
Campbell used DFT calculations to study the electronic inter-
action between platinum and reduced ceria, and proposed the
new concept of electronic metal–support interactions (EMSI).[126]
Therefore studies of how to effectively regulate SMSI and thus
optimize the properties of heterogeneous catalysts are of great
interest. Calcination of LDH precursors followed by reduction
offers one promising way to achieve this goal.
Xu et al. used a NiTiLDH precursor to prepare TiO2−x-
modified Ni nanocatalysts. HRTEM images demonstrate
that the highly dispersed Ni particles were partially encapsu-
lated by a TiO2−x overlayer (Figure 6). They showed that the
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www.advancedsciencenews.com
Figure 6. A1–D1) TEM images of four Ni@TiO2−x samples (inset: the histogram of size distribution of Ni nanoparticles). A2–D2) HRTEM images of a
single Ni nanoparticle selected from (A1)–(D1), respectively. All panels reproduced with permission.[127] Copyright 2017, American Chemical Society.
metal–support interaction between Ni and the TiO2−x support
could be controlled by varying the synthesis parameters (e.g.,
heating rate, calcination and reduction temperature, and reduc-
tion atmosphere).[127] In situ EXAFS, in situ DRIFTS, and XPS
confirmed the formation of electron-rich Ni species (Niδ−),
resulting from electron transfer from the TiO2−x support to
interfacial Ni by SMSI during the reduction of NiTi-MMO. The
as-obtained optimized Ni@TiO2−x(450) catalyst exhibited excel-
lent catalytic activity (reaction rate: ≈356.8 µmolCO gcat−1 s−1;
TOF value: ≈3.8 s−1) in the water gas shift (WGS) reaction;
these values are much higher than those for Ni-based catalysts
prepared by conventional methods. Moreover, XPS combined
with XANES spectra at the Ti–L edge demonstrated that the
strong interaction between Ni particles and the TiO2−x sup-
port gives rise to the formation of abundant oxygen vacancy
(OvTi3+) sites and Niδ−OvTi3+ interface sites, which serve as
the dual-active-site for the WGS reaction (Ni metal sites activate
CO, while H2O molecules dissociate at oxygen vacancies). Fur-
thermore, in situ DRIFTS spectra (using CO as a probe mol-
ecule) were carried out to identify the strength of the SMSI at
Niδ−OvTi3+ interfacial sites in different materials. The rela-
tionship between the strength of the SMSI at Niδ−OvTi3+
interfacial sites and the catalytic performance was revealed by
quantitative analysis of reaction kinetics models. The results
demonstrate that interfacial sites (Niδ−OvTi3+) with mod-
erate SMSI afford the maximum activity in the WGS reaction.
The synergistic interactions between metal sites and acid–
base sites on supports have been shown to play an important
role in many heterogeneously catalyzed reactions, including
hydrogenation of α,β-unsaturated aldehydes, partial hydrogena-
tion of acetylene, and dehydrogenation of alcohols. Recently,
Chen et al. reported the preparation of acid–base-promoted
Ni nanocatalysts supported on NiAl-mixed metal oxides
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(denoted as Ni/NiAl-MMO) using calcination and reduction of
a NiAl-LDH precursor.[128] The quantity and strength of acid/
basic sites could be efficiently controlled via precisely tuning the
synthesis parameters (e.g., reduction temperature, atmosphere,
heating rate, flow rate). A cubic NiO-like phase (Al3+-doped
NiO structure) of Ni/NiAl-MMO catalysts was identified by in
situ EXAFS, in situ Raman spectroscopy, and in situ XRD. The
presence of medium-strong acid–base sites (Niδ+Oδ− pairs)
was demonstrated by CO2-TPD and NH3-TPD. In situ EXAFS
spectra demonstrate that the first NiO shell distance of the
NiO-like phase (≈2.05 Å) is smaller than that of the NiO refer-
ence material (2.08 Å); while the second NiNi shell (NiOAl)
bond is significantly larger than that of the NiO reference owing
to a severe distortion of the octahedral NiO coordination envi-
ronment, resulting from Al3+ doping and the formation of
NiOAl bonds. When used as catalyst for the dehydrogena-
tion of 2-octanol to 2-octanone under oxidant-free conditions,
the optimal Ni/NiAl-MMO(400) material shows much higher
activity than a conventional Ni/Al2O3 catalyst (with the TOF
values being 174.4 ± 1.59 h−1 and 55.2 ± 1.11 h−1, respectively).
