Research Article

www.acsami.org

2H → 1T Phase Change in Direct Synthesis of WS2 Nanosheets via

Solution-Based Electrochemical Exfoliation and Their Catalytic
Properties
Shi Xuan Leong,† Carmen C. Mayorga-Martinez,† Xinyi Chia,† Jan Luxa,‡ Zdeněk Sofer,‡
and Martin Pumera*,†
†
Division of Chemistry & Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University,
Singapore 637371, Singapore
‡
Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technicka 5, 166 28, Prague 6, Czech
Republic
*
S Supporting Information

ABSTRACT: Metallic 1T-WS2 has various interesting properties such as

increased density of catalytically active sites on both the basal planes and
edges as well as metallic conductivity which allows it to be used in
applications such as biosensing and energy devices. Hence, it is highly
beneficial to develop a simple, efficient, and low-cost synthesis method of 1T-
WS2 nanosheets from commercially available bulk 2H-WS2. In this study, we
reported WS2 nanosheets synthesized directly from bulk WS2 via solution-
based electrochemical exfoliation with bipolar electrodes and investigated
their electrocatalytic performances toward hydrogen evolution and oxygen
reduction reactions. We successfully synthesized WS2 nanosheets of regular
hexagonal symmetry with a 2H → 1T phase transition. This represents a
novel method of producing 1T-WS2 nanosheets from bulk 2H-WS2 without
compromising on its electrocatalytic properties.
KEYWORDS: 1T-phase, 2H-phase, transition metal dichalcogenides, downsized, bipolar electrochemistry

■ INTRODUCTION
Much research effort has been devoted toward enhancing
catalytic efficiency and stability of 2D transition metal
dichalcogenide (TMD) materials1−4 and fine-tuning their
properties to better tailor to different functions and
applications.5−7 The TMD material of interest to us is WS2,
which has demonstrated high catalytic ability. As such, WS2
nanosheets possess great potential in many applications,
including that of biosensing8−10 and energy devices.11,12
Commercial WS2 is usually available in bulk form,13−15 and
conventionally, many methods can be used for exfoliation and
size reduction of TMD. The more common methods include
vapor-phase synthesis, lithium intercalation, shear exfoliation,
solvothermal synthesis, and, more recently, sonication in
suitable solvent systems.16−28 Some of these methods, such
as Li intercalation, are capable of inducing phase transition from
2H natural phase, which is semiconducting for Group VI
TMDs, to 1T-phase, which is metallic and more catalytic.
In this study, we chose to employ a solution-based
electrochemical exfoliation with bipolar electrodes29−31 on
WS2 from different sources for downsizing of bulk WS2 to WS2
nanosheets and concurrent 2H → 1T phase transition. Bulk
WS2 from five different chemical providers was tested to test
consistency of the method. Exfoliation via this new bipolar
electrochemical method has various advantages including low
cost, high speed, and being comparatively straightforward.30,32
Furthermore, the bulk WS2 used as precursors can be prepared
in aqueous suspensions, making it compatible with potential
future applications we are interested in for our exfoliated WS2
nanosheets. In the solution-based electrochemical exfoliation
with bipolar electrodes, electrically conducting materials are
polarized in electric fields between two driving electrodes. This
leads to electrochemical polarization of the object at the two
extremities in the opposite polarity of the driving electrode
even in the absence of a direct ohmic contact.33
Previous research done on exfoliation and 2H → 1T phase
transitions focuses on producing nanoparticles from organo-
lithium exfoliated TMD materials, such as WS2 and MoSe2.30,32
In comparison, direct electrochemical synthesis of TMD
nanosheets from bulk TMD materials with no other pretreat-
ment poses an interesting and less complicated alternative
method if proven viable. With this consideration in mind, we
are interested in comparing the electrocatalytic abilities of 1T-
WS2 nanosheets prepared directly from bulk 2H-WS2.
Received: May 16, 2017
Accepted: July 7, 2017

