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Nanoscale
REVIEW
Published on 03 October 2016. Downloaded by Cornell University Library on 05/10/2016 03:11:38.
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.
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1
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
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 2
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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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
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 4
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
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
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 5
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
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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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
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 7
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
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 8
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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10. MoS2/porous silica Flower-like nanostructure -0.14V vs. Ag/AgCl 0.1M KOH 90
91
13. Pt/C -0.07V vs. SCE 0.1M KOH
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 9
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
+ -
Heyrovsky step H + Had+e H2
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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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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
nanosheets
4 Defected MoS2 Nanosheets -120 180 50 0.5 M H2SO4 67
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
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
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
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 11
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
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
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
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 12
-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 *
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
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 13
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
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 14
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
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 15
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.
This journal is The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 16
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