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Nanoscale

REVIEW
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Fabrication of Zero to Three Dimensional Nanostructured


Molybdenum Sulfides and their Electrochemical and
Received 00th January 20xx,
Accepted 00th January 20xx
Photocatalytic Applications
Zhe Lv,a Nasir Mahmood,a,b Muhammad Tahir,a, c Lun Pan,a Xiangwen Zhanga and Ji-Jun Zou*a

Nanoscale Accepted Manuscript


DOI: 10.1039/x0xx00000x

www.rsc.org/ Transition metal dichalcogenides (TMDs) are emerging as promising materials especially for electrochemical and
photochemical catalytic applications, among them molybdenum sulfides have got tremendous attentions due to their
novel electronic and optoelectronic characteristics. Several review articles have summarized recent progress on TMDs but
no critical and systematical summary exist about the nanoscale fabrication of MoS2 with different dimensional
morphologies. In this review article, first we will summarize the recent progress on morphological tuning and structural
evolution of MoS2 from zero-dimension (0D) to 3D. Then the different engineering methods and effect of synthesis
conditions on structure and morphology of MoS2 will be discussed. Moreover, the corrosponding change in electronic and
physicochemical properties of MoS2 induced by structure tuing will also be presented. Further, the applications of MoS2 in
various electrochemical systems e.g. hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), oxygen
evolution reaction (OER) and supercapacitors as well as photocatalytic hydrogen evolution will be highlighted. The review
article will also critically focus on challenges faced by researchers to tune the MoS2 nanostructures and resulted
electrochemical mechanism to enhance their performances. At the end, concluding remarks and future prospects for the
development of better MoS2 based nanostructured materials for aforementioned applications will be presented.

The structure and morphology of a catalyst have significant


1. Introduction influence on its catalytic activity, thus by tuning electronic
structure or surface chemistry, the catalytic activity of the
Nowadays to realize sustainable development of green
1-4 catalyst can be changed extensively. For example, reducing the
energy and environment protection is still a great challenge.
particle size to nanoscale often results higher surface to
The large consumption of quickly depleting fossil fuels such as 5, 6
volume ratio than the bulk counterpart. For catalysis that
petrol, natural gas and coal to maintain the energy needs of
occurs on the surface of catalyst, this increased surface to
the emerging society is alarming the bell to researchers for
volume ratio is highly favourable by bringing increased density
developing alternative energy sources. Therefore, a new
of active sites on the surface. Similarly, the surface complexity
energy production system as well as advanced energy storage
also plays important role in determining the catalyst activity
system needs to be established to meet the requirement of
1 e.g. morphologies with complex surface structure enable more
continuous energy supply. There are several advanced
exposed active sites at tangles and edges on the surface
technologies both for clean energy conversion (e.g. fuel and 7, 8
compared with the simple smooth surfaces. This
solar cells, water electrolysis, etc.) and storage (batteries,
phenomenon is much prominent in the layered materials like
supercapacitors, etc.). These devices are the central
MoS2, for which active sites are mostly linked at the edges
constituents for sustainable energy usage infrastructure and 9, 10
while basal planes are catalytically inert. Therefore,
have been widely studied both at lab and industrial scale. The
fabrication of nanostructure with appropriate size distribution
efficiency of all these devices mainly depends on their
and well-defined morphology is of significant importance for
electrode materials, thus currently intensive researches have
optimizing active edge density for high catalytic performance
been carried out to improve their working capabilities by 11
of MoS2.
developing new electrode materials.
Recently, nanostructured MoS2 has got tremendous
attention because of its vast applications in various fields such
12, 13
as heterogeneous catalysis, electrochemical hydrogen
14-17 18
generation, batteries and photocatalysis. The layered
structure makes MoS2 an ideal material for energy conversion
and storage application that can further be improved by
controlling the number of layers, edge morphologies, the
19
degree of crystallinity and doping of heteroatoms, . A critical

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innovation is highly important for engineering the production and storage systems including photocatalytic and
nanostructures of MoS2 i.e. different dimensional electrochemical hydrogen production. As nanostructured
morphologies and corresponding fabrication methods such as MoS2 with low dimensionality (e.g., zero-dimension (0D), 1D)
20-23 24
chemical and mechanical exfoliation, chemical vapor and fine thickness renders exceptional luminescence and high
25, 26 27 28-30
deposition, solvothermal and hydrothermal methods. electron and hole separation efficiency due to quantum
32, 33
The dimensionality evolution of MoS2 continues from simple confinement effect. Further nanoscale analysis of
0D to complex 3D morphologies, bringing extraordinary high monolayer MoS2 exhibits theoretical Bohr radius value of 0.93
surface areas and exposed more tangles and edges that nm that is much higher than the interlayer distance (0.62 nm)
6
contain larger number of active sites. Hence, a systematic of MoS2.
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analysis and deep knowledge of nanostructured MoS2 with Nanostructured MoS2 exhibit smaller particle sizes and
different dimensional morphologies is vital to understand increased specific surface area as compared with their bulk
active site-interrelated catalysis that will help to fabricate the materials. Considering the applications of MoS2 in
highly efficient catalysts for future energy systems. electrochemical catalysis and photocatalysis, nanostructured
There are several review articles about transition metal MoS2 other than their bulk counterparts show intriguing

Nanoscale Accepted Manuscript


dichalcogenides (TMDs) and 2D materials, which briefly potential in better catalytic activity. By tuning their structures
described about MoS2. But to the best of our knowledge, a and tailoring the surface chemistry, MoS2 based materials
comprehensive detail about the fabrication of MoS2 undergo a significant change in the electronic and
nanostructures with different morphologies and their physicochemical properties, such as the transform of band gap
applications especially in the field of electrochemistry (e.g. from indirect to direct, the increased conductivity from phase
34
hydrogen evaluation reaction (HER), oxygen evaluation change (2H-phase to 1T-phase). Nanostructured MoS2
reaction (OER), oxygen oxidation reaction (ORR), possesses sufficient contact between the electrode material
supercapacitors) is missing. Herein, in this review article we and electrolyte in electrochemical hydrogen/oxygen evolution,
will summarize various methods to fabricate nanostructured oxygen reduction and supercapacitors. As the particle size and
MoS2 with different dimensional morphologies and will explain layer thickness induce, nanostructured MoS2 will expose more
the possible solution to the challenges faced by these edge sites which are highly linked with the catalytic activity,
technologies. Then we will highlight the advantages of these electronic and physicochemical changes enable fast
nanostructured MoS2 and discuss its applications in several electrons transfer and better conductivity.
energy production and storage systems, especially in ORR, OER,
HER, photocatalytic hydrogen generation and supercapacitors
etc. Finally at the end, the conclusions on current research 3. Nanostructural Design and Fabrication of MoS2
achievement, solution to associated challenges and future Designing of MoS2 in nanoscale will alter its optical,
research directions aiming to inspire more exciting studies in mechanical and electronic properties compared with its bulk
the near future will be discussed. counterparts since the size of the object has significant
influence over the catalytic performance. Such alteration of
the electronic structures and morphologies can expand the
2. Electronic and Physicochemical Properties of application spectrum of MoS2 in various fields ranging from
Nanostructured MoS2 energy conversion and storage, chemical transformation to
MoS2 is typical two-dimensional layered material and chemical and biological sensing etc. To realize these promising
possesses sandwich-like S-Mo-S structure which stacks utilizations, it requires appropriate designing and fabrication of
together via weak van der Waals interactions in hexagonal nanostructured MoS2. The most significant and effective way is
arrangement to form the bulk material.12, 31 The existence of to synthesize the nanostructures of MoS2 in 0D, 1D, 2D, 3D
weak van der Waals forces among the layers provides an networks or complex hierarchical nanostructures assembled
opportunity to play with the structure of MoS2 to tune its using the aforementioned building blocks. The fabrications of
properties. The weak coupling among the layers in contrast well-defined nanostructured MoS2 give the advantage of
with the strong inner layer covalent bonds enables prominent enriched basal edges, which are highly linked with the number
35-38
anisotropic properties that can be engineered to tune the of active sites. Hence, it is of significant importance to
electronic structure of MoS2 with specific utilization. fabricate nanostructures of MoS2 with homogenously
Nanostructured MoS2 possesses unique electronic structure distributed edge sites to inhibit the restacking of MoS2 layers.
and distinctive chemical and physical properties compared to In order to improve the catalytic performance of MoS2
the bulk counterpart. For example, bulk MoS2 is typical based materials, there are mainly two aspects to consider:
39
semiconductor with indirect band gap of about 1.2eV,12 but large specific area and high electrical conductivity. The large
the single layer MoS2 exhibits band gap transformation from specific area will guarantee the amount of active edge sites
indirect to direct owing to the quantum confinement effect in and high electrical conductivity will boost the transfer of
the d-electron system. electrons for efficient redox reaction to obtain the desired
Nanostructured MoS2 brings exceptional electronic and performance. The surface area of MoS2 can be increased by
physical features that play pivotal role in efficient energy designing hierarchical nanostructures as these structures bring

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Table 1. Lateral size of MoS2 QDs fabricated by various methods

Method Source of Mo Source of Usage Size Average Ref


Sulfur range/nm size/nm

Electrochemical exfoliation Bulk MoS2 HER 2.5~6 40


1
Mutil-exfoliation based on Bulk MoS2 HER 2~10 41
2
Li intercalation
Solvent exfoliation MoS2 crystal 3~8 5.43 42
3
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Liquid exfoliation MoS2 flakes HER 0.5~4.5 2.5 43


4
Sonication combined with MoS2 powder Bioimaging 1.5~7 3.5 44
5
ion intercalation
Sonication Raw MoS2 HER 2.70.3 45
6
Sulfuric acid-assisted MoS2 powder Intracellular 3.5 46

Nanoscale Accepted Manuscript


7
ultrasonic route microRNA
detection&
multiphoton
bioimaging
Solvothermal Na2MoO42H2O Thiocarbamide Photodegradati 2~3 47
8
on
Ethanolthermal MoS2 powder 1.2~4.2 2.9 48
9
Hydrothermal Na2MoO42H2O L-cysteine Photoluminesc 2.150.34 49
10
ence probe
Hydrothermal Na2MoO42H2O dibenzyl HER 1~7 3.6 50
11
disulfides

higher surface to volume ratio that will exposed maximum are several kinds of methods to fabricate MoS2 QDs that have
edge sites, resulting large number of redox active centers at been summarized in Table 1 along with the average particle
surface for both catalysis and ionic storage. The electrical size and source materials for specific MoS2 QDs.
conductivity of MoS2 can be enhanced by making hybrids with The methods for synthesis of MoS2 QDs follow two simple
carbon-based materials (e.g., carbon black,10 CNT,51 carbon approaches that are top-down and bottom-up. The former one
paper,52 graphene,53, 54 and reduced graphene oxide,55-59 etc.). utilizes exfoliated MoS2 nanosheets or bulk MoS2 powder as
These hybrid formations can also increase the overall surface precursor with the help of different solvent such as
area for better electrode/electrolyte contact. It is also deionization water, ethanol, N,N-Dimethylformamide (DMF) or
observed that change in phase state of MoS2 will influence the N-methyl-2-pyrrolidone (NMP). While the latter one mostly
conductivity as well, e.g. 1T-MoS2 with metallic phase exhibits utilizes molybdenum metal salts or molybdate as the source of
higher conductivity as compared with 2H-MoS2 that is typical Mo and organic materials containing sulfur as S precursor to
semiconducting phase. Besides, composite formation with obtain MoS2 QDs. For further clarification, the top-down
conductive materials, fabrication of well-defined approach utilizes bulk MoS2 and breaks it down into small
nanostructure to increase the number of easily accessible particles and thin layers, while in bottom-up synthesis, MoS2
redox sites and doping of heteroatoms in the basal planes of QDs are generated from atomic or molecular species that work
MoS2 are also the effective ways to increase the conductivity as building blocks for QDs.
by disturbing the density of state (DOS) of MoS2 as well as the Liquid exfoliation is one of the most fundamental strategies
number of redox sites at each defect point created by the to fabricate fascinating nanostructures of MoS2 and generally
doping of heteroatoms. In the following sections, we will carried out in two successive steps: the first one is insertion of
provide an overview on the fabrication of nanostructured ions into the interlayers of MoS2 and second one utilizes shear
MoS2 with different dimensions and the corresponding force to separate the layers of MoS2. Among various methods,
designing strategies. liquid exfoliation method is extensively used by various
research groups to obtain zero dimensional MoS2 with good
3.1 Zero-dimensional MoS2 properties. Li et al. synthesized MoS2 QDs with the assistance
of solvent NMP via ultrasonic exfoliation.45 Here, NMP
By decreasing the particle size to few nanometers, possessing an equivalent surface energy with MoS2 that can
preferable properties such as higher specific surface area, provide proper dispersion and inhibit the agglomeration of as-
more edge sites and improved luminescence efficiency make obtained MoS2 QDs.43 Dai et al. utilized sulfuric acid as solvent
MoS2 quantum dots (QDs) a promising catalyst both in the
fields of electrochemical and analytical chemistry.44, 45There

