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Angewandte

Chemie

DOI: 10.1002/anie.201307475

Electrocatalysis

Two-Dimensional Hybrid Nanosheets of Tungsten Disulfide and
Reduced Graphene Oxide as Catalysts for Enhanced Hydrogen
Evolution**
Jieun Yang, Damien Voiry, Seong Joon Ahn, Dongwoo Kang, Ah Young Kim,
Manish Chhowalla,* and Hyeon Suk Shin*
Monolayers of transition-metal dichlacogenides (TMDs)
have been recently receiving interest for both fundamental
and technological investigations. One key to the realization of
the potential of TMDs is the synthesis of high-quality
materials. One interesting TMD compound is WS2 in which
the electrical properties can be varied from metallic and
semiconducting by tuning the crystal structure and the
number of layers.[1] Conventionally mono- or few-layered
WS2 can be obtained by mechanical exfoliation or grown by
chemical vapor deposition (CVD), using precursors such as
WOCl4 and HS(CH2)2SH.[1a, 2] In addition, chemical methods
for large-scale synthesis of layered WS2 have been reported.
For example, WS2 nanosheets with lateral dimensions of
100 nm have been synthesized from one-dimensional (1D)
W18O49 with assistance of surfactants through a rolling-out
method.[3] Recently, a powder of WS2 nanosheets was
obtained by a two-step process that involves mixing WO3
and S by ball milling and heating the mixture and S powder to
600 8C in Ar.[4] A solid-state reaction with tungstic acid and
thiourea in N2 atmosphere at 773 K has also produced layered
WS2.[5]
The hydrothermal reaction is known to be a facile method
for large scale manufacturing of TMD nanosheets at relatively low temperature. The synthesis of MoS2 sheets has been
well studied using precursors such as sodium molybdate and
thioacetamide or thiourea as the S source.[6] Although
inorganic fullerene-like (IF) WS2 nanoparticles, 1D nano[*] J. Yang,[+] S. J. Ahn, D. Kang, A. Y. Kim, Prof. H. S. Shin
Interdisciplinary School of Green Energy and
Low Dimensional Carbon Materials Center
Ulsan National Institute of Science and Technology(UNIST)
UNIST-gil 50, Ulsan 689-798 (Republic of Korea)
E-mail: shin@unist.ac.kr
D. Voiry,[+] Prof. M. Chhowalla
Materials Science and Engineering Department
Rutgers University
607 Taylor Road, Piscataway, NJ (USA)
E-mail: manish1@rci.rutgers.edu
[+] These authors contributed equally to this work.
[**] This work was supported by the Basic Science Research Program
(2011-0013601) and a grant (grant number 2011-0031630) from the
Center for Advanced Soft Electronics under the Global Frontier
Research Program through the National Research Foundation
funded by the Ministry of Science, ICT and Future Planning, Korea.
We thank Prof. Sang Hoon Joo for helpful discussion.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201307475.

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2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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Angew. Chem. Int. Ed. 2013, 52, 1 – 5

tubes, or 1D rods have been obtained by the hydrothermal
method,[7, 8] synthesis of WS2 sheets by the hydrothermal
reaction has yet to be realized. The primary reason for this is
due to the fact that the WOx precursor required for the
formation of WS2 nanosheets does not occur in 2D form.
Instead WOx prefers to form 1D or zero-dimensional (0D)
nanostructures. Thus sulfurization of the WOx favors the
formation of 0D fullerene-like or 1D nanotube/nanorod like
WS2 nanostructures. This is in contrast to MoS2 nanosheets in
which the MoO3 precursor is a layered compound.[9, 10] The
absence of a facile WS2 nanosheet synthesis method has also
prevented the study of WS2/graphene hybrid structures,
despite their potentially useful applications. We therefore
develop a hydrothermal method for synthesis of WS2 nanosheets and then we integrate rGO nanosheets into the reactor
to fabricate novel WS2/rGO hybrids. We report detailed
structural analyses of the synthesized products and investigate
their potential catalysts for the hydrogen evolution reaction
(HER). The primary uniqueness of our work is the synthesis
of WS2 and rGO/WS2 nanosheets using a scalable hydrothermal method and their implementation as efficient catalysts for HER.
MoS2 nanostructures are promising electrocatalysts for H2
production.[11] The overpotential of MoS2 catalysts is 200– 
150 mV and Tafel slopes are in a range of 55–40 mV dec1
(millivolts per decade).[11–13] Recent results have suggested
that WS2 nanosheets could be interesting as HER electrocatalysts. An overpotential of 60 mV and a Tafel slope of
about 70 mV dec1 have been measured for WS2 sheets
synthesized by the ball-milling method[4] while values of 
150 mV and about 70 mV dec1 have been obtained for WS2
particles on carbon cloth.[12] Voiry et al. showed that both the
overpotential (100 mV) and Tafel slopes (60 mV dec1) can
be lowered by used WS2 nanosheet catalysts that contain
a high concentration of the metallic 1T phase.[14]
Herein, we report the synthesis of WS2 and WS2/rGO
nanosheets using an one-pot hydrothermal reaction process at
low temperature. We show that WS2 nanosheets are selectively fabricated using tungsten chloride and thioacetamide
precursors. We also show that WS2 nanosheets readily
hybridize with rGO nanosheets when GO is added in the
reaction vessel. This is one of the first reports on selective
synthesis of WS2 and WS2/rGO hybrid nanosheets by the
hydrothermal reaction. We further demonstrate that WS2/
rGO nanosheets exhibit good catalytic activity for hydrogen
evolution. Based on impedance measurements, the better
catalytic performance is attributed to enhanced charge trans-

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The scanning electron microscopy (SEM) images of WS2 and WS2/rGO hybrid nanosheets are shown in Figure 1. The rGO hydrogels consist 2 Ü Ü Scheme 1. (See Supporting Information for experimental details. 8] The WOx nanoparticles or 1D structures act as templates for the formation of WS2.[7] In a typical process. whereas no WS2 has been synthesized below 240 8C. a) As-prepared WS2/rGO hybrid nanosheets and b) the magnified image of the marked area in (a). TEM images of WS2/rGO hybrid nanosheets. c) Folded edges of WS2 sheets on rGO and d) the highresolution image of (c). The WS2 sheets on rGO were characterized by highresolution transmission electron microscopy (HR-TEM). The reaction process is supposed to be as shown in Scheme 1 and Equations (1) and (2). 1 – 5 .. 52. www. The WS2 nanosheets maintain their structure without any noticeable change after freeze-drying. The conversion of WOx to WS2 is not fully explained yet. which can be attributed to Figure 2. only WS2 sheets are synthesized.[15. Synthesis of WS2/rGO hybrid sheets by the hydrothermal reaction. the as-prepared WS2/rGO hybrid nanosheets were found to shrink after freeze-drying. The inset shows a magnified image of some folded edges of WS2 sheets. and f) freeze-dried WS2/rGO after annealing. The inset in (b) indicates the diffraction pattern of 2H-WS2. thioacetamide (TAA). tungstate precursors such as Na2WO4 or (NH4)10W12O41 react with acid to condense WOx nanoparticles or 1D nanostructures that are sulfurized to give WS2. SEM images of a) as-prepared WS2. Bilayer WS2 nanosheets could be identified in some areas in Figure 2 a. respectively. and graphene oxide (GO) to produce WS2/rGO hybrid sheets. 16] The hydrothermal method was carried out at 265 8C for 24 hrs using WCl6. Int.[7. Chem. Ed. Weinheim These are not the final page numbers! Angew. In this study.[16] C2 H5 NS þ 2 H2 O ! H2 S þ NH3 þ CH3 COOH ð1Þ WCl6 þ 3 H2 S ! WS2 þ 6 HCl þ S ð2Þ Here. d) as-prepared WS2/rGO. b) freeze-dried WS2. WCl6 and TAA produces WS2 on GO sheets and GO is reduced to rGO. Angewandte Communications fer kinetics due to the intimate contact between the catalytic WS2 nanosheets and the rGO support. we employ WCl6 as a precursor for W which has been used for vapor phase rection in CVD and not induced WOx.angewandte.  2013 Wiley-VCH Verlag GmbH & Co. H2S is released from TAA and reduce WCl6 to form WS2 by sulfurization. As-prepared WS2 and WS2/rGO hybrid nanosheets are shown in Figure 1 a and d. of flexible rGO nanosheets that are physically cross-linked. As-prepared WS2/rGO hybrid sheets are then freeze-dried and annealed at 300 8C to improve the crystallinity of the nanosheets. possibly due to removal of water adsorbed on rGO (Figure 1 e).[17] Further annealing of both types of nanosheets at 300 8C did not affect the morphology of the samples as shown in Figure 1 c and f.) In the absence of GO. The diffraction pattern unambiguously suggests that the WS2 is configured in the 2H phase. An image of the as-prepared WS2/rGO hybrid sample in Figure 2 a shows overlapping nanosheets. The microstructure shown in Figure 1 e is very similar to rGO hydrogels formed by hydrothermal reaction and freeze-drying of GO. 2013. Images of freeze-dried samples are shown in Figure 1 b and e. c) freeze-dried WS2 after annealing. KGaA. e) freezedried WS2/rGO.org Figure 1. Moire pattern and a selected-area electron diffraction (SAED) pattern from the indicated position are shown in Figure 2 b. Closer examination of the diffraction pattern shows two sets of hexagonal reflections from two overlapping layers. The hydrothermal synthesis of WS2 is known to be sensitive to temperature. During the hydrothermal reaction. 1D WS2 structures have been synthesized at 265 8C through WO3 intermediates. However.

respectively.angewandte. 2013.Angewandte Chemie Figure 3.62 nm. which corresponds to the d spacing of WS2.7 eV was observed only in the freeze-dired WS2/rGO sheets. which is much higher than that observed for freeze-dried WS2/rGO (7 mA cm2) and WS2 (5 mA cm2).5 and 34. The presence of pure WS2 nanosheets after annealing was also confirmed by HR-TEM imaging of the hexagonal phase (see Figure S2). the cathode current density was 23 mA cm2.28 for as-prepared WS2 and freezedried WS2 nanosheets. The (002) peak of rGO was absent from the XRD samples. Int. Ed. the peak at 35.[3. The lowand high-magnification TEM images of WS2/rGO hybrid sheets after annealing are shown in Figure 2 c and d.48 and were sharper.38. The folded region in Figure 2 c was selected for high-magnification observation of the edges (Figure 2 d). These peaks were broader than those of WS2/rGO after annealing. 19] Our results suggest that GO acts to facilitate the growth of WS2 nanosheets. and 58 mV dec1 for freeze-dried WS2/rGO after annealing.85 eV and at 161.[12] These peaks in the hybrid nanosheets were identical to those of pure WS2 with high crystallinity.[22] Our analyses suggest that it is possible to fabricate highquality WS2 and WS2/rGO hybrids by hydrothermal synthesis. The much lower Tafel slope value for freeze-dried WS2/rGO after annealing is due to the formation of an interconnected conducting network by the underlying rGO so that rapid electron transport from the electrode to the less-conducting WS2 can occur. indicate the presence of the hexagonal phase. At 300 mV. the peaks in the hybrid samples are slightly less sharp.28. We also determined the stoichiometry of WS2 from EDAX mapping and the W:S ratio was found to be 1:2. The overpotential of pure WS2 nanosheets was measured to be 350 mV vs. The crystallinity of WS2 in the hybrid nanosheets also improved after annealing. and D and G bands of rGO can be clearly seen. which may be attributed to the strong interactions between the functional groups on GO and precursors. we carried out EDAX mapping of the WS2/ rGO hybrid sheets at the location indicated in Figure 2 a (see Figure S1 in the Supporting Information).6 eV. consisting with lack of substantial stacking of these layers. KGaA.4 and 162. In case of as-prepared WS2/rGO hybrid nanosheets. To demonstrate their feasibility in technologically important applications. freeze-dried WS2/rGO hybrid nanosheets after annealing (blue curve). (See Figure S3) The low values of surface areas in the hybrid sheets may be attributed to intimate contacts of rGO and WS2 sheets. The representative Raman spectrum of WS2/ rGO hybrid nanosheets is shown in Figure 3 b. 6c. We have also measured the Braun–Emmet– Teller (BET) surface of the pure and hybrid nanosheets and found them to range from 10–20 m2 g1). For the freeze-dried WS2/rGO. we investigated the electrocatalytic HER properties of WS2/rGO hybrid nanosheets deposited on a glassy carbon electrode. doublet peaks for binding energy of W 4f7/2-5/2 appeared at 32.[21] Furthermore.2 and163. a) XRD patterns of freeze-dried WS2 after annealing (black curve). they disappeared after annealing. and freeze-dried WS2/rGO hybrid nanosheets (red curve). corresponding to (002).[5. For the WS2/rGO sheets after annealing. 1 – 5 is also consistent with JPCDS card number 084-1398 for pure hexagonal WS2. freeze-dried WS2/rGO hybrid nanosheets after annealing (blue curve). Characteristic peaks for WS2 at 350 cm1 and 415 cm1 corresponding to the E2g and A1g modes.[3] The WS2 nanosheets on rGO consist of 4 to 12 layers as indicated in Figure 2 d.3 eV. 58.org Ü Ü a rotation angle of 25. b) Raman spectrum of the hybrid. We could not observe any edges of rGO sheets consistent with their atomically thin nature. The Tafel plots derived from these data are shown in Figure 4 b where the linear portions were fitted to the Tafel equation to determine the slopes. 52. 20] W 4f7/2-5/2 and S 2p3/2-1/2 binding energies obtained from Xray photoelectron spectroscopy (XPS) are shown in Figure 3 c and d. and freeze-dried WS2/rGO hybrid nanosheets (red curve). (100). the doublet peaks for the binding energy of W 4f7/2-5/2 and S 2p3/2-1/2 appear at 31. 5] Although some impurity peaks including those of WO2 were observed. The peaks for WS2 nanosheets after annealing appeared at 14. and the doublet peaks for S 2p1/2-3/2 appeared at 162. X-ray diffraction (XRD) spectra of WS2 and WS2/rGO hybrid nanosheets are shown in Figure 3 a and Figure S4.[18] The impurities may be from oxidation of WS2.1 degrees from the bilayers.[13b. some impurity peaks were present along with slight shifts of peak positions and broadening. Thd d-spacing of 0. There was a shift of about 1 eV which can be attributed to adsorption of oxygen and water molecules. and 58. The inset in Figure 2 d clearly indicates the interlayer spacing of WS2 is 0. XPS analysis of c) W 4f7/2-5/2 peaks and d) S 2p3/2-1/2 for the freeze-dried WS2 nanosheets after annealing (black curve). 338. The reflections at 14. However. Weinheim 3 www. consistent with the TEM result. The Tafel plots reveal a slope of 140 mV dec1 for annealed WS2. suggesting improved crystallinity.4 eV.18. and (110) planes. The XRD pattern These are not the final page numbers! . To confirm the existence of rGO. respectively. suggesting that the presence of rGO induces small disorder in the WS2 structure. indicating an oxidation state of W4+ (Figure 3 c). The polarization curves (I–V plot) from electrodes made from freeze-dried WS2/rGO and freeze-dried WS2/rGO after annealing yielded overpotentials ranging from 150–200 mV versus reversible hydrogen electrode (RHE).[13b]  2013 Wiley-VCH Verlag GmbH & Co. Angew.62 nm.67 and 33. was calculated from the primary (002) diffraction peak. indicating S2 (Figure 3 d). RHE. 33. indicating existence of rGO. 100 mV dec1 for freeze-dried WS2/rGO. Chem. Considerable carbon and oxygen elements were detected. which may be due to WO2.

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thioacetamide. 1 – 5 Composite materials: Tungsten disulfide and WS2/reduced graphene oxide (WS2/ rGO) nanosheets were fabricated by hydrothermal synthesis using tungsten chloride. Voiry. S.org Ü Ü Electrocatalysis These are not the final page numbers! .Angewandte Chemie Communications J. The WS2/rGO hybrid nanosheets show much better electrocatalytic activity for the hydrogen evolution reaction (see picture) than WS2 nanosheets alone. 52. Weinheim 5 www. KGaA. D. Ahn.* H. Chem. Kim. Yang. A. Y. J. D. Chhowalla.angewandte. Int.  2013 Wiley-VCH Verlag GmbH & Co. Shin* &&&&—&&&& Two-Dimensional Hybrid Nanosheets of Tungsten Disulfide and Reduced Graphene Oxide as Catalysts for Enhanced Hydrogen Evolution Angew. The WS2 nanosheets are efficiently templated on the rGO layer. Kang. M. Ed. and graphene oxide (GO) as starting materials. 2013. S.