Operando time-resolved EXAFS spectra combined with kinetic
isotope effect mesurements were carried out to study the struc-
ture–property correlation: the presence of Ni0 sites accelerates
α-CH bond cleavage, while the presence of medium-strong
acid–base sites facilitates OH bond cleavage. This work clearly
shows careful choice of the reaction conditions during calcina-
tion and reduction of LDH precursors and offers an effective
way to tailor the synergistic interactions between the metal and
acid/base sites in the resulting supported metal catalysts.
Generally, the surface defect structure (e.g., oxygen vacancies)
of a support determines the nature of surface acid/base sites,
and thus has a significant influence on catalytic performance.
Hu et al. prepared Mn-containing spinel-supported copper
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www.advancedsciencenews.com
nanocatalysts via calcination and reduction of a CuMnAl-LDH
precursor.[129] XPS and H2-temperature-programmed reduc-
tion (TPR) experiments confirmed the presence of highly
dispersed Cu0 nanoparticles, together with abundant surface
oxygen vacancies and Mn2+ species. The optimal catalyst dis-
played exceptional performance in the catalytic hydrogenation
of various biomass-derived compounds containing carbonyl
groups (e.g., gas-phase hydrogenation of dimethyl succinate
(DMS) to γ-butyrolactone). The correlation between the catalytic
reaction rate and parameters such as the Cu+/(Cu++Cu0) ratio
and number of oxygen vacancies was investigated in detail. The
results showed that surface oxygen vacancies (defect structure)
contribute to catalytic activity, and in situ FTIR measurements
of DMS adsorbed on different catalysts demonstrate that the
surface oxygen vacancies adjacent to metallic copper species
substantially promote the adsorption of DMS molecules. Simul-
taneously, Mn2+ species are oxidized to Mn3+ by the CO group
with concomitant formation of CO σ bonds, which deceases
the barrier for DMS hydrogenation. This work shows that the
synergistic interactions between active metal sites and the sur-
face defect structure of the support can significantly enhance
the activity and selectivity of catalytic hydrogenation reactions.
4.2. LDH-Based Bimetallic Catalysts
The geometric and electronic effects generated in supported
bimetallic catalysts can lead to them having significantly
improved catalytic performance when compared with the indi-
vidual component metals alone. Examples include selective
hydrogenation,[130–133] steam reforming,[112,134] and the conversion
of synthesis gas.[135,136] In particular, the selectivity of catalytic
reactions can be significantly enhanced as a result of selective
adsorption and activation of functional groups in the reactant
molecules. Bimetallic catalysts can be divided into bimetallic
alloys, bimetallic heterostructures, and intermetallic compounds
(IMCs). Since LDHs can be prepared containing two (or more)
transition metal ions in the layers, calcination and reduction of
such LDH precursors should be an attractive way to prepare uni-
formly and highly dispersed supported bimetallic catalysts.[8,11,12]
4.2.1. Bimetallic Alloy Catalysts
Gao et al. prepared core–shell structure Cu@(CuCo-alloy)
nanocatalysts embedded on a Al2O3 matrix via a facile two-step
process: an in situ growth of a CuCoAl-LDHs precursor on an
aluminum substrate followed by calcination and reduction.[137]
HRTEM and HAADDF-STEM images demonstrated that the
as-obtained CuCo-alloy catalysts (nanoparticles: 15–20 nm
in diameter) show a core–shell structure with a uniform and
homogeneous distribution of Cu and Co (Cu in the core with
a CuCo-alloy as the exterior shell). When compared with
powdered-CuCo/Al2O3, Co/Al2O3, and Cu/Al2O3 catalysts, the
core–shell Cu@(CuCo-alloy)/Al2O3 catalysts showed signifi-
cantly better catalytic performance in the hydrogenation of
CO to higher alcohols The C6+ 1-alcohol slate selectivity of the
optimal catalyst (Cu/Co = 1/2) reached 48.9% at a CO conver-
sion of 21.5%. XPS provided evidence of electron transfer from
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Cu to Co, indicating a strong electronic interaction between two
metallic species. In situ CO-FTIR spectra demonstrated that the
adsorbed CO molecule gradually migrated from a bridge-type
to linear-type adsorption as the Cu content increased; this was
attributed to electron transfer and active-site isolation effects. It
was found that Cu-rich catalysts with predominantly bridge-type
CO adsorption give higher selectivity for hydrocarbons, while
Co-rich catalysts favor the formation of oxygenated compounds.