© XXXX American Chemical Society A DOI: 10.1021/acsami.7b06898

ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces
■ RESULTS AND DISCUSSION
The materials from the providers investigated in this work will
be referred to as follows: WS2 from STREM (WS2 S), WS2
from Sigma-Aldrich (WS2 SA), WS2 from Alfa-Aesar (WS2 AA),
WS2 from Lower Friction (WS2 LF), and WS2 from Santa Cruz
Biotechnology (WS2 SC).
Preparation of WS2 nanosheets was achieved by applying
constant DC potentials of 10 V across two Pt driving electrodes
using bulk WS2 from different chemical providers. WS2 sheets
will fragment into thinner nanosheets due to induced potential
at the two poles of the particles by external electrical field.
Exfoliated WS2 samples were purified with dialysis prior to
characterization analyses (see Scheme 1).
Scheme 1. Schematization of the Solution-Based
Electrochemical Exfoliation Method
Characterization of electrochemically exfoliated nanosheets
indicates a 2H → 1T phase transition with the occurrence of
regularly shaped WS2 nanosheets after application of solution-
based electrochemical exfoliation with bipolar electrodes to the
bulk material. This is consistent throughout all five bulk WS2
materials tested which will be demonstrated below.
Characterization of synthesized nanosheets was performed
using UV−vis spectroscopy, transmission electron microscopy
(TEM), energy-dispersive spectroscopy (EDS), X-ray photo-
electron spectroscopy (XPS), and atomic force microscopy
(AFM), as well as dynamic light scattering (DLS). The
electrocatalytic ability of WS2 nanosheets toward oxygen
reduction reaction (ORR) and hydrogen evolution reaction
(HER) was investigated by linear sweep voltammetry.
Inspection by UV−vis spectroscopy suggests the successful
synthesis of WS2 nanosheets. The UV−vis spectra of bulk and
exfoliated WS2 solutions are shown in Figure S1 (Supporting
Information).
The size and composition of WS2 nanosheets were further
probed with TEM/EDS, as shown in Figure 1. After
electrochemical exfoliation, all the samples display the presence
of individual, thin-layer exfoliated sheets. The elemental
compositions of WS2 samples were confirmed using EDS.
High-resolution TEM characterization of the electrochemi-
cally exfoliated WS2 and the corresponding selective area
electron diffraction (SAED) shows the presence of WS2
nanosheets of sizes up to 1 μm (Figure 2). Regular hexagonal
symmetry of WS2 is also observed, as well as the presence of
hexagonal atomic arrangement typical of 1T-WS2-phase.
Further inspection by XPS (Figure 3) corroborated the
existence of exfoliated WS2 in its 1T-phase. Across all five
materials, W4f XPS reveals peaks in the range of 31.6−32.2 eV,
B DOI: 10.1021/acsami.7b06898
Research Article
Figure 1. (A−E) Transmission electron microscopy and energy-
dispersive spectroscopy analysis of WS2 nanosheets from different
suppliers (STREM (WS2 S), Sigma-Aldrich (WS2 SA), Alfa-Aesar
(WS2 AA), Lower Friction (WS2 LF), and Santa Cruz Biotechnology
(WS2 SC).
consistent with literature values of 1T-WS2.34−36 Further
deconvolution of the main W4+4f peak into component peaks
suggests a doublet at ∼31.5−31.9 eV and ∼32.3−32.6 eV,
corresponding to W4f(7/2) and W4f(5/2), respectively. Hence,
there is a strong indication that the metallic 1T polymorph is
the dominant phase in the synthesized nanosheets. Addition-
ally, the energy positions of the minor peaks (∼36.7−37.1 eV
and ∼38.5−39.3 eV) correspond to the W6+ state, in good
agreement with literature values as well.34−36 This shows that a
certain degree of oxidation to W6+ can be observed in all
samples, with the greatest extent in WS2 SA (Figure 3B) and
WS2 AA (Figure 3C).
The sizes of the synthesized nanosheets were measured by
DLS and the average values tabulated in Table 1, and the
particle size distribution curves were shown in the SI (see
Figure S2).
The thickness of the WS2 nanosheets was studied using
AFM. As seen from the height traces, the thickness ranges from
16 to 35 nm (Figure 4). Consistent height and size uniformities
were observed across all five materials.
The electrocatalytic ability of the various WS2 materials in
their bulk and exfoliated forms toward oxygen reduction
reaction (ORR) was evaluated using linear sweep voltammetry
in 0.1 M KOH supporting electrolyte at a low scan rate of 2 mV
s−1. Figure 5 shows the ORR polarization curves on WS2
catalysts from different chemical providers in their bulk and
electrochemically exfoliated forms.
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces Research Article