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Nanoscale Accepted Manuscript


Fig. 1 (a) UV-vis absorption, PL excitation and PL spectra of MoS2 QDs aqueous solution. Reproduced with permission from ref.46.
Copyright 2015, John Wiley and Sons. (b) Experimental set up for electrochemical exfoliation of MoS2 QDs; TEM and HRTEM images of
MoS2 QDs synthesized by using (c), (d) LiTFSI electrolyte and (e), (f) [BMIM]Cl electrolyte. Reproduced with permission from ref.40.
Copyright 2015, Royal Society of Chemistry. (g) Schematic illustration for preparation of nanoporous MoS2 nanosheets and MoS2 QDs via
eletro-Fenton method. Reproduced with permission from ref.42. Copyright 2014, Royal Society of Chemistry. (h) Mechanism for the
photodegradation of RhB under simulated sunlight irradiation. Reproduced with permission from ref.47. Copyright 2014, Royal Society of
Chemistry.

with assistance of ultrasonic power to exfoliate the bulk MoS2 lithium salt (LiTFSI) or 1-Butyl-3-methylimidazolium ([BMIM]Cl)
46 40 - -
and obtained well-defined MoS2 QDs. The as-obtained QDs in a two electrode cell. The insertion of anions (TFSI or Cl )
exhibit significant fluorescence under ultraviolet irradiation into MoS2 interlayers results small particles of MoS2 (Fig. 1(b)).
with blue green color compared with bulk MoS2 as shown in The as-prepared MoS2 QDs as shown in Fig. 1(c)-(f) possess
Fig. 1(a). Dong et al. introduced the use of small particle size distribution and clear lattice fringes. By
tetrabutylammonium as inserting species to exfoliate the MoS2 varying the voltage and concentration of the electrolyte, the
60
via ethanol ultra-sonication. Considering the aforementioned morphology and particle size distribution can easily be
examples, mechanism of liquid exfoliation can be described as controlled during the synthesis of MoS2 QDs. Besides using
ions first insert into MoS2 interlayers and after inducing power MoS2 directly as electrode to obtain QDs, Li et al. synthesized
by sonication the inserted MoS2 could be separated into QDs. MoS2 QDs via electrochemical induced Fenton reaction, the
However, liquid exfoliation technology is facing many MoS2 nanosheets are dispersed in the aqueous electrolyte and
challenges e.g. high power consumption, time consuming and reacted with the electro-generated hydroxyl radicals to
42
associated environmental concerns due to the usage of produce MoS2 QDs as shown in Fig. 1(g).
organic solvent (i.e., NMP, DMF etc). Hence electrochemically Solvo and hydrothermal methods are effective, facile and
coupled exfoliation method is one possible solution to the simple ways to fabricate MoS2 QDs and have been utilized
aforementioned problems as it has advantages of cost extensively. Gao et al. synthesized MoS2 QDs via a one-pot
effectiveness, eco-friendliness and rapidity and have been solvothermal method using Na2MoO4 and thiocarbamide as
47
studied as an alternative way to fabricate MoS2 QDs. During corresponding precursors of Mo and S, respectively. During
the electrochemical exfoliation process, bulk MoS2 is used as the fabrication process, graphene oxide (GO) and commercial
anode where ions are inserted to exfoliate it and results in the TiO2 are utilized for hybrid fabrication of MoS2 QDs-graphene-
formation of MoS2 QDs. Gopalakrishnan et al. used a single- TiO2, which exhibit improved photocatalytic activity. Its worth
step electrochemical exfoliation method to fabricate mentioning that the functional groups on GO have a significant
luminescent MoS2 QDs from bulk MoS2 powder in aqueous influence on the formation of MoS2 QDs because they serve as
ionic liquid solution i.e. bis-trifluoromethane sulfonamide the nucleation centers and also prevent MoS2 QDs from

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aggregation as well, hence the obtained MoS2 QDs possess foam via hydrothermal method with the help of
19
better separation of photogenerated electrons (Fig. 1(h)). Ren polyvinylpyrrolidone (PVP) (Fig. 2(a)). During the fabrication
et al. synthesized MoS2 QDs through hydrothermal route using process, the addition of PVP is of great importance for the
sodium molybdate and dibenzyl disulfides as Mo and S source, desired core-shell nanofiber structure, for the individual PVP
50
respectively. They demonstrated that MoS2 with few-layer polymer chains can interact with each other and self-assemble
nanostructure via proper designing possesses improved into polymer fibers. These transformed fibers can act as soft
65
conductivity and enriched with highly exposed active sites at template to control the tubular structure.
edges. These enhanced properties of MoS2 QDs compared It was observed that the change in reaction time has great
with the bulk counterpart are favorable for excellent impact on the growth of the core-shell 1D nanostructures as
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electrocatalytic performance. Clark et al. have reported an shown in Fig. 2(b)-(h). With the increasing reaction time
extension to hydrothermal fabrication of MoS2 QDs by randomly grown MoS2 nanosheets on Ni3S2 (5 h) starts
designing hybrids of ZnS-MoS2 QDs to enhance the wrapping around Ni3S2 (8 h) and further increase to 12 h
photoluminescence properties of hybrid and open up way to results highly fascinating Ni3S2@MoS2 coaxial nanofibers with
decorate metal chalcogenides on MoS2 for various extremely complex surface which provides large ionic storage

Nanoscale Accepted Manuscript


applications.61 Xu et al. explored several different solvents (e.g. for sodium ion batteries. In another work, they have
DMF, NMP, dimethyl-imidazolidinone (DMEU)) to exfoliate synthesized MoS2 nanotubes comprised of MoS2 nanosheets
bulk MoS2 during solvothermal synthesis of MoS2 QDs,62 which (Fig. 2(i)).63 These hierarchical MoS2 tubular structures exhibit
proved to be good solvents for efficient top-down preparation high surface curvature that results a large amount of exposed
of MoS2 as well as prevent its agglomeration. edge sites and high surface area, thus leading to fascinating
electrocatalytic hydrogen evolution performance.
3.2 One-dimensional MoS2 Shi et al. utilized octylamine directing the fabrication of
Nanostructured MoS2 with rod-, wire- or tube-like MoS2-C nanotubes as shown in Fig. 2(j)-(l).66 During the
morphology has been demonstrated good performance for the solvothermal process, octylamine capped outside Mo and S,
energy conversion and storage devices as 1D structure offers forming octylamine containing MoS2 and at last result in
fast electronic movement and can shorten the ionic diffusion MoS2:C inter-over-lapped nanosheets after carbonizing of the
distance. Mostly the growth of 1D nanostructures of MoS2 is capping molecules (Fig. 2 (m)). The insertion of C into MoS2
template-assisted process, thus requiring a soft or hard interlayers causes enlarged inter-layer distance (0.98 nm) as
template like organic polymers, surfactant solution or/and compared with pristine MoS2 nanosheets (0.62 nm), which
metal belts in the reaction system.63, 64 Wang et al. fabricated provides larger space for enhanced accommodation of ions.
Ni3S2@MoS2 core-shell nanofibers on graphene coated 3D Ni Such functionalized MoS2 nanosheets that assembled into

Fig. 2 (a) Schematic illustration for the synthesis of MoS2/Ni3S2@MoS2; (b)(d) SEM images, (e) schematic illustration and corresponding
(f)(h) TEM images with different reaction time. Reproduced with permission from ref.19. Copyright 2016, Elsevier. (i)TEM and illustration
for MoS2 nanotubes. Reproduced with permission from ref.63. Copyright 2016, Royal Society of Chemistry (j), (k) TEM and HRTEM images,
(l) profile plot of calibration for measuring the spacings in panel (k), (m) schematic illustration for MoS2:C nanosheets. Reproduced with
permission from ref.66. Copyright 2016, Elsevier

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tube-like morphology bring improved performance for ionic favorable for active catalysis.Ye et al. fabricated two kinds of
batteries as they have larger space for ionic storage and highly defect-rich MoS2 nanosheets through oxygen plasma and
conductive carbon act as highway for faster electronic hydrogen annealing treatment and successfully introduced
25
movements. cracks and voids in MoS2 basal planes (Fig. 3(f), (i)). Although
the performance is still not that excellent, compared with
3.3 Two-dimensional MoS2 untreated counterpart the defected MoS2 nanosheets possess
2D designing of nanostructured MoS2 in the form of increased density of active sites and exhibit lower onset
nanosheets is the most commonly used morphology as it potential (300 mV) and the Tafel slope value (147 mV/dec)
offers easy manipulation of electronic and compositional (see in Fig. 3(g)-(k)).
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tuning. Well-crystalline pristine MoS2 nanosheets have poor Here, we will outline two main strategies to prepare highly
activity due to inert nature of basal planes and limited number active MoS2 nanosheets for various applications: (i) by
of edge sites. The number of edge sites and activity of basal fabricating hybrid structures of MoS2 with other conductive
planes can be modified by inducing defects into the basal materials (carbonaceous or inorganic structures) and (ii) by
plane. Xie et al. highlighted a scalable method to make defect- tuning the electronic structure through introduction of

Nanoscale Accepted Manuscript


rich MoS2 nanosheets.67 It is found that by adjusting the molar heteroatoms (metallic or non-metallic) in the basal planes of
ratio of hexaammonium heptamolybdate tetrahydrate MoS2 nanosheets. To tackle with the issue of low conductivity
((NH4)6Mo7O244H2O) and thiourea in a hydrothermal reaction, of MoS2, carbon with excellent electrical conductivity can be
defect-rich and defect-free MoS2 nanosheets could be employed to make hybrid structures which provide better
assembled as shown in Fig. 3(a)-(c). Note that the excess of catalytic activity for electrochemical hydrogen evolution and
thiourea is essential for the fabrication of defect-rich MoS2 ionic storage in batteries. Xie et al. synthesized MoS2
because it serves both as reductant as well as additive to nanosheets vertically aligned on carbon fibers via
stabilize the ultrathin nanosheets. Moreover the existence of hydrothermal method as given in Fig. 4(a), (b).68 The obtained
excessive thiourea inhibits the growth of MoS2 (002) basal MoS2 nanosheets exhibit a charge capacity of 286 mA h g-1 at
plane (Fig. 3 (d), (e)), which correspondingly increase the edge 160 mA g-1 for sodium ion batteries, an improved result
sites in basal plane. The much thinner and defect-rich comparing with the one without MoS2 (172 mA h g-1) (Fig. 4(c)).
nanosheets possess more exposed edge sites that are

Fig. 3 (a) Structural models of defect-free and defect-rich structures; (b), (c) HRTEM of defect-rich MoS2 nanosheets; (d), (e) Atomic
reconstruction of (b), (c). Reproduced with permission from ref.67. Copyright 2013, John Wiley and Sons. (f) SEM images of monolayer
MoS2 with oxygen plasma exposure, (g) LSV curves and (h) Tafel plots for MoS2 with oxygen plasma treatment; (i) STEM images of MoS2
after H2 annealing treatment, and corresponding (j) LCV curves, (k) Tafel plots. Adapted with permission from ref.25. Copyright 2016,
American Chemical Society.