The following reaction mechanism was proposed: negatively
charged Co sites facilitate the dissociative adsorption of CO,
CC chain growth, and the formation of *CnHz groups, while
the electron-deficient Cu sites serve as the active site for asso-
ciative adsorption of CO to afford CO* species. The construc-
tion of core–shell structures via the calcination and subsequent
reduction of LDH precursors is thus clearly a promising way
to maximize the synergistic effects in bimetallic alloy catalysts.
The rational design and modulation of the surface/inter-
face microstructure of bimetallic catalysts is another effective
strategy to enhance catalytic performance, and a core–shell
nanostructure containing a transition metal core encapsu-
lated by a noble metal based alloy shell is a good demonstra-
tion of this strategy. Recently, Li et al. reported the prepara-
tion of a Ni@(RhNi-alloy) nanocatalyst with a Ni metal core
and a RhNi-alloy shell (≈2 nm) using an LDH precursor.[138]
The synthesis involved the following three steps: 1) the for-
mation of highly dispersed Ni nanoparticles supported on an
Al2O3 substrate obtained by calcination and hydrogenation of
a NiAl-LDHs precursor; 2) preparation of a Ni@Rh/Al2O3 cata-
lyst by chemical etching of this material with RhCl3 solution; 3)
calcination of Ni@Rh/Al2O3 to afford Ni@(NiRh-alloy)/Al2O3
catalysts. HRTEM images reveal the surface defect structures
of the Ni@(NiRh-alloy) nanocatalyst (e.g., the lattice disorder
at the core–shell interface and the contraction/expansion of the
lattice fringe in the shell). The material has excellent catalytic
performance in hydrogen generation from N2H4BH3 (a rate of
1.2 mol H2 per min⋅mol⋅metal). The utilization efficiency of the
noble metal is substantially enhanced, since it is only present in
the alloy shell rather than the whole nanoparticle, and this method
can be extended to the preparation of other noble metal catalysts.
In addition to achieving high dispersion of supported alloy
nanoparticles, another challenging goal is increasing cata-
lyst stability by inhibiting the sintering of active species. He
and co-workers prepared a CoGa-alloy catalyst by calcina-
tion of a CoGaZnAl-LDH precursor in a reducing atmosphere
(Figure 7).[139] HRTEM images showed a mean particle size of
12.3 nm with a high degree of exposure of (111) facets. Interest-
ingly, HAADF images with element mapping and linescan pro-
files demonstrated that CoGa nanoparticles become trapped in
the MMO support formed during the topotactic transformation
of the CoGaZnAl-LDH precursor. The as-obtained CoGa-alloy
catalyst exhibits excellent catalytic performance in syngas conver-
sion to higher alcohols (43.5% CO conversion and 59% selectivity
for alcohols). Moreover, the formation of the trapped structure
helps to increase catalyst stability by inhibiting sintering (the CO
conversion and selectivity for alcohols remained stable during
reaction for 100 h). Co K-edge EXAFS, CO-FTIR, and CO-TPD
measurements demonstrated that the formation of the CoGa
alloy promotes the electron transfer from Ga to Co, and the
resulting electron-enriched Co serves as the site for dissociative
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Figure 7.  Schematic illustration of the preparation of trapped CoGa particles using LDH precursors. A) XRD patterns of (a) γ-Al2O3, (b) CoZnGaAl-
LDHs/γ-Al2O3, (c) CoZnAl-LDHs/γ-Al2O3, (d) ZnGaAl-LDHs/γ-Al2O3, and (e) ZnAl-LDHs/γ-Al2O3. B) SEM image of CoZnGaAl-LDHs/γ-Al2O3
with cross-sectional image inset. C) SEM–EDS elemental mapping images for Co, Ga, and Zn of the corresponding region (yellow frame in (B)) of
CoZnGaAl-LDHs/γ-Al2O3. All panels reproduced with permission.[139] Copyright 2017, Elsevier.

adsorption of CO, which facilitates the CC bond coupling
needed for carbon-chain growth. In addition, the isolated Co
site (Co atom separated by contiguous Ga atoms) is responsible
for the linear nondissociative adsorption of CO, promoting the
CO insertion step and the formation of alcohols. Therefore, the
trapped structure leads to the maximum matching of CO insertion
and CC coupling, accounting for the very high catalytic activity
and exceptional selectivity for alcohols in syngas conversion.