Figure 2. (A−E) Transmission electron microscopy (TEM) images

(left) of 1T-WS2 nanosheets from different suppliers (STREM (S),
Sigma-Aldrich (SA), Alfa-Aesar (AA), Lower Friction (LF), and Santa
Cruz Biotechnology (SC)). High-resolution TEM images (center) of
1T-WS2 show the dominant presence of metallic 1T-phase as observed Figure 3. (A−E) W 4f high-resolution XPS spectra of electrochemi-
by the hexagonal atomic arrangement typical of 1T-phase. Selective cally exfoliated WS2 nanosheets from different suppliers (S, SA, AA,
area electron diffraction (SAED) patterns (right). LF, and SC).

Table 1. Average Particle Size for Electrochemically

Based on Figure 5F, which summarizes the peak positions at
Exfoliated WS2 Nanosheets Measured by Dynamic Light
which ORR occurred, improvements in ORR electrocatalytic
Scattering
ability after solution-based electrochemical exfoliation of the
bulk WS2 from all five sources were observed, with the sample av size/nm
exception of WS2 AA. The slight improvement is encouraging WS2 S 342
since exfoliated WS2 nanosheets were used at low concen- WS2 SA 531
trations in small amounts in the experiment. Thus, this may WS2 AA 106
translate into more pronounced improvements if a larger WS2 LF 459
amount was used. WS2 SC 531
The hydrogen evolution electrocatalytic efficiency of the
various bulk and exfoliated WS2 materials was also investigated
using linear sweep voltammetry in 0.5 M H2SO4 supporting onset potential is defined as the potential corresponding to the
electrolyte at a low scan rate of 2 mV s−1. current density of −10 mA cm−2 in this case.
The HER performance indicators used are onset potentials As observed from Figure 6F, which summarizes the onset
and Tafel slope values. Figures 6 and 7 show respectively the potentials of the bulk and exfoliated WS2 materials, the onset
HER polarization curves and the Tafel slopes on WS2 catalysts potentials remain relatively consistent after exfoliation across all
from different chemical companies. The onset potential refers five WS2 materials. This suggests that electrochemical
to the potential at which the current density begins to fall exfoliation of bulk WS2 materials do not degrade the HER
steeply due to proton reduction. The Tafel slope is the increase electrocatalytic properties of WS2. Enhanced performance was
in overpotential required to result in a magnitude rise in current observed in the case of WS2 SA even.
density. Better HER performance is characterized by onset Figure 7F summarizes the Tafel slope values of the WS2
potentials smaller in magnitude and lower Tafel slopes. The materials. The two sets of results are in good agreement and
C DOI: 10.1021/acsami.7b06898
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces Research Article

Figure 4. (A−E) AFM images (3 × 3 μm2; left) of electrochemically exfoliated WS2 nanosheets from different suppliers (S, SA, AA, LF, and SC).
Three-dimensional topographic maps show WS2 nanosheets of generally consistent thickness (center). Height profiles taken along the black arrows
in the AFM images (right).