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Fig. 4 (a) Schematic illustration for sodium ion and electron pathways in MoS2 vertically aligned on carbon paper, (b) SEM images and (c)
cycling performance on carbon fiber electrode with MoS2 and without MoS2. Reproduced with permission from ref.68. Copyright 2016,
John Wiley and Sons. (d) Illustration process for MoS2 nanosheets, TEM images (e) and corresponding electrochemical performance (f), (g).
Reproduced with permission from ref.69. Copyright 2015, John Wiley and Sons.

The utilization of carbon paper for dispersing MoS2 nanosheets The catalytic activity of MoS2 could be improved by
could compensate the intrinsic low conductivity, thus increasing specific surface area and exposing more active sites
improving the electrochemical performance Yu et al. at edge. In this regard, Zhang et al. synthesized MoS2
synthesized MoS2 hybrid structures by decorating MoS2 hierarchical nanosheets by vertically decorating them on
nanosheets on N-doped hollow carbon nanoboxes via freestanding carbon nitride substrate by calcining the mixture
69 7
hydrothermal method as illustrated in Fig. 4(d), (e). The N- of melamine and (NH4)2MoS4. The polymerization of
doped carbon backbone could improve the electronic melamine into carbon nitride could direct the horizontal
conductivity and the hollow structure could bring higher ionic growth of MoS2 nanosheets and also provides large area for
diffusivity. As a result, the hybrids possess higher current as-prepared catalysts. Beyond hybrid fabrication, doping of
2
density (40 mA/cm ) comparing with bare MoS2 nanosheets non-metallic elements e.g. nitrogen could modify the chemical
2
(10 mA/cm ) at overpotential of 200 mV for HER catalysis (Fig. and physical properties of MoS2 nanosheets and could also
4(f), (g)). enhance the conductivity and the catalytic activities at the
It is worth mentioning that the usage of carbon materials same time. Qin et al. carried out in situ doping of nitrogen to
not only improves the integral conductivity but also provides a MoS2 nanosheets by heating powders of molybdemun chloride
73
way to fabricate binder free electrodes. Since the as-prepared and thiourea in a tube furnace and the resulted MoS2 hybrids
MoS2 nanosheets on carbon cloth could be directly used as possess better electrical conductivity and improved
-1
electrode for electrochemical test, thus preventing the performance by delivering a specific capacity of 998.0 mA h g
-1
utilization of polymer binder. This could minimize the inactive at 500 mA g after 100 cycles as anode of Li-ion batteries.
volume and lower the contents of non-conductive species in
electrode film. Zhang et al. fabricated 3D vertical graphene on 3.4 Three-dimensional MoS2
carbon cloth and used it as substrate to grow MoS2 Presently, the tuning of MoS2 properties by changing its
70
nanosheetsthrough hydrothermal method. The obtained dimensions at nanoscale got much attention. Typically, 3D
MoS2 composites exhibit onset potential as low as 50 mV (vs. MoS2 nanostructures e.g. nanospheres, nanocages,
2
RHE) and overpotential of only 78 mV (vs. RHE) at -10 mA/cm nanoclusters exhibit high value of both surface to volume ratio
for HER, which is among the best results for MoS2 based and the specific surface area. Many properties are dependent
materials. Similar to the carbon material induced MoS2, many on this particle size transformation especially the amount of
other TMDs materials have also show improved active edge sites, which is highly correlated with the catalytic
electrochemical conductivity and better electrons transfer activity of MoS2. Hence analysis of strategies for fabricating
71 72
rate, e.g. MoSe2-rGO , WS2-rGO etc. active 3D nanostructures of MoS2 is essential for

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Nanoscale Accepted Manuscript


Fig. 5 (a) Schematic of the formation mechanism for MoS2 nanocages, and TEM (b) and HRTEM (c) images. Reproduced with permission
from ref.74. Copyright 2016, Royal Society of Chemistry. (d) Schematic illustration of the synthesis procedure for M-MoS3 hollow structure
and corresponding (e)-(h) TEM, FESEM images. Reproduced with permission from ref.75. Copyright 2016, John Wiley and Sons. (i) atoms
model and optical photograph of (NH4)2Mo3S13. Reproduced with permission from ref.76. Copyright 2014, Nature Publishing Group.

2- 2-
understanding the relationship between physicochemical [Mo2S12] clusters besides [Mo3S13] , the as-prepared dimeric
2-
properties and performance of MoS2 that will further be [Mo2S12] clusters have a low overpotential of 161 mV (vs. RHE)
2
inspiring for effective synthesize of catalytically more active at 10 mA/cm and small Tafel slope of 39 mV/dec. In particular,
2-
MoS2. Zuo et al. synthesized hollow MoS2 nanocages via the hydrogen adsorption energy of [Mo2S12] clusters (-0.05
74
solution-phase reduction of (NH4)2MoS2. The in situ evolved eV) is much lower than Pt(111) (-0.09 eV), contributes to the
10
NH3 gases act as bubble template for the formation of hollow superior HER activity.
MoSx as illustrated in Fig. 5(a). The as-synthesized MoSx Besides the aforementioned nanostructured MoS2, many
transformed into well-defined MoS2 nanocages with the wall researchers have also studied other traditional metal
thickness of 15 nm (Fig. 5(b), (c)) after ex situ thermal dichalcogenides nanostructure, e.g. David Lous group has
annealing for recrystallizing. Similar to the above mechanism, reported a series of novel 3D nanostructures like MoS2 hollow
77 78 79
Yu et al. fabricated hollow structures (prism, sphere, nanospheres , Ni-Co-MoS2 nanoboxes , CoS2 nanobubble ,
80
polyhedron) of M-MoS3 (M=Co, Ni) ternary sulfides via a metal doped Co3S4 hollow tubular with Ni, Mn, Zn etc. These
simple precipitation process of M precursors and ammonium novel hierarchical 3D nanostructured TMDs exhibit good
75
tetrathiomolybdate ((NH4)2MoS4) (Fig. 5(d)). Cobalt or nickel activity and show intriguing potential in electrochemical
precursors with corresponding structures guide the formation energy conversion and storage.
of specific hollow structure and act both as source of transition
metal element and template. This protocol is versatile for
yielding a series of M-MoS3 with different 3D hollow structures 4. Applications of MoS2 Nanostructures
as shown in Fig. 5(e)-(h). The easy manipulation of morphology, variety of structures
Mo-S based molecules and clusters provide maximum and room for electronic modifications make MoS2 very
exposure of edge density and hence results in better catalytic attractive for large number of applications. Here, we will
activity. Kibsgaard and co-workers synthesized MoS2 analogues highlight the applications of MoS2 nanostructures in
2-
trimer [Mo3S13] nanocluster, in these nanoclusters most electrochemical energy conversion and storage such as ORR,
76
sulfur atoms exhibit active site towards HER (Fig. 5(i)). The HER, OER, supercapacitors and photocatalytic hydrogen
2-
clusters of thiomolybdate [Mo3S13] exhibit better HER evolutions.
turnover frequency (TOF) with small onset overpotential of
0.10-0.12 V (vs. RHE) and 0.18-0.22 V (vs. RHE) at the current 4.1 Electrochemical Oxygen Reduction Reaction (ORR)
2
density of 10 mA/cm among other molybdenum sulfides
76 The oxygen reduction is the main constituent for the
fabricated by wet-chemistry. Huang et al. fabricated dimeric
conversion of chemical energy into electrical energy in the fuel

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cells and storage of electrical energy to chemical bonds in the basal planes of MoS2 which exhibits good ORR activity.
metal-air batteries. The catalysts activity towards ORR can be Further, C3N4 was used as a support matrix to provide a large
judged mainly based on four parameters : (1) peak potential; area due to its porous structure that will increase the
(2) onset potential; (3) half-wave potential; (4) and the electrolyte/electrode contact area as well as increase the
81
electron transfer number (n) during reduction process. conductivity. These modulated MoS2 hybrids have a good
-
selectivity of 4e pathway and bear positive onset potentials of
Table 2. ORR reactions in alkaline aqueous solution 0.96 V for P-doped MoS2 nanosheets and 0.94 V for O-
incorporated MoS2 vs. RHE.
ORR reactions electron transfer number (n) Wang et al. studied the MoS2 particle size influence on the
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- - electrocatalytic oxygen reduction by preparing the bulk MoS2


O2+H2O+4e 4OH 4 into ultra small nanoparticles with the aid of N,N-
82
- - - dimethylformamide . As smaller size particles will expose
O2+H2O+2e HO2 +OH 2
more Mo active sites on surface because of increased surface
to volume ratio. Their results show that the obtained MoS2
HO2-+H2O+2e-3OH- 2

Nanoscale Accepted Manuscript


nanoparticles exhibit size-dependent ORR activity and the
catalytic activity increases with the decreasing particle size,
while 2 nm particles show the best activity for ORR and follow
In Table 2 we have summarized the possible reactions in -
4e pathway. Furthermore, the Mo active sites in oxygen
alkaline aqueous solution for ORR, from where it can be seen
- evolution catalysis are demonstrated by covering the particle
that the 4e pathway exhibits higher efficiency and the
- surface with ethylenediaminetetraacetic acid (EDTA) which
intermediates are less hazardous than the 2e process. The
- blocks the Mo edges. After treatment with EDTA the typical
mild reaction process of 4e pathway is also important for long
reduction peaks of MoS2 nanoparticles disappear in CV curve
cycling duration of the equipment. In this regard, catalyst that
- for ORR performance. This change in electrochemical
can catalyze the oxygen reduction by transferring 4e
performance indicates that the Mo edge sites contribute to
isdesignated as efficient and promising candidate.
the catalytic activity.
Nanostructured MoS2 has been widely studied to catalyze ORR
Combining highly conductive materials (like graphene) with
with significant activity (Table 3) and it has been demonstrated
MoS2 could compensate the poor conductivity of MoS2 and
that the exposed Mo atom are the active sites that contribute
82 improve its electrocatalytic performance. Du et al. synthesized
towards the catalysis process.
MoS2 nanodots on porous nitrogendoped graphene via in situ
Doping of foreign elements in nanostructured MoS2 basal 85
pyrolysis reaction. N-acetyl-L-cysteine was used as capping
planes could modulate the electronic properties and thus
agent since it can prevent the obtained MoS2 from aggregation
tuning its catalytic activity. Huang et al. induced low-
83 84
electronegative phosphorus and oxygen heteroatoms into
Table 3. Comparative ORR performance of MoS2

Material Morphology Onset potential/V vs RHE Electrolyte Ref


a 82
1. Bulk MoS2 Microparticles -0.44V vs. SCE 0.1M KOH
a 82
2. MoS2 Nanoparticles -0.35~ -0.4V vs. SCE 0.1M KOH