4.2.2. Bimetallic Heterostructure Catalysts
Precise modulation of the surface defect structure of supported
metal nanoparticles should have a significant influence on cata-
lytic selectivity. A facile and effective approach is to immobilize
clusters of a second metal onto the surface of nanoparticles of a
different metal, so as to modify the original surface defects and
form a new bimetallic heterostructure. Recently, Chen et al.
reported a defect-induced synthesis of heterogeneous bime-
tallic RuNi catalysts, in which Ru clusters (1.1 ± 0.4 nm) were
immobilized on the surface of Ni nanoparticles, as confirmed by
HRTEM (Figure 8).[140] PAS further confirmed that Ru clusters
are anchored on the surface of Ni vacancy cluster defects, which
enhances the average electron density of Ni, as revealed by
EXAFS. Moreover, HRTEM combined with Fourier-transform
EXAFS spectra verified that the formation of a RuNi inter-
face induces an interfacial strain due to the lattice expansion
of Ni nanoparticles. The as-obtained Ru0.8–Ni/H–Al2O3 catalyst
showed excellent catalytic performance in the ethanol steam
reforming reaction, with a H2 yield of 4.2 molH2/molEtOH at
350  °C. In situ FTIR measurements and catalytic evaluation
confirmed that the RuNi interface substantially promotes
CC bond cleavage and efficiently inhibits the CO bond rup-
ture during the reaction, accounting for the very high H2 yield.

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Figure 8.  HRTEM images of Ni/H–Al2O3: A) an overall image, B) one nanoflake with embedded Ni nanoparticles (inset: lattice fringes of Ni nanopar-
ticle), C–E) a single Ni nanoparticle (the scale bar is 1 nm). HRTEM images of Ru0.8–Ni/H–Al2O3: F) an overall image, G) a single RuNi nanoparticle
(inset: a large magnification image), H) EDS mapping of Ni (green, NiK) and Ru (red, RuK) elements for two selected RuNi nanoparticles, I) the
cross-sectional image of one RuNi nanoparticle (inset: a large magnification image), J) the image of the RuNi interface, K) the top-view image of
one Ru cluster embedded on the surface of a Ni nanoparticle. All panels reproduced with permission.[140] Copyright 2016, American Chemical Society.

DFT calculations were carried out to investigate the d-band pro-
jected densities of states for Ni atoms located at a Ni terrace
(111), a Ni step (311), and the perimeter of the RuNi interface.
It was found that Ni vacancy cluster defects with step-edge sites
have a strong ability to simultaneously break CC and CO
bonds, while the RuNi interface sites with a moderate d-band
center position facilitate CC bond cleavage but inhibit CO
bond cleavage. Therefore, modulation of metal surface defects
via the construction of a bimetallic heterostructure can shift the
metal d-band center position to a moderate energy state, which
gives rise to the desired bond-breaking selectivity.
Liu et al. reported the preparation of Cu-decorated Ru bime-
tallic catalysts supported on MgAl-LDH via a facile two-step
procedure: i) the concomitant calcination and reduction of
RuCl3-impregated CuMgAl-LDH by heating at 400 °C in a
hydrogen atmosphere; ii) rehydration of the resulting RuxCuy/
MgAl-MMO to obtain RuxCuy/MgAl-LDH).[141] HRTEM images
showed the presence of uniform and highly dispersed Ru
nanoparticles (mean particle size: ≈2.1 nm) anchored to the
surface of the platelet-like matrix. Moreover, HRTEM combined
with CO-TPD and in situ FTIR demonstrates that Cu preferen-
tially occupies Ru sites with a low coordination number. XPS
showed that there was no electron transfer between Ru and
Cu atoms, indicating the formation of a RuCu bimetallic het-
erostructure rather than a RuCu alloy. The optimal Ru1.0Cu0.5/
MgAl-LDH catalyst exhibited excellent catalytic activity in the
selective hydrogenation of benzene (with a maximum
cyclohexene yield of 44.0% at 150 °C and 5.0 MPa without any
additives). Kinetic investigations demonstrated that the reaction
rate of benzene hydrogenation over Cu-decorated Ru catalysts

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decreased to some extent with increasing Cu content, while the
selectivity for cyclohexene increased significantly. DFT calcu-
lations confirmed that low-coordination Ru sites facilitate the
dissociation of hydrogen, but are unfavorable for the desorp-
tion of cyclohexene, while Cu-decorated Ru sites slightly depress
hydrogen dissociation, but significantly promote the desorption
of cyclohexene leading to a substantial improvement in selectivity
for cyclohexene. Thus, the rational design and effective construc-
tion of bimetallic heterostructures based on the topotactic trans-
formation of LDH precursors provides a feasible approach for
the preparation of high-performance heterogeneous catalysts for
use in systems where consecutive reactions can occur.