lead to the same conclusion that electrochemical exfoliation of

WS2 has not resulted in significant degradation of the HER
electrocatalytic properties of WS2. However, it is of note that
there were greater differences between the Tafel slope values
obtained for the bulk and exfoliated forms as compared to that
of the onset potentials.
Additionally, as seen from Figure 7F, Tafel slopes of 154−
190 mV/dec on electrodes coated with exfoliated WS2 materials
indicate hydrogen adsorption as the limiting step. The Volmer
adsorption step has a theoretical limiting value of 120 mV/dec
and is described as such:37
H3O+ + e− → Hads + H 2O
D DOI: 10.1021/acsami.7b06898
■ CONCLUSION
In conclusion, in this study, WS2 nanosheets were successfully
synthesized directly from bulk WS2 across different providers
using solution-based electrochemical exfoliation with bipolar
electrodes without any prior pretreatment. A 2H → 1T phase
transition, which was previously not observed in prior research,
was confirmed by XPS and TEM. It was also observed that the
synthesized WS2 nanosheets took on a regular hexagonal
symmetry. Electrocatalytic properties toward oxygen reduction
reaction (ORR) and hydrogen evolution reaction (HER) of
synthesized WS 2 nanosheets were also examined. We
determined that electrochemical exfoliation of bulk WS2 via
this new electrochemical method does not significantly degrade
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces
Figure 5. (A−E) ORR polarization curves on bulk and electrochemi-
cally exfoliated WS2 from different chemical providers. Potentials are
measured with reference to the Ag/AgCl electrode. Conditions: 0.1 M
KOH; scan rate, 2 mV s−1. (F) Peak positions of ORR. Measurements
done with bare GC and Pt/C electrodes were included as reference.
Error bars correspond to standard deviations based on triplicate
measurements.
Figure 6. (A−E) HER polarization curves on bulk and exfoliated WS2
from different chemical providers. Potentials measured are with
reference to the reversible hydrogen electrode (RHE). Conditions: 0.5
M H2SO4; scan rate, 2 mV s−1. (F) Onset potentials required for the
HER at −10 mA cm−2 current density. Error bars correspond to
standard deviations based on triplicate measurements. Bare glassy
carbon electrodes and platinum catalyst on carbon are also included
for comparison.
the HER electrocatalytic properties of WS2. Overall slight
enhancement was even observed in ORR electrocatalytic
properties. This is encouraging because this may represent an
efficient and straightforward method of exfoliating bulk WS2
such that these materials can be used in applications such as
biosensing that require particles in the nanoscale without
compromising on and even possibly enhancing its electro-
catalytic properties.
E DOI: 10.1021/acsami.7b06898
Research Article
Figure 7. (A−E) Tafel plots for the HER of bulk and exfoliated WS2
materials from different providers. Potentials recorded are with
reference to the Ag/AgCl reference electrode. (F) Tabulated values
for the Tafel slopes. Error bars correspond to standard deviations
based on triplicate measurements. Bare glassy carbon electrodes and
platinum catalyst on carbon are also included for comparison.
■
EXPERIMENTAL METHODS