3. P-MoS2 Nanosheets 0.96 0.1M KOH 83

4. MoS2/N-graphene Nanodots 0.95 0.1M KOH 85

5. O-MoS2-87 Nanosheets 0.94 0.1M KOH 84

6. Co(OH)2-MoS2/rGO Cauliflower-like structure 0.855 0.1M KOH 86

7. MoS2/rGO Nanosheets 0.8 0.1M KOH 87

8. MoS2-CMPs Layered hybrid -0.21V vs. Ag/AgCl 0.1M KOH 88

9. MoS2/rGO Nanosheets -0.17V vs. Ag/AgCl 0.1M KOH 89

10. MoS2/porous silica Flower-like nanostructure -0.14V vs. Ag/AgCl 0.1M KOH 90

11. MoS2/N-graphene Nanosheets -0.12V vs. SCE 0.1M KOH 91

12. Au NPs/MoS2 Nanoparticles -0.1V vs. SCE 0.1M KOH 92

91
13. Pt/C -0.07V vs. SCE 0.1M KOH

a: ORR peak reduction potential

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2-
and can be removed easily to expose the active sites. growth of MoS2 to form more exposed terminal S2 sites,
Compared with bare MoS2, the hybrid of MoS2 nanodots with which is demonstrated to be catalytically active for improved
N-graphene exhibits 200 mV positive shift at onset potential HER performance.
towards ORR. lllathvalappil et al. fabricated Co(OH)2 decorated As aforementioned, combination of MoS2 with conductive
MoS2 nanosheets on reduced graphene oxide via a one step materials could improve the electrocatalytic activity
86
hydrothermal method. The as-prepared Co(OH)2-MoS2/rGO significantly. Yang et al. synthesized MoS2 nanosheets
hybrids significantly improve the onset potential with 0.855 V supported on porous metallic MoO2 via hydrothermal method,
(vs. RHE), nearly 147 mV positive shift as compared with the which possess one-dimensional channel-like structures and
96
pristine MoS2. Furthermore, ORR catalysed by other layered exhibit high conductivity (Fig. 6). The decoration of MoS2
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TMDs such as MoSe2, WS2, and WSe2 exhibit similar but less nanosheets on the surface of MoO2 brings improved
significant electrochemical performance than nanostructured electrochemical hydrogen evolution activity with the small
93 -1
MoS2. Tafel slope of 76.1 mV dec and onset potential of -104 mV (vs.
RHE), almost 100 mV lower than bare MoS2. Generally, the
4.2 Electrochemical Hydrogen Evolution Reaction (HER) basal plane of MoS2 is thought to be catalytic inert for

Nanoscale Accepted Manuscript


hydrogen evolution due to lack of active edge sites. Besides,
Nanostructured MoS2 is known as a geologically abundant semiconductor 2H-phase MoS also hinders its fast electron
2
semiconductor and a robust and efficient alternative catalyst transfer through the reaction. However, by tuning the
27
for HER. Both theoretical and experimental studies have interaction between MoS and substrate, charge transfer
2
revealed that the active sites for efficient HER activity kinetics could be improved. Voiry et al. studied the electronic
10, 11
corresponds to S atoms at edge (i.e. S edge sites). However, coupling between MoS and the substrate and concluded that
2
as bulk MoS2 is comprised of stacked MoS2 monolayers with the catalytic activity of 2H-phase MoS could be improved
2
low level of exposed active edge sites, hence suffers from poor comparable to metallic 1T-phase via proper contact with the
catalytic activity towards HER. Therefore, fabricating substrate.97 By lowering the resistance between MoS and the
2
nanostructured MoS2 with large amount of active sites, high substrate, electrons could be injected into MoS from the
2
catalytic activity of each site and efficient contact between the support sufficiently and efficiently hence improving the
active sites and electrolyte are key points to optimizing the integral hydrogen evolution performance.
hydrogen evolution activity.94

Table 4. Hydrogen Evolution Mechanism

Volmer step H++e-Had

+ -
Heyrovsky step H + Had+e H2

Tafel step 2HadH2

There are three possible steps (Table 4) in HER process and


for every specific catalyst it may follow the Volmer-Heyrovsky
95
mechanism or the Volmer-Tafel mechanism. Both of these
mechanisms involve the adsorption of hydrogen ion on the
surface of electrode, thus catalyst with the free energy of
hydrogen adsorption (GH) close to zero is favorable as both
too low or high values affect the effective adsorption step and
the following desorption. Increasing the amount of active sites
of MoS2 can significantly improve HER performance. The
comparative HER performances have been summarized in
2
Table 5, where the overpotential at -10 mA/cm is taken as the Fig. 6 (a) Polarization curves and (b) Tafel slope of MoS2/MoO2-
basic parameter for comparative performance and it is found 6h(6: the hydrothermal time). (c) Schematic illustration of the
that MoS2 based materials exhibit overpotential around 200 preparation process.(d)-(e) TEM images and (f) selected area
mV, some even less than 100 mV. Gao and coworkers electron diffraction patterns of MoS2/MoO2-6h. Reproduced
synthesized MoS2/CoSe2 hybrid with superior HER activity, the with permission from ref.96. Copyright 2015, Royal Society of
2
overpotential at -10 mA/cm is as low as 68 mV (vs. RHE) and Chemistry.
-1 27
small Tafel slope of 36 mV dec , which is the best result
among non-noble metal based materials for HER catalysts
(Table 5). The addition of CoSe2 nanobelts can mediate the

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Similarly, Yi Xies group studied the phase transformation of due to their intriguing catalytic activity and high abundance as
other TMDs materials during the fabrication process, e.g. V- compared with Pt based materials, which exhibit excellent
98 99 100
doped semimetallic MoS2, CoS2, VS2 in energy conversion performance but still suffer from high cost. Jaramillos group
and storage utilization. As these TMDs materials are typical have made many inroads in exploring new electrode materials
semiconductors thus hinder efficient electron transfer during that exhibit low onset overpotential and high current density
electrochemical and photocatalytic catalysis, the phase change in HER. They studied a large amount of materials for
from semiconductor to semimetallic or even metallic state will electrochemical catalysis in both HER and OER and made
highly increase the conductivity of the integral materials. several benchmarks for quick analysis of the materials
101, 102
Other typical TMDs such as WS2, WSe2 and MoSe2 have also performance.
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aroused much interest in electrochemical hydrogen evolution


Table 5. Comparative HER performances of MoS2

Material Morphology Onset potential Overpotential (mV vs Tafel slop Electrolyte Ref
(mV vs RHE) RHE)@ -10mA cm-2 (mV/dec)
1 MoS2 Quantum dots -120 220 69 0.5 M H2SO4 41

Nanoscale Accepted Manuscript


2 MoS2 Nanosheets -80 217 90 0.5 M H2SO4 103

3 H-MoS2 Hierarchical 167 70 0.5 M H2SO4 7

nanosheets
4 Defected MoS2 Nanosheets -120 180 50 0.5 M H2SO4 67

5 Metallic phase Nanosheets 175 41 0.5 M H2SO4 17

MoS2
6 Semiconductor Nanosheets 274 135 0.5 M H2SO4 17

phase MoS2
7 Chemically Nanosheets -100 220 40 0.5 M H2SO4 11

exfoliated MoS2
8 Chemically Nanosheets 187 43 0.5 M H2SO4 104

exfoliated
MoS2/graphite
9 Edge- Nanosheets -103 150 49 0.5 M H2SO4 14

terminated&interla
yer-expanded MoS2
10 Edge-terminated Column-like -125 190 39 0.5 M H2SO4 105

MoS2 structure
11 Vertically alighed Nanofilms 210 44 0.5 M H2SO4 16

MoS2
12 Hollow micro/nano Nanosphere -112 214 74 0.5 M H2SO4 35

MoS2
13 Mesoporous MoS2 Double-gyroid -150~-200 50 0.5 M H2SO4 106

14 O2 plasma Triangular 171 0.5 M H2SO4 25

exposured MoS2
15 H2 annealed MoS2 Triangular -300 147 0.5 M H2SO4 25
107
16 Defect-&S-rich Nanosheets 135 48 0.5 M H2SO4
MoS2/N-carbon
nanofiber
17 Defect- Nanosheets -103 159 56.1 0.5 M H2SO4 8

MoS2/carbon
18 O-incorporated Nanosheets 120 180 55 0.5 M H2SO4 36

MoS2
19 Co-MoS2 Nanosheets -90 135 50 0.5 M H2SO4 108

20 MoS2/rGO Nanosheets -125 232 98 0.5 M H2SO4 87

21 MoS2/rGO Nanosheets -100 150 41 0.5 M H2SO4 109

22 Graphene Nanosheets -110 180 43.4 0.5 M H2SO4 110

nanoribbon@MoS2
23 MoS2/G Hydrogel -107 86.3 0.5 M H2SO4 39
b 111
24 MoS2/SNG Nanosheets -120 220 45 0.5 M H2SO4
25 MoS2/vertical Hierarchical -50 78 53 0.5 M H2SO4 70

graphene/carbon composite
cloth structure

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a a 37
26 MoSx/graphene/Ni 3D architecture -75 150 42.8 0.5 M H2SO4
foam
27 MoSx-CNTs Subnanometer -48 106 37 0.5 M H2SO4 112

particles/nanot
ubes
28 MoSx/N-CNT Layer/nanotube ~-75 110 40 0.5 M H2SO4 51
52
29 Li-MoS2/CFP Nanoparticles 110 62 0.5 M H2SO4
30 MoS2/MoO2 Nanosheets -104 240 76.1 0.5 M H2SO4 96

31 MoS2/CoSe2 Nanosheets -11 68 36 0.5 M H2SO4 27


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113
32 Cu7S4@MoS2 Hetero- 133 48 0.5 M H2SO4
nanoframes
33 MoS2/Ni3S2 Nanosheets on -50 110 83 1 M KOH 114

nanoparticles
34 PBI-MoS2 Nanoplates -50 160 50.6 0.5 M H2SO4 115

Nanoscale Accepted Manuscript


2- 76
35 [Mo3S13] clusters -100~-120 180~220 38-40 0.5 M H2SO4
2- 116
36 [Mo2S12] clusters 161 39 0.5 M H2SO4
a: approximate value; b: overpotential at 15mA/cm2

4.3 Electrochemical Oxygen Evolution Reaction (OER) conductive Ni foam with high surface area provides good
OER is the process to generate O2 through oxidation of H2O, contact with MoS2 microspheres and thus these hybrids show
which is a typical half reaction during water splitting117 and high current density and reduced overpotential towards
charging process of rechargeable metal-air batteries.118 The OER.127 The OER activities of the as-prepared MoS2 in 1 M KOH
chemisorptions and dissociation of OH- followed by generation at 20 mA/cm2 occurred at overpotential of 310 mV (vs. RHE).
of oxygen-containing and hydrogen intermediates are main
factors that determine the oxidation of water,119 while up till 4.4 Supercapacitors
now only the chemisorptions part has been considered for Supercapacitors are potential energy storage devices with
advanced OER electrocatalysts.120-122 Furthermore, high power density and excellent rate capability.128-131 The
molybdenum disulfide nanostructures have been analyzed energy density (E) of supercapacitor is determined by using the
comprehensively both by experimental methods and DFT equation E=1/2CV2,52, 132-136 therefore to increase E it is
calculations for hydrogen evolution,9, 52 but for OER very desirable to enhance the specific capacitance (C) of electrode
limited efforts have been devoted. The tuning of materials and increase the voltage windows (V).
undercoordinated metal sites on the surface of MoS2 may Supercapacitors mainly follow two charge storage
bring good performance for the catalyst of OER. As these sites mechanisms.137, 138 One is charge separation at the interface
are considered vital for water oxidation especially transition- between electrolyte and electrode (electrochemical double
metal (Fe, Co and Ni) based sulfides123, metal oxide layer capacitors (EDLCs)), while the other one occurring via
materials124, Ni based hydroxides125, and Co based redox reactions undergoes Faradaic process and is called
phosphates126. MoS2 for OER with reasonable activities and pseudocapacitors. Due to high density of charge storage
stabilities in alkaline are not much reported. It appears that through the redox process, pseudocapacitors bear higher
application for hydrogen evolution dominates a large part of specific capacitance than EDLCs. The layered structure of MoS2
MoS2 utilizations, since theoretical studies for OER to offers enormous ways to tune the morphology, structure and
thoroughly understand the mechanisms of MoS2 activities are surface chemistry that make it very attractive in the field of
still in its infancy. energy storage especially for batteries and supercapacitors.139
Zhang and co-workers fabricated MoS2 and Ni3S2 interface MoS2 potentially exhibits high capacitance due to its dual
heterostructures on nickel foam with highly efficient OER.114 electrochemical charge storage abilities by double-layer within
MoS2 nanosheets are fabricated as the outer coat on Ni3S2 its layered structure as well as Faradaic process at its dangling
nanoparticles, which directly grow from the nickel foam in edge structure and defects on surface as illustrated in Table 6
hydrothermal reaction with the existence of sulfur source. The Mo elements own a wide range of oxidation states from +2 to
hybrids exhibit overpotential of 218 mV at 10 mA/cm2 in 1 M +6 and have ability to participate in redox reaction.140-142 The
KOH, much better than bare Ni3S2 and MoS2. Moreover, the continuous redox reactions eliminate the dead time which is
obtained MoS2 hybrids are tested in alkaline electrolyzer for the main concern of metallic oxides, sulfides andhydroxides in
water splitting and the cell voltage at 10 mA/cm2 is as low as their application for supercapacitors.
1.56 V. Their DFT results show that the in situ formation of Both the charge separation efficiency and redox reaction
interfaces between NiO and MoS2 as well as Ni3S2 and MoS2 activity are based on the available active surface area and the
give the optimum chemisorptions of H on MoS2 as well as HO surface chemistry. Hence improving the active surface area of
on nickel sulfide and nickel oxide, which result in improved MoS2 by tuning the surface topology or chemistry can
OER and HER activity. Further, Yan et al. demonstrated that significantly increase its specific capacitance when used as an