4.2.3. Intermetallic Compound Catalysts
IMCs with a definite composition and crystal structure have
attracted considerable attention as heterogeneous catalysts in
reactions such as selective hydrogenation, methanol steam
reforming, and electrocatalytic oxidation.[8,11,12] Although great
effort has been devoted to developing syntheses of IMCs with
controlled structure and morphology, many of the methods
employed suffer from the need to use toxic solvents and/or
complicated procedures. Therefore, the development of facile
and green synthetic routes is a key goal. Recently, various IMC
catalysts supported on MMO supports have been prepared by
taking advantage of the topotactic calcination and reduction of
LDH precursors. Li et al. developed a method to prepare different
NiIn IMC catalysts (Ni3In, Ni2In, NiIn, and Ni2In3) with tun-
able particle size and morphology by in situ reduction of NixIny-
LDH precursors.[142] The atom-scale interspersion of Ni2+ and
In3+ in the brucite-like host layers of the LDH precursor facili-
tates the preparation of highly dispersed IMCs under moderate
reduction conditions. Moreover, the particle size and crystal
phase can be controlled by simply adjusting the Ni/In ratio and
reduction temperature. The as-obtained NiIn IMC catalysts
exhibited excellent catalytic performance in the hydrogenation of
α,β-unsaturated aldehydes (e.g., furfural, 1-phenylethanol, and
crotonaldehyde). EXAFS and DFT calculations showed that the
formation of NiIn IMCs induces electron transfer from In to Ni
due to the polarization of the NiIn bonds, leading to electron-
rich Ni species (Niδ−). This favors the hydrogenation of the nucle-
ophilic CO group at Niδ− sites and simultaneously inhibits the
hydrogenation of the electrophilic alkene (CC) moiety, resulting
in the observed high selectivity for unsaturated alcohols.
Although the in situ topotactic calcination and reduction
of LDH precursors offers a way to prepare IMC catalysts with
controllable composition and particle size, as well as high dis-
persion, it requires that both metallic components of the IMC
can be simultaneously incorporated into the host layers of LDH
precursors. However, some large metal ions (e.g., Sn, Pb, Sb,
and Bi) as well as noble metal elements (e.g., Pt, Ir, Rh, Au,
and Pd) are difficult or impossible to incorporate into the host
layers. Recently, Zhou et al. reported a modified procedure to
overcome this problem. Supported CoSn IMC catalysts with
various compositions (Co2.9Sn2, CoSn, CoSn2) were prepared
via a two-step procedure[143] (Figure 9): CoZnAl-LDHs were
homogeneously impregnated with Na2SnO4, followed by a core-
duction process to obtain supported CoSn IMCs with uniform
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particle size (≈20 nm). The as-prepared CoSn IMC catalysts
show much higher selectivity than comparable monometallic
Co catalysts in the hydrogenation of α,β-unsaturated aldehydes.
EXAFS and DFT calculations showed that this can be attributed
to electron transfer from Sn to Co, and effective isolation of the
active sites by Sn. According to H2-TPD measurements, four
different Co sites (labeled as α, β, γ, and σ) can be identified on
the surface of CoSn IMCs, and DFT calculations demonstrate
that the β-adsorption site (CoSn coordination) serves as the
active center for hydrogenation of the CO bond.