Materials. Tungsten(IV) sulfides were obtained from STREM
(United States), Sigma-Aldrich (Singapore), Alfa-Aesar (Germany),
Lower Friction (Canada), and Santa Cruz Biotechnology (USA).
Sodium sulfate, concentrated sulfuric acid, potassium chloride,
potassium ferrocyanide, potassium ferricyanide, and 20 wt % platinum
on graphitized carbon (Pt/C) were obtained from Sigma-Aldrich
(Singapore). Glassy carbon (GC) electrodes and a platinum electrode
(Pt) purchased from CH Instruments (Austin, TX, USA) of 3 mm
diameters were used as working and auxiliary electrodes, respectively.
An Ag/AgCl (1 M KCl) electrode served as the reference. Ultrapure
Milli-Q water was used in the preparation of solutions.
Apparatus. UV−vis spectroscopy was conducted on a Thermo
Fisher Multiskan GO spectrophotometer, and data were processed
using the SkanIt software. The absorbance region was recorded from λ
= 200 to 800 nm.
Transmission electron microscopy (TEM) and SAED measure-
ments were conducted with an EFTEM Jeol 2200 FS microscope
(Jeol, Japan). EDS measurements were made using a X-MaxN 80 T
detector (Oxford Instruments) at 200 keV acceleration voltage. For
sample preparation, WS2 suspensions were drop casted on a TEM grid
(Cu; 200 mesh; Formvar/carbon) and dried for 12 h at 60 °C.
X-ray photoelectron spectroscopy (XPS) was performed using an X-
ray photoelectron Phoibos 100 spectrometer (SPECS, Germany),
equipped with a monochromatic Mg Kα X-ray radiation source. All
spectra were calibrated to the C 1s peak at 284.5 eV.
Dynamic light scattering measurements were taken of exfoliated
WS2 samples with a Zetasizer Nano ZS (Malvern Instruments, United
Kingdom) to conduct particle size analysis. All voltammetric
measurements were performed using an AutoLab PGSTAT 101
electrochemical analyzer (Eco Chemie, Utrecht, The Netherlands),
controlled with a NOVA version 1.8 software (Eco Chemie).
Atomic force microscopy (AFM) was performed on NaioAFM
microscope (Liestal, Switzerland). NaioAFM was fitted with an ACL-A
cantilever tip (AppNano, CSInstruments, France) with the following
dimensions: length, 225 μm; width, 43 μm; tip radius, 6 nm. The
cantilever spring constant is 48 N m−1. The NaioAFM microscope was
connected to a personal computer, and the analyses of the five samples
were performed on Nanosurf, Naio control software (version 3.8.0.8)
and Nanosurf, easyScan 2 control software. The AFM images were
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces
recorded in air and at room temperature when the microscope was
operated under dynamic force at vibration amplitude of 200 mV. An
AFM imaging size of 3 μm by 3 μm was acquired. The resonance
frequency of the AFM probe in air is about 190 kHz. Typical quality
factors are in a range Q = 50−500 in air. The AFM is mounted on an
airtable TS-150 (Herzan, California, USA) for all measurements.
Electrochemical Exfoliation of WS2. Exfoliation of WS2 was
conducted following a protocol previously used by our group.30
Aqueous dispersions of tungsten sulfide (WS2), from five different
providers, were prepared in ultrapure water at 5.0 mg mL −1
concentration and subject to first time sonication for 10 min to
obtain a well-dispersed suspension. The solutions were then diluted to