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Table 6. Comparative supercapacitor parameters of MoS2

Material Morphology Specific capacitance Electrolyte Process Ref


(F g-1)

-1 138
1. MoS2 Flower-like 168@1A g 1 M KCl Electrical double-
nanosphere layer capacitance
-1 143
2. MoS2 Flower-like 218@5mVs 1 M KCl Electrical double-
nanosphere layer capacitance
3. MoS2 Mesoporous 376@1mVs-1 1 M Na2SO4 Electrical double- 144
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layer capacitance
403@1mVs-1 1 M KCl Electrical double-
layer capacitance
4. SnS2/MoS2 Flower-like 105.7@2.35A g-1 1 M KCl Electrical double- 145

layer capacitance
-1 *

Nanoscale Accepted Manuscript


5. Ti/TiO2/MoS2 Solid-state fiber 230.2@5mVs Electrical double- 146

layer capacitance
-1 142
6. Ni3S4@amporphous Core/shell 1440.9@2A g 6 M KOH Pseudocapacitors
MoS2 nanospheres
-1 147
7. C@Ni3S2@MoS2 Double core-shell 1544@2A g 6 M KOH Pseudocapacitors
nanorods
-1 148
8. MoS2@PANI Nanoneedle 669@1A g 0.5 M H2SO4 Pseudocapacitors
arrays on
nanosheets
-1 149
9. MoS2/PANI Nanowire arrays 552@0.5A g 1 M H2SO4 pseudocapacitors
on tubular MoS2
10. MoS2/PPy Nanosheets 695@0.5A g-1 1M KCl Electrical double- 150

layer capacitance
11. MoS2/G Nanosheets 270@0.1A g-1 1M Na2SO4 Electrical double- 135

layer capacitance
-1 151
12. MoS2-graphene Nanosheets 282@20mV s 1M Na2SO4 Electrical double-
layer capacitance
-1 140
13. MoS2/rGO Layer structure 265@10mV s 1M HClO4 Electrical double-
layer capacitance&
pseudocapacitors
*The electrochemical performance was evaluated by fiber supercapacitor with planar format

electrode of supercapacitors. Further by increasing the specific the entire range of scan rates due to the ease of ionic hopping
143
surface area, electrical conductivity of MoS2 and combining it in ionic liquid medium.
with other redox-active materials could enhance its By increasing the surface area of MoS2 or making its hybrid
148
performance with high value of pseudocapacitance. Wang nanostructures with conductive materials or combining both
et al. fabricated flower-like MoS2 nanospheres through a two- of these two factors could significantly improve the
step hydrothermal method using as-prepared MoO3 nanorod performance of MoS2. This improved activity is due to good
138
as sacrificial precursors, and convert them to MoS2 by ions intercalation and fast transport of electrons. Leite s group
sulfidation reaction. The as-prepared MoS2 nanospheres synthesized MoS2/reduced graphene oxide hybrids with MoS2
140
possess the EDLCs behavior as there is no peak found in their layers covalently bonded on the surface of rGO. At low
-1
CV curves and deliver capacitance of 168 F g at current concentration of MoS2, only small islands of MoS2 grow on rGO
-1
density of 1 A g which is among the best value than any other while restacking of MoS2 nanosheets is observed through van
reported value of pure MoS2 (comparison is presented in Table der Waals interactions with folded edges on increasing the
152-154
6). Even though good results for bare MoS2 have been amount of MoS2 as illustrated in Fig. 7(a). This increased
achieved in this work, its usage as an electrode for amount of MoS2 results in the transformation of
supercapacitors is still limited due to low conductivity and electrochemical storage mechanism from EDLCs to Faradaic
138,
inefficient surface interaction with ions of the electrolyte. process. Thus, by changing the amount of MoS2 loaded, it is
141
Further, Pandey et al. have investigated the effect of possible to tune the electrochemical supercapacitive behavior
electrolyte nature on the electrochemical capacitance of of the MoS2/rGO hybrids. When the amount of MoS2 is low
MoS2by testing its performance both in aqueous and ionic (i.e., LCMoS2/rGO), the hybrids undergo a typical double-layer
-1
liquid media. It is found that MoS2 delivers higher specific process and exhibit a specific capacitance of 1558 F g at 10
-1
capacitance in ionic liquids than aqueous electrolytes within mV s as shown in Fig. 7(b). As the amount of MoS2 increases
(i.e., MCMoS2/rGO and HCMoS2/rGO), significant redox

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Nanoscale Accepted Manuscript


Fig. 7 (a) MoS2/RGO with three different concentrations of MoS2 and the cross sectional view of the interaction between MoS2 and RGO;
Cyclic voltammogram for (b) LCMoS2/RGO and (c) HCMoS2/RGO. Reproduced with permission from ref.140. Copyright 2014, John Wiley
and Sons.

processes deriving from Mo (IV), Mo (V) and Mo (VI) pseudocapacitive behavior (Fig. 8(c)). Zhang et al. fabricated
contribute to the total capacitance (Fig. 7(c)). It is noticed that amorphous MoS2 nanospheres via a simple hydrothermal
too high concentration of MoS2 in MoS2/rGO hybrids also method.142 The specific capacitance of amorphous MoS2 is
hinders the activity as it increases the amount of stacked MoS2 1440.9 F g-1 at 2 A g-1, which is 1.6 times higher than that of
on rGO, which in some way blocks the active sites and slowers crystalline MoS2. The high specific capacitance is attributed
down the ionic and electronic movements, resulting in poor much to the disordered structures, which may offer more
capacitive performance. active sites and transportation channels for ions.
Zhu et al. fabricated the polyaniline (PANI) nanoneedles Solid-state supercapacitor is considered as an excellent
arrays on exfoliated MoS2 nanosheets as shown in Fig. 8(a).148 alternative to the liquid counterpart for the reason that it can
PANI nanoarrays vertically standing on MoS2 nanosheets help prevent liquid leakage and also obsesses long life cycles.155
to hold more ions than pure MoS2 and also offer a fast These advantages make it fascinating for the application of
pathway for electrons as illustrated in Fig. 8(b). The resulting wearable electronics.156 Nevertheless the obstacles hindering
MoS2@PANI architectures render specific capacitance of 853 F its activity lie in how to combine the high specific capacitance
g-1 at current density of 1 A g-1 and undergo a typical with flexibility, conductivity and high density of energy. As for

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Fig. 8. (a) FESEM images of MoS2@PANI, (b) illustration of electrons and electrolyte transportation in MoS2@PANI electrodes, (c) specific
capacitances calculated from galvanostatic charge/discharge profiles at various current densities. Reproduced with permission from ref.148.
Copyright 2015, John Wiley and Sons. (d) Specific capacitance vs. scan rate and (e) schematic of self-powered system. Reproduced with
permission from ref.146. Copyright 2016, Elsevier.

MoS2 applied for solid-state supercapacitors, many inroads Photocatalytic hydrogen evolution is one of the most
have been made in making hybrids to compensate the poor fascinating methods to store solar energy into chemical energy
161, 162
conductivity for high performance. Li et al. synthesized novel that can be used as fuel energy. As a result of sluggish
Ti/TiO2/MoS2 coaxial fibers structure which can be directly hydrogen production efficiency on bare semiconductor alone,
146
used in planar format for supercapacitors. The as-obtained most of the photocatalysts consist of co-catalyst in order to
-1 163-165
hybrids exhibit specific capacitance of 230.2 F g at scan rate realize high hydrogen evolution rate via solar irradiation.
-1
of 5 mV s as shown in Fig. 8(d). Furthermore, these solid state The utmost steps in photocatalytic hydrogen evolution lie in
hybrid fibers can be applied into self-powered photodetection the effective separation of charge carriers (i.e. quantum yield)
166
system (in Fig. 8(e)) as the energy storage part due to their and the reaction kinetics at the interface of catalysts. Noble
steady energy storage performance. Hao et al. synthesized metals are effective co-catalysts to improve the quantum yield
MoS2 nanosheets for flexible all-solid-state supercapacitors by but suffer from limited earth abundance and high price. Hence,
157
incorporating Ni(OH)2. The insertion of Ni(OH)2 is able to non-noble metals with considerable photocatalytic activity
weaken the restacking of MoS2 layers, which is of significant have been viewed as good alternatives among which MoS2 has
importance for efficient ion-accessible surface and high been manifested to be a potential co-catalyst for
158
capacitance. Though not that widely studied as MoS2, other photocatalytic hydrogen evolution with significantly improved
167-169
TMDs materials like MoSe2 also shows potential for the activity. Li et al. synthesized MoS2 monolayer combined
159, 160
utilization as an electrode of supercapacitors. MoSe2 with Bi12O17Cl2 monolayers which perform much improved
-1 -
with the similar sandwich structure as that of MoS2 exhibits visible induced hydrogen evolution rate with 33 mmol h g
1 170
comparative capacitance and rate capability. .
Resistance along the basal plane of MoS2 is much smaller
94, 171
4.5 Photocatalytic Hydrogen Evolutions than that through the layers and the edges of MoS2 are

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Fig. 9 Schematic illustration of (a) MoS2 nanosheets stand vertically on TiO2 and (b) MoS2 nanosheets connect with TiO2 along basal plane,
(c) H2 evolution rate on TiO2 and two kinds of MoS2/TiO2, (d) transport pathway of photoexcited electrons on MoS2 vertically aligned on
TiO2. Reproduced with permission from ref.166. Copyright 2016, John Wiley and Sons. (e) Schematic illustration of charge-transfer behavior
and H2 evolution active sites for 1T-MoS2 and 2H-MoS2, and (f) photocatalytic average rates under UV light irradiation (<400 nm).
Reproduced with permission from ref.172. Copyright 2015, Springer.