4.3. Metal Phosphide Catalysts
Supported metal phosphide catalysts have attracted consider-
able interest as heterogeneous catalysts, due to their versatile
chemical composition, flexible structural architecture, and unu-
sual electronic properties. Traditional methods for the synthesis
of metal phosphide catalysts (e.g., Fe2P, CoP, Ni2P, and MoP),
including solvothermal reactions,[144] solid-state reactions,[145]
and high temperature reduction of oxide precursors,[146] have
been developed, but these methods normally involve organic rea-
gents and rigorous reaction conditions and the products suffer
from self-agglomeration. Chen et al. have reported an alternative
way to prepare uniform and highly dispersed nickel phosphide
(Ni12P5, Ni2P, and NiP2) catalysts anchored to an Al2O3 matrix
based on a modified LDH precursor approach[147] involving the
following two steps: 1) highly dispersed Ni nanoparticles sup-
ported on Al2O3 were prepared by an in situ topotactic calcination
and reduction of a NiAl-LDHs precursor; 2) various supported
nickel phosphides with different crystal phases were obtained
via a solid–gas reaction between the Ni nanoparticles and red
phosphorus. The chemical composition, structure, and particle
size can be controlled by precisely modulating the calcination/
reduction reaction parameters (e.g., heating rate and reduction
temperature) and molar ratio of metal/red phosphorous. A Ni2P/
Al2O3 catalyst shows excellent catalytic activity and selectivity
for the selective hydrogenation of phenylacetylene (conversion:
98.6%, styrene selectivity: 88.2%; 100 °C, 0.3 MPa, 3 h). In situ
FTIR, EXAFS, XPS combined with DFT calculations showed that
the Ni active sites are isolated by P atoms and electron transfer
occurs from Ni to P, resulting in the formation of Niδ+ centers
with reduced electron density. EXAFS shows that the NiNi
bond length increased to 0.264 nm. Both experimental studies
and DFT calculations demonstrated that the active site isolation
effect and the electron-deficient nature of the Ni site facilitates
di-π(CC) adsorption, but decreases the desorption energy of
the alkene initially formed and thus improves the selectivity for
this species. In addition, due to the strong anchoring on the sup-
port, the as-obtained catalyst exhibits good stability without any
obvious sintering/aggregation after long-term use. This approach
can also be extended to the preparation of other supported metal
phosphides (e.g., CoP and Fe2P).
5. LDHs as Catalysts Supports
LDH materials have been widely used as catalyst supports.
The structure LDH materials (e.g., 2D surface area, flexible
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 9.  A) Normalized intensity of Co K-edge XANES spectra for the CoSn IMCs and Co
foil. B) corresponding Fourier transform k3-weighted EXAFS spectra in R space compared with
Co foil. Atomic arrangement and chemical bonding of the preferential crystal facet of Co and
CoSn IMCs (based on XRD diffraction): C) Co (111) face, D) Co2.9Sn2 (004) face, E) CoSn
(201) face, F) CoSn2 (211) face. All panels reproduced with permission.[143] Copyright 2016,
Royal Society of Chemistry.
composition, confinement effect) allow a series of supported
noble metal (Ru, Pd, Pt, and Au) catalysts[148–150] to be prepared;
the metal particles in these materials have a high degree of
dispersity, as well as structural stability resulting from the
strong anchoring effect of the support. The presence of surface
hydroxyl groups and defect structures (e.g., oxygen vacancies)
located in the brucite-like host layers can significantly influ-
ence the particle size, morphology, and electronic structure of
the supported metal catalysts. An additional advantage of LDHs
is that a wide range of anionic metal complexes can be inter-
calated into the interlayer galleries in a regular arrangement,
offering an alternative to conventional impregnation as a way to
introduce precursors to catalytically active metal particles.
The nature of the exposed crystal facets and surface
hydroxyl groups in different LDH materials play an impor-
tant role in determining the particle size and electronic struc-
ture of supported metal nanoparticles. Mori et al. reported a
stable and well-defined single-atom Ru catalyst anchored to
MgAl-LDH.[151] EXAFS showed that the strongly basic surface
hydroxyl groups promote the formation of electron-rich Ru
centers, due to the strong electronic metal–support interactions.
The obtained single-atom catalyst immobilized on MgAl-LDH
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shows excellent catalytic performance in the
selective hydrogenation of CO2 to formic acid
under mild conditions (2.0 MPa, 100 °C).
The strong Brønsted base type OH− groups
(as electron donors) boost the adsorption and
activation of CO2 molecules and facilitate
the subsequent isomerization step in basic
media. The catalytic activity of single-atom
Ru/MgAl-LDH can be tuned by modulating
the ratio of Mg2+/Al3+, since this changes the
base strength. This work shows how LDH
materials can be a very effective support for
the preparation of single-atom metal catalysts
with specific electronic structure.