0.5 mg mL−1 using ultrapure water, and 0.5 M Na2SO4 was added. The
electrochemical exfoliation was carried out in an electrochemical cell at
room temperature. Two platinum electrodes were placed into the
solution, and a constant DC potential of 10 V was applied for 30 min
under constant stirring conditions. Subsequently, the suspensions were
left to settle for a minimum of 48 h, and the supernatant was collected.
Electrochemical measurements. Electrochemical analyses were
performed at room temperature. Prior to each electrochemical
measurement, the samples were sonicated for 30 s to ensure
homogeneous dispersions. Samples, in 3.0 μL aliquots were then
drop casted on GC electrodes and dried to yield a modified electrode
surface with 15 μg of the material of interest. GC electrode surfaces
were renewed prior to new measurements by polishing with 0.05 μm
alumina particle slurry on a polishing pad and thoroughly washed with
ultrapure water.
Hydrogen Evolution Reaction Studies on Bulk and Exfoliated
WS2. Hydrogen evolution reaction (HER) of the various WS2
materials was studied by linear sweep voltammetry in 0.5 M H2SO4
supporting electrolyte at a low scan rate of 2 mV s−1. The measured
potentials are adjusted for comparison against the reversible hydrogen
electrode (RHE) using the following equation: ERHE = EAg/Agcl +
0.059pH + E0Ag/AgCl where EAg/Agcl is the measured potential, the pH of
0.5 M H2SO4 electrolyte is zero, and E0Ag/AgCl is the standard potential
of Ag/AgCl in 1.0 M KCl at 298 K, which is +0.235 V.
Oxygen Reduction Reaction Studies on Bulk and Exfoliated WS2.
Oxygen reduction reaction of the various WS2 materials was studied by
linear sweep voltammetry in 0.1 M KOH supporting electrolyte at a
low scan rate of 2 mV s−1.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.7b06898.
UV−vis spectra and DLS distribution figures (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: pumera.research@gmail.com.
ORCID
Zdeněk Sofer: 0000-0002-1391-4448
Martin Pumera: 0000-0001-5846-2951
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
M.P. acknowledges a Tier 1 grant (01/13) from the Ministry of
Education, Singapore. Z.S. and J.L. were supported by the
Czech Science Foundation (GACR No. 17-11456S) and by
specific university research (MSMT No. 20-SVV/2017).
■
REFERENCES
(1) Gupta, A.; Sakthivel, T.; Seal, S. Recent Development in 2D
materials Beyond Graphene. Prog. Mater. Sci. 2015, 73, 44−126.
F DOI: 10.1021/acsami.7b06898
Research Article
(2) Wang, H.; Feng, H.; Li, J. Graphene and Graphene-like Layered
Transition Metal Dichalcogenides in Energy Conversion and Storage.
Small 2014, 10, 2165−2181.
(3) Huang, X.; Tan, C.; Yin, Z.; Zhang, H. 25th Anniversary Article:
Hybrid Nanostructures Based on Two-Dimensional Nanomaterials.
Adv. Mater. 2014, 26, 2185−2204.
(4) Komsa, H.-P.; Krasheninnikov, A. V. Two-Dimensional
Transition Metal Dichalcogenide Alloys: Stability and Electronic
Properties. J. Phys. Chem. Lett. 2012, 3, 3652−3656.
(5) Lu, Q.; Yu, Y.; Ma, Q.; Chen, B.; Zhang, H. 2D Transition-Metal-
Dichalcogenide-Nanosheet-Based Composites for Photocatalytic and
Electrocatalytic Hydrogen Evolution Reactions. Adv. Mater. 2016, 28,
1917−1933.
(6) Voiry, D.; Yang, J.; Chhowalla, M. Recent Strategies for