9, 10, 94,
more active than the plane towards hydrogen evolution, efficiency as illustrated in Fig. 9(e), (f). Besides, amorphous
109
hence fabricating MoS2 with the edges connected to the MoS2 as compared with crystalline MoS2 possesses more
main catalysts and active sites exposed as much as possible is disordered crystal structure which enables more unsaturated S
highly desired for high H2 evolution activity, in this way the atoms. Yu et al. fabricated amorphous MoSx as electron
photo-excited electrons could transport from the main catalyst cocatalyst for photocatalytic hydrogen evolution with improve
173
to the co-catalyst directly along the basal plane of the MoS2, activity than the crystalline counterpart.
much reducing the transportation resistance. He et al.
synthesized MoS2 with good control on growth direction on
TiO2 for efficient photocatalytic hydrogen evolution as 5. Conclusion and Perspectives
166
presented in Fig. 9(a), for comparison MoS2 nanosheets MoS2 has aroused great interest since it was found
grow along basal plane is also fabricated. The obtained hybrids catalytically active towards both electrochemical and
of MoS2 nanosheets vertically aligned on TiO2 nanorods exhibit photocatalytic procedures. The chemical composition,
-1 -1
much improved hydrogen evolution activity (4300 mol h g structure, crystal size and surface chemistry have potential
at the load of 3 wt% MoS2) as compared with MoS2 grow along influence on both electrochemical and photocatalytic activity
its basal plane on TiO2 nanorods (see in Fig. 9(b), (c)). This of MoS2. Considering the aim to have a thorough
improved performance is due to the fast electrons understanding of MoS2, in this review article we have
transportation along the basal plane directly from the main summarized the morphological evolution of MoS2 and
catalysts as given in Fig. 9(d). discussed its different morphologies like quantum dots, 1D, 2D
Other than tuning the growth direction of MoS2 on the and 3D nanostructures and respective fabrication methods.
substrate to expose active edge sites, the phase condition of We have also outlined various strategies to improve the
MoS2 also influences the integrated performance extensively. performance of MoS2 towards electrochemical hydrogen and
As 1T metallic phase MoS2 exhibits much higher conductivity oxygen evolution, oxygen reduction, supercapacitors and
than 2H phase MoS2 which is typical semiconductor. photocatalytic hydrogen evolution, e.g. engineering the
Fabricating metallic phase MoS2 as co-catalyst is an surface chemistry via introducing defects within the MoS2
intriguingway to improve the photocatalytic hydrogen monolayers, doping of heteroatoms and formation of hybrid
generation rate. Bai et al. synthesized metallic MoS2 (1T phase) nanostructures with conductive materials like carbonaceous
nanosheets as support for photocatalytic water splitting with matrixes, inorganic structures, organic materials, etc. as well as
172
enhanced activity as compared with semiconducting MoS2. template guided growth of MoS2 to increase its surface area.
The enhanced conductivity of 1T MoS2 nanosheets provides MoS2 as the typical transition metal disulfides (TMDs)
high mobility and efficient transport of photoexcited electrons possess unique band gap, which gives it special properties that
thus resulted in much improved electron-hole separation make it suitable for electro and photo-chemical application.

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But one thing should be kept in mind that MoS2 still suffers 17. X. Geng, W. Sun, W. Wu, B. Chen, A. Al-Hilo, M. Benamara, H.
from inert nature of its basal plane that limits its activity Zhu, F. Watanabe, J. Cui and T. P. Chen, Nature communications,
2016, 7, 10672.
towards catalysis, efforts have been made to improve this 18. K. Chang, X. Hai and J. Ye, Advanced Energy Materials, 2016,
aspect, however, it still needs a long way to go. As existing 6, 1502555.
methods to tune electronic structure and surface chemistry 19. J. Wang, J. Liu, H. Yang, D. Chao, J. Yan, S. V. Savilov, J. Lin
modifications bring poor stability for MoS2, further and Z. X. Shen, Nano Energy, 2016, 20, 1-10.
advancements are still desirable on effective synthesis of 20. M. Acerce, D. Voiry and M. Chhowalla, Nature
Nanotechnology, 2015, 10, 313-318.
stable MoS2 with better chemical functionalization strategies 21. A. Ambrosi, Z. Sofer and M. Pumera, Small, 2015, 11, 605-
for advanced catalysts in energy conversion and storage 612.
Published on 03 October 2016. Downloaded by Cornell University Library on 05/10/2016 03:11:38.

devices. 22. R. Lv, J. A. Robinson, R. E. Schaak, D. Sun, Y. Sun, T. E.


Mallouk and M. Terrones, Accounts of chemical research, 2015,
48, 56-64.
Acknowledgements 23. E. P. Nguyen, B. J. Carey, T. Daeneke, J. Z. Ou, K. Latham, S.
Zhuiykov and K. Kalantar-zadeh, Chemistry of Materials, 2015,
The authors appreciate the support from the National Natural 27, 53-59.

Nanoscale Accepted Manuscript


Science Foundation of China (21676193, 21506156) and the 24. H. Li, J. Wu, Z. Yin and H. Zhang, Accounts of chemical
Tianjin Municipal Natural Science Foundation research, 2014, 47, 1067-1075.
25. G. Ye, Y. Gong, J. Lin, B. Li, Y. He, S. T. Pantelides, W. Zhou, R.
(15JCZDJC37300). Vajtai and P. M. Ajayan, Nano letters, 2016, 16, 1097-1103.
26. Q. Ji, Y. Zhang, Y. Zhang and Z. Liu, Chemical Society reviews,
2015, 44, 2587-2602.
Notes and references 27. M. R. Gao, J. X. Liang, Y. R. Zheng, Y. F. Xu, J. Jiang, Q. Gao, J.
Li and S. H. Yu, Nature communications, 2015, 6, 5982.
28. J.-Y. Liao, B. D. Luna and A. Manthiram, J. Mater. Chem. A,
1. F. Y. Cheng, J. Chen and X. L. Gou, Advanced materials, 2006, 2016, 4, 801-806.
18, 2561-2564. 29. L. Yang, D. Zhong, J. Zhang, Z. Yan, S. Ge, P. Du, J. Jiang, D.
Sun, X. Wu and Z. Fan, ACS nano, 2014, 8, 6979-6985.
2. Z.-F. Huang, J. Song, K. Li, M. Tahir, Y.-T. Wang, L. Pan, L. 30. H. Ji, C. Liu, T. Wang, J. Chen, Z. Mao, J. Zhao, W. Hou and G.
Wang, X. Zhang and J.-J. Zou, Journal of the American Chemical Yang, Small, 2015, 11, 6480-6490.
Society, 2016, 138, 1359-1365. 31. S. Su, M. Zou, H. Zhao, C. Yuan, Y. Xu, C. Zhang, L. Wang, C.
3. Z.-F. Huang, J. Song, L. Pan, Z. Wang, X. Zhang, J.-J. Zou, W. Fan and L. Wang, Nanoscale, 2015, 7, 19129-19135.
Mi, X. Zhang and L. Wang, Nano Energy, 2015, 12, 646-656. 32. H. Shi, R. Yan, S. Bertolazzi, J. Brivio, B. Gao, A. Kis, D. Jena, H.
4. L. Pan, T. Muhammad, L. Ma, Z.-F. Huang, S. Wang, L. Wang, G. Xing and L. Huang, ACS Nano, 2013, 7, 1072-1080.
J.-J. Zou and X. Zhang, Applied Catalysis B: Environmental, 2016, 33. S. Butun, S. Tongay and K. Aydin, Nano letters, 2015, 15,
189, 181-191. 2700-2704.
5. H. Li, Q. Zhang, C. C. R. Yap, B. K. Tay, T. H. T. Edwin, A. 34. Y. Yin, J. Han, Y. Zhang, X. Zhang, P. Xu, Q. Yuan, L. Samad, X.
Olivier and D. Baillargeat, Advanced Functional Materials, 2012, Wang, Y. Wang, Z. Zhang, P. Zhang, X. Cao, B. Song and S. Jin,
22, 1385-1390. Journal of the American Chemical Society, 2016, DOI:
6. T. Cheiwchanchamnangij and W. R. L. Lambrecht, Physical 10.1021/jacs.6b03714.
Review B, 2012, 85, 205302. 35. B. Guo, K. Yu, H. Li, H. Song, Y. Zhang, X. Lei, H. Fu, Y. Tan and
7. J. Zhang, S. Liu, H. Liang, R. Dong and X. Feng, Advanced Z. Zhu, ACS applied materials & interfaces, 2016, DOI:
materials, 2015, 27, 7426-7431. 10.1021/acsami.5b10252.
8. L. Yang, W. Zhou, J. Lu, D. Hou, Y. Ke, G. Li, Z. Tang, X. Kang 36. J. Xie, J. Zhang, S. Li, F. Grote, X. Zhang, H. Zhang, R. Wang, Y.
and S. Chen, Nano Energy, 2016, 22, 490-498. Lei, B. Pan and Y. Xie, Journal of the American Chemical Society,
9. T. F. Jaramillo, K. P. Jrgensen, J. Bonde, J. H. Nielsen, S. 2013, 135, 17881-17888.
Horch and I. Chorkendorff, Science, 2007, 317, 100-102. 37. Y.-H. Chang, C.-T. Lin, T.-Y. Chen, C.-L. Hsu, Y.-H. Lee, W.
10. B. Hinnemann, P. G. Moses, J. Bonde, K. P. Jrgensen, J. H. Zhang, K.-H. Wei and L.-J. Li, Advanced materials, 2013, 25, 756-
Nielsen, S. Horch, I. Chorkendorff and J. K. Nrskov, Journal of 760.
the American Chemical Society, 2005, 127, 5308-5309. 38. L. Tao, X. Duan, C. Wang, X. Duan and S. Wang, Chemical
11. D. Voiry, M. Salehi, R. Silva, T. Fujita, M. Chen, T. Asefa, V. B. Communications, 2015, 51, 7470-7473.
Shenoy, G. Eda and M. Chhowalla, Nano letters, 2013, 13, 6222- 39. W. Zhou, K. Zhou, D. Hou, X. Liu, G. Li, Y. Sang, H. Liu, L. Li
6227. and S. Chen, ACS applied materials & interfaces, 2014, 6, 21534-
12. L. Yuwen, F. Xu, B. Xue, Z. Luo, Q. Zhang, B. Bao, S. Su, L. 21540.
Weng, W. Huang and L. Wang, Nanoscale, 2014, 6, 5762-5769. 40. D. Gopalakrishnan, D. Damien, B. Li, H. Gullappalli, V. K. Pillai,
13. J. Chen, S.-L. Li, Q. Xu and K. Tanaka, Chemical P. M. Ajayan and M. M. Shaijumon, Chemical Communications,
Communications, 2002, DOI: 10.1039/b205109e, 1722-1723. 2015, 51, 6293-6296.
14. M. R. Gao, M. K. Chan and Y. Sun, Nature communications, 41. W. Qiao, S. Yan, X. Song, X. Zhang, Y. Sun, X. Chen, W. Zhong
2015, 6, 7493. and Y. Du, Rsc Advances, 2015, 5, 97696-97701.
15. J. Staszak-Jirkovsky, C. D. Malliakas, P. P. Lopes, N. Danilovic, 42. B. L. Li, L. X. Chen, H. L. Zou, J. L. Lei, H. Q. Luo and N. B. Li,
S. S. Kota, K. C. Chang, B. Genorio, D. Strmcnik, V. R. Nanoscale, 2014, 6, 9831-9838.
Stamenkovic, M. G. Kanatzidis and N. M. Markovic, Nature 43. D. Gopalakrishnan, D. Damien and M. M. Shaijumon, Acs
materials, 2016, 15, 197-203. Nano, 2014, 8, 5297-5303.
16. H. Wang, Z. Lu, S. Xu, D. Kong, J. J. Cha, G. Zheng, P. C. Hsu, K. 44. J.-Y. Wu, X.-Y. Zhang, X.-D. Ma, Y.-P. Qiu and T. Zhang, Rsc
Yan, D. Bradshaw, F. B. Prinz and Y. Cui, Proceedings of the Advances, 2015, 5, 95178-95182.
National Academy of Sciences of the United States of America, 45. F. Li, J. Li, Z. Cao, X. Lin, X. Li, Y. Fang, X. An, Y. Fu, J. Jin and R.
2013, 110, 19701-19706. Li, Journal of Materials Chemistry A, 2015, 3, 21772-21778.

This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 17

Please do not adjust margins


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not adjust margins Page 18 of 20
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DOI: 10.1039/C6NR06836G
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46. W. Dai, H. Dong, B. Fugetsu, Y. Cao, H. Lu, X. Ma and X. 78. X.-Y. Yu, Y. Feng, Y. Jeon, B. Guan, X. W. Lou and U. Paik,
Zhang, Small, 2015, 11, 4158-4164. Advanced materials, 2016, DOI: 10.1002/adma.201601188, n/a-
47. W. Gao, M. Wang, C. Ran and L. Li, Chemical n/a.
Communications, 2015, 51, 1709-1712. 79. L. Yu, J. F. Yang and X. W. Lou, Angewandte Chemie
48. W. Gu, Y. Yan, X. Cao, C. Zhang, C. Ding and Y. Xian, Journal International Edition, 2016, DOI: 10.1002/anie.201606776, n/a-
of Materials Chemistry B, 2016, 4, 27-31. n/a.
49. Y. Wang and Y. Ni, Analytical Chemistry, 2014, 86, 7463- 80. Y. M. Chen, Z. Li and X. W. Lou, Angewandte Chemie, 2015,
7470. 127, 10667-10670.
50. X. Ren, L. Pang, Y. Zhang, X. Ren, H. Fan and S. Liu, Journal of 81. Y. Nie, L. Li and Z. Wei, Chemical Society reviews, 2015, 44,
Materials Chemistry A, 2015, 3, 10693-10697. 2168-2201.
51. D. J. Li, U. N. Maiti, J. Lim, D. S. Choi, W. J. Lee, Y. Oh, G. Y. 82. T. Wang, D. Gao, J. Zhuo, Z. Zhu, P. Papakonstantinou, Y. Li
Published on 03 October 2016. Downloaded by Cornell University Library on 05/10/2016 03:11:38.

Lee and S. O. Kim, Nano letters, 2014, 14, 1228-1233. and M. Li, Chemistry-a European Journal, 2013, 19, 11939-
52. H. Wang, Z. Lu, D. Kong, J. Sun, T. M. Hymel and Y. Cui, ACS 11948.
Nano, 2014, 8, 4940-4947. 83. H. Huang, X. Feng, C. Du and W. Song, Chemical
53. Z. Wang, T. Chen, W. Chen, K. Chang, L. Ma, G. Huang, D. Communications, 2015, 51, 7903-7906.
Chen and J. Y. Lee, Journal of Materials Chemistry A, 2013, 1, 84. H. Huang, X. Feng, C. Du, S. Wu and W. Song, Journal of
2202-2210. Materials Chemistry A, 2015, 3, 16050-16056.

Nanoscale Accepted Manuscript


54. S. H. Choi, Y. N. Ko, J.-K. Lee and Y. C. Kang, Advanced 85. C. Du, H. Huang, X. Feng, S. Wu and W. Song, Journal of
Functional Materials, 2015, 25, 1780-1788. Materials Chemistry A, 2015, 3, 7616-7622.
55. W. Qin, T. Chen, L. Pan, L. Niu, B. Hu, D. Li, J. Li and Z. Sun, 86. R. Illathvalappil, S. M. Unni and S. Kurungot, Nanoscale,
Electrochimica Acta, 2015, 153, 55-61. 2015, 7, 16729-16736.
56. F. Li, L. Zhang, J. Li, X. Lin, X. Li, Y. Fang, J. Huang, W. Li, M. 87. J. Zhou, H. Xiao, B. Zhou, F. Huang, S. Zhou, W. Xiao and D.
Tian, J. Jin and R. Li, Journal of Power Sources, 2015, 292, 15-22. Wang, Applied Surface Science, 2015, 358, Part A, 152-158.
57. F. Meng, J. Li, S. K. Cushing, M. Zhi and N. Wu, Journal of the 88. K. Yuan, X. Zhuang, H. Fu, G. Brunklaus, M. Forster, Y. Chen,
American Chemical Society, 2013, 135, 10286-10289. X. Feng and U. Scherf, Angewandte Chemie International Edition,
58. C.-B. Ma, X. Qi, B. Chen, S. Bao, Z. Yin, X.-J. Wu, Z. Luo, J. Wei, 2016, 55, 6858-6863.
H.-L. Zhang and H. Zhang, Nanoscale, 2014, 6, 5624-5629. 89. K. Gopalakrishnan, K. Pramoda, U. Maitra, U. Mahima, M. A.
59. J. Liu, Z. Zeng, X. Cao, G. Lu, L.-H. Wang, Q.-L. Fan, W. Huang Shah and C. N. R. Rao, Nanomaterials and Energy, 2015, 4, 9-17.
and H. Zhang, Small, 2012, 8, 3517-3522. 90. C. Suresh, S. Mutyala and J. Mathiyarasu, Materials Letters,
60. H. Dong, S. Tang, Y. Hao, H. Yu, W. Dai, G. Zhao, Y. Cao, H. Lu, 2016, 164, 417-420.
X. Zhang and H. Ju, ACS applied materials & interfaces, 2016, 8, 91. K. Zhao, W. Gu, L. Zhao, C. Zhang, W. Peng and Y. Xian,
3107-3114. Electrochimica Acta, 2015, 169, 142-149.
61. R. M. Clark, B. J. Carey, T. Daeneke, P. Atkin, M. Bhaskaran, K. 92. T. Wang, J. Zhuo, Y. Chen, K. Du, P. Papakonstantinou, Z. Zhu,
Latham, I. S. Cole and K. Kalantar-zadeh, Nanoscale, 2015, 7, Y. Shao and M. Li, Chemcatchem, 2014, 6, 1877-1881.
16763-16772. 93. A. Y. S. Eng, A. Ambrosi, Z. Sofer, P. imek and M. Pumera,
62. S. Xu, D. Li and P. Wu, Advanced Functional Materials, 2015, ACS Nano, 2014, 8, 12185-12198.
25, 1127-1136. 94. A. B. Laursen, S. Kegnaes, S. Dahl and I. Chorkendorff, Energy
63. J. Wang, J. Liu, H. Yang, Z. Chen, J. Lin and Z. X. Shen, Journal & Environmental Science, 2012, 5, 5577-5591.
of Materials Chemistry A, 2016, 4, 7565-7572. 95. J. D. Benck, T. R. Hellstern, J. Kibsgaard, P. Chakthranont and
64. D. Kong, H. He, Q. Song, B. Wang, W. Lv, Q.-H. Yang and L. T. F. Jaramillo, ACS Catalysis, 2014, 4, 3957-3971.
Zhi, Energy & Environmental Science, 2014, 7, 3320-3325. 96. L. Yang, W. Zhou, D. Hou, K. Zhou, G. Li, Z. Tang, L. Li and S.
65. P. Qiu and C. Mao, ACS Nano, 2010, 4, 1573-1579. Chen, Nanoscale, 2015, 7, 5203-5208.
66. Z.-T. Shi, W. Kang, J. Xu, Y.-W. Sun, M. Jiang, T.-W. Ng, H.-T. 97. D. Voiry, R. Fullon, J. Yang, C. de Carvalho Castro e Silva, R.
Xue, D. Y. W. Yu, W. Zhang and C.-S. Lee, Nano Energy, 2016, 22, Kappera, I. Bozkurt, D. Kaplan, M. J. Lagos, P. E. Batson, G.
27-37. Gupta, A. D. Mohite, L. Dong, D. Er, V. B. Shenoy, T. Asefa and M.
67. J. Xie, H. Zhang, S. Li, R. Wang, X. Sun, M. Zhou, J. Zhou, X. W. Chhowalla, Nature materials, 2016, 15, 1003-1009.
Lou and Y. Xie, Advanced materials, 2013, 25, 5807-5813. 98. X. Sun, J. Dai, Y. Guo, C. Wu, F. Hu, J. Zhao, X. Zeng and Y. Xie,
68. X. Xie, T. Makaryan, M. Zhao, K. L. Van Aken, Y. Gogotsi and Nanoscale, 2014, 6, 8359-8367.
G. Wang, Advanced Energy Materials, 2016, 6, 1502161. 99. P. Chen, K. Xu, S. Tao, T. Zhou, Y. Tong, H. Ding, L. Zhang, W.
69. X.-Y. Yu, H. Hu, Y. Wang, H. Chen and X. W. Lou, Angewandte Chu, C. Wu and Y. Xie, Advanced materials, 2016, 28, 7527-7532.
Chemie-International Edition, 2015, 54, 7395-7398. 100. J. Feng, X. Sun, C. Wu, L. Peng, C. Lin, S. Hu, J. Yang and Y.
70. Z. Zhang, W. Li, M. F. Yuen, T.-W. Ng, Y. Tang, C.-S. Lee, X. Xie, Journal of the American Chemical Society, 2011, 133, 17832-
Chen and W. Zhang, Nano Energy, 2015, 18, 196-204. 17838.
71. H. Tang, K. Dou, C.-C. Kaun, Q. Kuang and S. Yang, Journal of 101. C. C. McCrory, S. Jung, I. M. Ferrer, S. M. Chatman, J. C.
Materials Chemistry A, 2014, 2, 360-364. Peters and T. F. Jaramillo, Journal of the American Chemical
72. J. Yang, D. Voiry, S. J. Ahn, D. Kang, A. Y. Kim, M. Chhowalla Society, 2015, 137, 4347-4357.
and H. S. Shin, Angewandte Chemie International Edition, 2013, 102. C. C. McCrory, S. Jung, J. C. Peters and T. F. Jaramillo,
52, 13751-13754. Journal of the American Chemical Society, 2013, 135, 16977-
73. S. Qin, W. Lei, D. Liu and Y. Chen, J. Mater. Chem. A, 2016, 4, 16987.
1440-1445. 103. S. Muralikrishna, K. Manjunath, D. Samrat, V. Reddy, T.
74. X. Zuo, K. Chang, J. Zhao, Z. Xie, H. Tang, B. Li and Z. Chang, J. Ramakrishnappa and D. H. Nagaraju, RSC Adv., 2015, 5, 89389-
Mater. Chem. A, 2016, 4, 51-58. 89396.
75. L. Yu, B. Y. Xia, X. Wang and X. W. Lou, Advanced materials, 104. M. A. Lukowski, A. S. Daniel, F. Meng, A. Forticaux, L. Li
2016, 28, 92-97. and S. Jin, Journal of the American Chemical Society, 2013, 135,
76. J. Kibsgaard, T. F. Jaramillo and F. Besenbacher, Nature 10274-10277.
chemistry, 2014, 6, 248-253. 105. J. Ding, Y. Zhou, Y. Li, S. Guo and X. Huang, Chemistry of
77. Y. Wang, L. Yu and X. W. Lou, Angewandte Chemie Materials, 2016, 28, 2074-2080.
International Edition, 2016, 55, 7423-7426.

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Journal Name ARTICLE

106. J. Kibsgaard, Z. Chen, B. N. Reinecke and T. F. Jaramillo, 134. P. J. Hall, M. Mirzaeian, S. I. Fletcher, F. B. Sillars, A. J.
Nature materials, 2012, 11, 963-969. Rennie, G. O. Shitta-Bey, G. Wilson, A. Cruden and R. Carter,
107. Y. Guo, X. Zhang, X. Zhang and T. You, Journal of Energy & Environmental Science, 2010, 3, 1238-1251.
Materials Chemistry A, 2015, 3, 15927-15934. 135. R. Thangappan, S. Kalaiselvam, A. Elayaperumal, R.
108. X. Dai, K. Du, Z. Li, M. Liu, Y. Ma, H. Sun, X. Zhang and Y. Jayavel, M. Arivanandhan, R. Karthikeyan and Y. Hayakawa,
Yang, ACS applied materials & interfaces, 2015, 7, 27242-27253. Dalton transactions, 2016, 45, 2637-2646.
109. Y. Li, H. Wang, L. Xie, Y. Liang, G. Hong and H. Dai, Journal 136. D. Pech, M. Brunet, H. Durou, P. Huang, V. Mochalin, Y.
of the American Chemical Society, 2011, 133, 7296-7299. Gogotsi, P.-L. Taberna and P. Simon, Nat Nano, 2010, 5, 651-654.
110. H. Gu, L. Zhang, Y. Huang, Y. Zhang, W. Fan and T. Liu, Rsc 137. J. W. Kim, V. Augustyn and B. Dunn, Advanced Energy
Advances, 2016, 6, 13757-13765. Materials, 2012, 2, 141-148.
111. X. Ren, X. Ren, L. Pang, Y. Zhang, Q. Ma, H. Fan and S. Liu, 138. X. Wang, J. Ding, S. Yao, X. Wu, Q. Feng, Z. Wang and B.
Published on 03 October 2016. Downloaded by Cornell University Library on 05/10/2016 03:11:38.

International Journal of Hydrogen Energy, 2016, 41, 916-923. Geng, Journal of Materials Chemistry A, 2014, 2, 15958-15963.
112. P. Li, Z. Yang, J. Shen, H. Nie, Q. Cai, L. Li, M. Ge, C. Gu, X. 139. M. Yang, S.-K. Hwang, J.-M. Jeong, Y. S. Huh and B. G.
a. Chen, K. Yang, L. Zhang, Y. Chen and S. Huang, ACS applied Choi, Synthetic Metals, 2015, 209, 528-533.
materials & interfaces, 2016, 8, 3543-3550. 140. E. G. da Silveira Firmiano, A. C. Rabelo, C. J. Dalmaschio,
113. J. Xu, J. Cui, C. Guo, Z. Zhao, R. Jiang, S. Xu, Z. Zhuang, Y. A. N. Pinheiro, E. C. Pereira, W. H. Schreiner and E. R. Leite,
Huang, L. Wang and Y. Li, Angewandte Chemie International Advanced Energy Materials, 2014, 4.

Nanoscale Accepted Manuscript


Edition, 2016, 55, 6502-6505. 141. J. M. Soon and K. P. Loh, Electrochemical and Solid-State
114. J. Zhang, T. Wang, D. Pohl, B. Rellinghaus, R. Dong, S. Liu, Letters, 2007, 10, A250-A254.
X. Zhuang and X. Feng, Angewandte Chemie, 2016, 55, 6702- 142. Y. Zhang, W. Sun, X. Rui, B. Li, H. T. Tan, G. Guo, S.
6707. Madhavi, Y. Zong and Q. Yan, Small, 2015, 11, 3694-3702.
115. M. Dinari, A. Nabiyan, A. A. Ensafi and M. Jafari-Asl, Rsc 143. K. Pandey, P. Yadav and I. Mukhopadhyay, Rsc Advances,
Advances, 2015, 5, 100996-101005. 2015, 5, 57943-57949.
116. Z. Huang, W. Luo, L. Ma, M. Yu, X. Ren, M. He, S. Polen, K. 144. A. Ramadoss, T. Kim, G.-S. Kim and S. J. Kim, New Journal
Click, B. Garrett and J. Lu, Angewandte Chemie, 2015, 127, of Chemistry, 2014, 38, 2379-2385.
15396-15400. 145. L. Wang, Y. Ma, M. Yang and Y. Qi, Rsc Advances, 2015, 5,
117. M. G. Walter, E. L. Warren, J. R. McKone, S. W. Boettcher, 89059-89065.
Q. Mi, E. A. Santori and N. S. Lewis, Chemical reviews, 2010, 110, 146. X. Li, X. Li, J. Cheng, D. Yuan, W. Ni, Q. Guan, L. Gao and
6446-6473. B. Wang, Nano Energy, 2016, 21, 228-237.
118. F. Cheng and J. Chen, Chemical Society reviews, 2012, 41, 147. L. Li, H. Yang, J. Yang, L. Zhang, J. Miao, Y. Zhang, C. Sun,
2172-2192. W. Huang, X. Dong and B. Liu, Journal of Materials Chemistry A,
119. I. C. Man, H.-Y. Su, F. Calle-Vallejo, H. A. Hansen, J. I. 2016, 4, 1319-1325.
Martnez, N. G. Inoglu, J. Kitchin, T. F. Jaramillo, J. K. Nrskov and 148. J. Zhu, W. Sun, D. Yang, Y. Zhang, H. H. Hoon, H. Zhang
J. Rossmeisl, ChemCatChem, 2011, 3, 1159-1165. and Q. Yan, Small, 2015, 11, 4123-4129.
120. Y. Jiao, Y. Zheng, M. Jaroniec and S. Z. Qiao, Chemical 149. L. Ren, G. Zhang, Z. Yan, L. Kang, H. Xu, F. Shi, Z. Lei and
Society reviews, 2015, 44, 2060-2086. Z.-H. Liu, ACS applied materials & interfaces, 2015, 7, 28294-
121. J. Zhang, S. Liu, H. Liang, R. Dong and X. Feng, Advanced 28302.
materials, 2015, 27, 7426-7431. 150. H. Tang, J. Wang, H. Yin, H. Zhao, D. Wang and Z. Tang,
122. J. Wang, W. Cui, Q. Liu, Z. Xing, A. M. Asiri and X. Sun, Advanced materials, 2015, 27, 1117-1123.
Advanced materials, 2016, 28, 215-230. 151. S. Patil, A. Harle, S. Sathaye and K. Patil, Crystengcomm,
123. W. Zhou, X.-J. Wu, X. Cao, X. Huang, C. Tan, J. Tian, H. Liu, 2014, 16, 10845-10855.
J. Wang and H. Zhang, Energy & Environmental Science, 2013, 6, 152. B. Hu, X. Qin, A. M. Asiri, K. A. Alamry, A. O. Al-Youbi and
2921-2924. X. Sun, Electrochimica Acta, 2013, 100, 24-28.
124. R. D. L. Smith, M. S. Prvot, R. D. Fagan, Z. Zhang, P. A. 153. K. Krishnamoorthy, G. K. Veerasubramani, S.
Sedach, M. K. J. Siu, S. Trudel and C. P. Berlinguette, Science, Radhakrishnan and S. J. Kim, Materials Research Bulletin, 2014,
2013, 340, 60-63. 50, 499-502.
125. M. Gao, W. Sheng, Z. Zhuang, Q. Fang, S. Gu, J. Jiang and 154. X. Zhou, B. Xu, Z. Lin, D. Shu and L. Ma, Journal of
Y. Yan, Journal of the American Chemical Society, 2014, 136, Nanoscience and Nanotechnology, 2014, 14, 7250-7254.
7077-7084. 155. L. Yuan, X.-H. Lu, X. Xiao, T. Zhai, J. Dai, F. Zhang, B. Hu, X.
126. M. W. Kanan, Y. Surendranath and D. G. Nocera, Wang, L. Gong, J. Chen, C. Hu, Y. Tong, J. Zhou and Z. L. Wang,
Chemical Society reviews, 2009, 38, 109-114. ACS Nano, 2012, 6, 656-661.
127. K. Yan and Y. Lu, Small, 2016, 12, 2975-2981. 156. G. Qu, J. Cheng, X. Li, D. Yuan, P. Chen, X. Chen, B. Wang
128. M. Winter and R. J. Brodd, Chemical reviews, 2004, 104, and H. Peng, Advanced materials, 2016, 28, 3646-3652.
4245-4270. 157. C. Hao, F. Wen, J. Xiang, L. Wang, H. Hou, Z. Su, W. Hu
129. Y. Zhu, S. Murali, M. D. Stoller, K. Ganesh, W. Cai, P. J. and Z. Liu, Advanced Functional Materials, 2014, 24, 6700-6707.
Ferreira, A. Pirkle, R. M. Wallace, K. A. Cychosz and M. 158. Y. Fang, B. Luo, Y. Jia, X. Li, B. Wang, Q. Song, F. Kang and
Thommes, Science, 2011, 332, 1537-1541. L. Zhi, Advanced materials, 2012, 24, 6348-6355.
130. J.-M. Tarascon and M. Armand, Nature, 2001, 414, 359- 159. J. Shen, J. Ji, P. Dong, R. Baines, Z. Zhang, P. M. Ajayan
367. and M. Ye, Journal of Materials Chemistry A, 2016, 4, 8844-8850.
131. N. Mahmood, C. Zhang, H. Yin and Y. Hou, Journal of 160. J. Shen, P. Dong, R. Baines, X. Xu, Z. Zhang, P. M. Ajayan
Materials Chemistry A, 2014, 2, 15-32. and M. Ye, Chemical Communications, 2016, 52, 9251-9254.
132. X. Yang, C. Cheng, Y. Wang, L. Qiu and D. Li, Science, 161. X. Chen, S. Shen, L. Guo and S. S. Mao, Chemical reviews,
2013, 341, 534-537. 2010, 110, 6503-6570.
133. V. Augustyn, J. Come, M. A. Lowe, J. W. Kim, P.-L. 162. R. M. Stolley and M. L. Helm, Nature chemistry, 2014, 6,
Taberna, S. H. Tolbert, H. D. Abrua, P. Simon and B. Dunn, 949-950.
Nature materials, 2013, 12, 518-522. 163. J. Yu and J. Ran, Energy & Environmental Science, 2011, 4,
1364-1371.

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Journal Name ARTICLE

164. MurdochM, G. I. N. Waterhouse, M. A. Nadeem, J. B.


Metson, M. A. Keane, R. F. Howe, LlorcaJ and IdrissH, Nature
chemistry, 2011, 3, 489-492.
165. J. Yang, H. Yan, X. Zong, F. Wen, M. Liu and C. Li,
Philosophical Transactions of the Royal Society a-Mathematical
Physical and Engineering Sciences, 2013, 371.
166. H. He, J. Lin, W. Fu, X. Wang, H. Wang, Q. Zeng, Q. Gu, Y.
Li, C. Yan, B. K. Tay, C. Xue, X. Hu, S. T. Pantelides, W. Zhou and Z.
Liu, Advanced Energy Materials, 2016, DOI:
10.1002/aenm.201600464.
167. Q. Xiang, J. Yu and M. Jaroniec, Journal of the American
Published on 03 October 2016. Downloaded by Cornell University Library on 05/10/2016 03:11:38.

Chemical Society, 2012, 134, 6575-6578.


168. J. Chen, X. J. Wu, L. Yin, B. Li, X. Hong, Z. Fan, B. Chen, C.
Xue and H. Zhang, Angewandte Chemie International Edition,
2015, 54, 1210-1214.
169. X. Zong, H. Yan, G. Wu, G. Ma, F. Wen, L. Wang and C. Li,
Journal of the American Chemical Society, 2008, 130, 7176-7177.

Nanoscale Accepted Manuscript


170. J. Li, G. Zhan, Y. Yu and L. Zhang, Nature communications,
2016, 7.
171. C. Liu, L. Wang, Y. Tang, S. Luo, Y. Liu, S. Zhang, Y. Zeng
and Y. Xu, Applied Catalysis B: Environmental, 2015, 164, 1-9.
172. S. Bai, L. Wang, X. Chen, J. Du and Y. Xiong, Nano
Research, 2015, 8, 175-183.
173. H. Yu, P. Xiao, P. Wang and J. Yu, Applied Catalysis B:
Environmental, 2016, 193, 217-225.

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