By taking advantage of the 2D confinement
effect and anion exchange properties of LDH
supports, a series of supported noble-based
catalysts have been prepared by intercalation
of appropriate precursor anions. Wang et al.
reported 2D gold nanosheet catalysts sup-
ported on MgAl-LDH,[152] which exhibited
excellent catalytic activity and stability in the
solvent-free selective oxidation of carbon–
hydrogen bonds (various phenylic alkanes
with primary and secondary CH bonds) with
molecular oxygen. The Au precursor (AuCl4−)
was first intercalated into the interlayer gallery
of the MgAl-LDH precursor, followed by chem-
ical reduction to afford ultrathin Au nanosheet
catalysts anchored on the MgAl-LDH support.
HRTEM, XPS, and EXAFS demonstrated that
the as-obtained ultrathin 2D gold nanosheets
are negatively charged with a thickness of
a few atomic layers; moreover, preferential
exposure of (001) facets and a low gold–gold
coordination number are observed. The high
catalytic activity of the materials was attributed
to the ultrathin properties and high degree of unsaturation of the
surface Au atoms. After treatment at high temperature, the Au/
LDH catalysts show no obvious sintering or serious aggregation,
suggesting that this is inhibited by the confinement effect of the
brucite-like host layers of the LDH support.
In addition to the immobilization of noble metal particles,
other catalytically active anions can be intercalated into the
interlayer galleries by anion exchange. Wang et al. reported the
immobilization of α-amino acids onto the surface of delami-
nated ZnAl-LDH nanosheets,[153] taking advantage of the elec-
trostatic interaction between the carboxylate groups and the
positively charged LDH nanosheets. The as-obtained catalysts
exhibit high enantioselectivity for the vanadium-catalyzed
epoxidation of allylic alcohols (yield of epoxy alcohol of ≈93%
(after 520 min), and ee values for trans isomers of ≈96% in
the case of L-glutamate-intercalated LDHs). This is due to the
highly dispersed active species confined on the surface of LDH
nanosheets (the rigid inorganic layers), together with a syner-
gistic effect between the active center and the support. By virtue
of this type of immobilization, the catalytic reaction occurs
under pseudo-homogeneous conditions, accounting for both
the fast reaction rate and high enantioselectivity. Therefore,
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
using delaminated LDH nanosheets as support to immobilize
homogeneous active sites (i.e., forming a pseudo-homogeneous
catalyst) is clearly an efficient approach to simultaneously
improve activity and enantioselectivity in asymmetric catalysis.
6. Summary and Perspectives
This Review has summarized recent progress in the design and
fabrication of LDH-based nanostructured catalysts as well as
highlighting structure–activity relationships in a variety of impor-
tant catalytic reactions. By taking advantage of the numerous
advantages of LDH precursors and their topotactic transforma-
tion conversion to MMOs, the surface/interface defect structures
(e.g., oxygen vacancy defects or metal defects), type, quantity and
strength of surface acid/base sites, geometric and electronic struc-
ture (e.g., particle size, composition, morphology, and electron
transfer), can be strategically engineered to give a catalyst with
high activity and excellent selectivity for a specific target reaction.
Moreover, the confinement effect of the host layers and anchoring
effect of the support contribute to the high stability of the cata-
lytically active sites. The geometric/electronic structure and sur-
face defect structure can be characterized by a range of advanced
techniques (e.g., HRTEM, STEM, XPS, DRIFTS, EXAFS, ESR,
Mössbauer spectra, and positron annihilation), which leads to a
fundamental understanding of structure–activity relationships.
Although great progress has been made, critical issues and
great challenges still remain to be addressed in the preparation
of high-performance LDH-based nanocatalysts, with the fol-
lowing three problems being the most important: i) More effi-
cient and simple ways of fabricating monolayer LDH nanosheets
are required. Although the preparation of monolayer LDH
nanosheets has been reported by traditional liquid phase exfo-
liation or dry delamination methods (Ar plasma etching), these
synthetic methods are either time-consuming, environmen-
tally unfriendly, or require rigorous conditions and/or sophis-
ticated techniques. This is a considerable barrier to developing
large-scale practical applications of these materials. ii) Based
on the topotactic transformation of LDH precursors, supported
monometallic or bimetallic catalysts can be prepared with a
high degree of dispersion. However, more precise methods of
engineering the geometric/electronic structure (e.g., metal and
oxygen vacancies) of interfacial sites in the as-obtained catalysts
are needed in order to optimize the catalytic performance of the
resulting materials. iii) The characterization and identification of
active sites are rather difficult at an atomic level, due to the com-
plexity of a heterogeneous reaction and the fact that the nature
of the active site may change under practical reaction conditions.
In the light of these challenges, future studies should focus
on developing new synthetic methods, particularly those which
are amenable to being scaled up, and a detailed and thorough
investigation of the mechanism of the topotactic transformation.
The development of improved synthetic approaches (bottom-up)
and delamination techniques (top-down) is necessary in order
to prepare monolayer LDH nanosheets. The reverse micro­
emulsion method can be tuned by precisely controlling the oil/
water ratio and the property of the oil phase so as to synthesize
uniform and single-layered LDH nanosheets. Scale-up of these
procedures would then allow practical industrial applications.
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Second, the fabrication of supported metal catalysts with SMSI
is an efficient strategy to precisely modulate the geometric/elec-
tronic structure of interfacial sites. If reducible metal cations
(e.g., Fe2+/Fe3+, Co2+/Co3+, Ni2+, and Cu2+) and reducible support
species (e.g., Ti3+/Ti4+, Mn3+/Mn4+, Zr4+, and Ce4+) can be simul-
taneously introduced into the host layers of LDH materials, this
would greatly increase the opportunities to prepare this type of
catalyst. The strength of the SMSI can be efficiently controlled by
simply regulating the calcination and reduction conditions (e.g.,
calcination/reduction temperature and atmosphere), since these
affect the geometric/electronic structure of the interfacial sites
due to the electron transfer associated with the SMSI and the
formation of oxygen defects located at the interface. Therefore,
detailed studies of the mechanism of the topotactic transfor-
mation during the calcination of LDH precursors should allow
the metal–support interactions to be more finely tuned. In situ
time-resolved characterization techniques (e.g., in situ EXAFS
and TG–MS) should be carried out to monitor the structure
evolution process during the whole process of calcination and
reduction of LDH precursors, including monitoring changes in
the electronic state, coordination number, and bond distance.
Third, based on reaction kinetics models, the establishment of
quantitative relationships between reaction rate and structure
(e.g., metal sites, defect sites, or interfacial sites) should allow a
better understanding of the structure of the active sites. In order
to acquire direct evidence about the actual active sites, in situ
characterization techniques are necessary to track catalytic reac-
tion process under in situ or even operando conditions. In situ/
operando XPS, in situ/operando EXAFS combined with in situ/
operando XRD can provide information about the structural
evolution and variation in electronic state of active sites under
practical reaction conditions. In the case of high-valent transi-
tion Fe based catalysts, in situ/operando Mössbauer spectros-
copy is an especially efficient approach to observe the change
of electronic structure and to identify intermediate active phases
of catalyst. In situ/operando DRIFTS combined with mass spec-
trometry can be used as a powerful tool to explore the adsorp-
tion and activation of a reactant molecule and to monitor reac-
tion intermediates. Combined studies of the surface geometric/
electronic structure of a catalyst and the surface chemisorbed
species should provide valuable evidence about the mechanism
of a catalytic reaction. However, the timescales of the structural
evolution of a catalyst and the formation of active intermediates
are normally transient and, therefore, the development of in situ
time-resolved characterization techniques is a necessary prereq-
uisite for obtaining such information. In addition, DFT calcula-
tions serve as a valuable supplementary tool to study activation
energy barriers, transition states, and reaction intermediates,
and to simulate the whole reaction process. As well as providing
a reasonable explanation for experimental observations, DFT
calculations can also be used to make predictions about future
reactions. In summary, the combination of advanced in situ
characterization methodology and DFT calculations is neces-
sary to reveal details about the intrinsic structure of catalytically
active sites, and to provide a fundamental understanding of a
catalytic mechanism at the molecular/atomic level. To overcome
the challenges mentioned above, more creative investigations
should be carried out to boost the development of new LDH
materials for heterogeneous catalysis.
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Acknowledgements
This work was supported by the National Key Research and
Development Programme (Grant No. 2017YFA0206804), the National
Natural Science Foundation of China (NSFC), and the Fundamental
Research Funds for the Central Universities (buctylkxj01). The authors
are thankful for the support of the BSRF (Beijing Synchrotron Radiation
Facility) during the XAFS measurements at the beamline 1W1B, 1W2B
and 4B9B.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
catalyst support, delamination, heterogeneous catalysis, layered double
hydroxides, topotactic transformation
Received: April 30, 2018
Revised: July 11, 2018
Published online:
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