Improving the Catalytic Activity of 2D TMD Nanosheets Toward
the Hydrogen Evolution Reaction. Adv. Mater. 2016, 28, 6197−6206.
(7) Tan, C.; Zhang, H. Two-dimensional Transition Metal
Dichalcogenide Nanosheet-Based Composites. Chem. Soc. Rev. 2015,
44, 2713−2731.
(8) Yang, G.; Zhu, C.; Du, D.; Zhu, J.; Lin, Y. Graphene-like Two-
Dimensional Layered Nanomaterials: Applications in Biosensors and
Nanomedicine. Nanoscale 2015, 7, 14217−14231.
(9) Yuan, Y.; Li, R.; Liu, Z. Establishing Water-Soluble Layered WS2
Nanosheet as a Platform for Biosensing. Anal. Chem. 2014, 86, 3610−
3615.
(10) Pumera, M.; Loo, A. H. Layered Transition-metal Dichalcoge-
nides (MoS2 and WS2) for Sensing and Biosensing. TrAC, Trends Anal.
Chem. 2014, 61, 49−53.
(11) Ratha, S.; Rout, C. S. Supercapacitor Electrodes Based on
Layered Tungsten Disulfide-Reduced Graphene Oxide Hybrids
Synthesized by a Facile Hydrothermal Method. ACS Appl. Mater.
Interfaces 2013, 5, 11427−11433.
(12) Lei, T.; Chen, W.; Huang, J.; Yan, C.; Sun, H.; Wang, C.; Zhang,
W.; Li, Y.; Xiong, J. Multi-Functional Layered WS2 Nanosheets for
Enhancing the Performance of Lithium−Sulfur Batteries. Adv. Energy.
Mater. 2017, 7, 1601843.
(13) Lin, J.; Peng, Z.; Wang, G.; Zakhidov, D.; Larios, E.; Yacaman,
M. J.; Tour, J. M. Enhanced Electrocatalysis for Hydrogen Evolution
Reactions from WS2 Nanoribbons. Adv. Energy Mater. 2014, 4,
1301875.
(14) Wu, Z.; Fang, B.; Bonakdarpour, A.; Sun, A.; Wilkinson, D. P.;
Wang, D. WS2 Nanosheets as a Highly Efficient Electrocatalyst for
Hydrogen Evolution Reaction. Appl. Catal., B 2012, 125, 59−66.
(15) Cheng, L.; Huang, W.; Gong, Q.; Liu, C.; Liu, Z.; Li, Y.; Dai, H.
Ultrathin WS2 Nanoflakes as a High-Performance Electrocatalyst for
the Hydrogen Evolution Reaction. Angew. Chem., Int. Ed. 2014, 53,
7860−7863.
(16) Shi, Y.; Li, H.; Li, L.-J. Recent Advances in Controlled Synthesis
of Two-Dimensional Transition Metal Dichalcogenides via Vapour
Deposition Techniques. Chem. Soc. Rev. 2015, 44, 2744−2756.
(17) Li, H.; Wu, J.; Yin, Z.; Zhang, H. Preparation and Applications
of Mechanically Exfoliated Single-Layer and Multilayer MoS2 and
WSe2 Nanosheets. Acc. Chem. Res. 2014, 47, 1067−1075.
(18) Lv, R.; Robinson, J. A.; Schaak, R. E.; Sun, D.; Sun, Y.; Mallouk,
T. E.; Terrones, M. Transition Metal Dichalcogenides and Beyond:
Synthesis, Properties, and Applications of Single- and Few-Layer
Nanosheets. Acc. Chem. Res. 2015, 48, 56−64.
(19) Coleman, J. N.; Lotya, M.; O’Neill, A.; Bergin, S. D.; King, P. J.;
Khan, U.; Young, K.; Gaucher, A.; De, S.; Smith, R. J.; Shvets, I. V.;
Arora, S. K.; Stanton, G.; Kim, H.-Y.; Lee, K.; Kim, G. T.; Duesberg, G.
S.; Hallam, T.; Boland, J. J.; Wang, J. J.; Donegan, J. F.; Grunlan, J. C.;
Moriarty, G.; Shmeliov, A.; Nicholls, R. J.; Perkins, J. M.; Grieveson, E.
M.; Theuwissen, K.; McComb, D. W.; Nellist, P. D.; Nicolosi, V. Two-
Dimensional Nanosheets Produced by Liquid Exfoliation of Layered
Materials. Science 2011, 331, 568−571.
(20) O’Neill, A.; Khan, U.; Coleman, J. N. Preparation of High
Concentration Dispersions of Exfoliated MoS2 with Increased Flake
Size. Chem. Mater. 2012, 24, 2414−2421.
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces Research Article

(21) Aldakov, D.; Lefrancois, A.; Reiss, P. Ternary and Quaternary

Metal Chalcogenide Nanocrystals: Synthesis, Properties and Applica-
tions. J. Mater. Chem. C 2013, 1, 3756−3776.
(22) Huang, X.; Zeng, Z.; Zhang, H. Metal Dichalcogenide
Nanosheets: Preparation, Properties and Applications. Chem. Soc.
Rev. 2013, 42, 1934−1946.
(23) Nicolosi, V.; Chhowalla, M.; Kanatzidis, M. G.; Strano, M. S.;
Coleman, J. N. Liquid Exfoliation of Layered Materials. Science 2013,
340, 1226419.
(24) Zhang, H. Ultrathin Two-Dimensional Nanomaterials. ACS
Nano 2015, 9, 9451−9469.
(25) Reale, F.; Sharda, K.; Mattevi, C. From Bulk Crystals to
Atomically Thin Layers of Group VI-Transition Metal Dichalcoge-
nides Vapour Phase Synthesis. Appl. Mater. Today 2016, 3, 11−22.
(26) He, Z.; Que, W. Molybdenum Disulfide Nanomaterials:
Structures, Properties, Synthesis and Recent Progress on Hydrogen
Evolution Reaction. Appl. Mater. Today 2016, 3, 23−56.
(27) Li, S.; Wang, S.; Tang, D.-M.; Zhao, W.; Xu, H.; Chu, L.; Bando,
Y.; Golberg, D.; Eda, G. Halide-assisted Atmospheric Pressure Growth
of Large WSe2 and WS2 Monolayer Crystals. Appl. Mater. Today 2015,
1, 60−66.
(28) Varrla, E.; Backes, C.; Paton, K. R.; Harvey, A.; Gholamvand, Z.;
McCauley, J.; Coleman, J. N. Large-Scale Production of Size-
Controlled MoS2 Nanosheets by Shear Exfoliation. Chem. Mater.
2015, 27, 1129−1139.
(29) Mayorga-Martinez, C. C.; Mohamad Latiff, N.; Eng, A. Y. S.;
Sofer, Z.; Pumera, M. Black Phosphorus Nanoparticle Labels for
Immunoassays via Hydrogen Evolution Reaction Mediation. Anal.
Chem. 2016, 88, 10074−10079.
(30) Mayorga-Martinez, C. C.; Khezri, B.; Eng, A. Y. S.; Sofer, Z.;
Ulbrich, P.; Pumera, M. Bipolar Electrochemical Synthesis of WS2
Nanoparticles and Their Application in Magneto-Immunosandwich
Assay. Adv. Funct. Mater. 2016, 26, 4094−4098.
(31) Toh, R. J.; Mayorga-Martinez, C. C.; Sofer, Z.; Pumera, M.
MoSe2 Nanolabels for Electrochemical Immunoassays. Anal. Chem.
2016, 88, 12204−12209.
(32) Loget, G.; Roche, J.; Kuhn, A. True Bulk Synthesis of Janus
Objects by Bipolar Electrochemistry. Adv. Mater. 2012, 24, 5111−
5116.
(33) Fosdick, S. E.; Knust, K. N.; Scida, K.; Crooks, R. M. Bipolar
Electrochemistry. Angew. Chem., Int. Ed. 2013, 52, 10438−10456.
(34) Lin, L.; Xu, Y.; Zhang, S.; Ross, I. M.; Ong, A. C. M.; Allwood,
D. A. Fabrication of Luminescent Monolayered Tungsten Dichalco-
genides Quantum Dots with Giant Spin-Valley Coupling. ACS Nano
2013, 7, 8214−8223.
(35) Martin-Litas, I.; Vinatier, P.; Levasseur, A.; Dupin, J. C.;
Gonbeau, D.; Weill, F. Characterisation of R.F. Sputtered Tungsten
Disulfide and Oxysulfide Thin Films. Thin Solid Films 2002, 416, 1−9.
(36) Dartigeas, K.; Gonbeau, D.; Pfister-Guillouzo, G. Core and
Valence Spectra of TaS2 and WS2. Experimental and Theoretical
Studies. J. Chem. Soc., Faraday Trans. 1996, 92, 4561−4566.
(37) Li, Y.; Wang, H.; Xie, L.; Liang, Y.; Hong, G.; Dai, H. MoS2
Nanoparticles Grown on Graphene: An Advanced Catalyst for the
Hydrogen Evolution Reaction. J. Am. Chem. Soc. 2011, 133, 7296−
7299.

G DOI: 10.1021/acsami.7b06898
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX