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Energy, Environmental, and Catalysis Applications

Design of MoS2/Graphene Van der Waals Heterostructure
as Highly Efficient and Stable Electrocatalyst for
Hydrogen Evolution in Acidic and Alkaline Media
Xianbo Yu, Guangyu Zhao, Shan Gong, Chao Liu, Canlong
Wu, Pengbo Lyu, Guillaume Maurin, and Naiqing Zhang
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.0c04838 • Publication Date (Web): 11 May 2020
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Page 1 of 26 ACS Applied Materials & Interfaces
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Design of MoS2/Graphene Van der Waals
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Heterostructure as Highly Efficient and Stable
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Electrocatalyst for Hydrogen Evolution in Acidic
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20 and Alkaline Media
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25 Xianbo Yu,† Guangyu Zhao,*,‡ Shan Gong,† Chao Liu,† Canlong Wu,† Pengbo Lyu,*,§ Guillaume
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27 Maurin,§ and Naiqing Zhang*,‡
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30 † School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin,
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33 Heilongjiang, 150001, China
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36 ‡ Interdisciplinary Science Research Center, Harbin Institute of Technology, Harbin,
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38 Heilongjiang, 150001, China
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§ Institut Charles Gerhardt Montpellier, UMR 5253 CNRS, Université de Montpellier,
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44 Montpellier, 34095, France
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KEYWORDS: Molybdenum disulfide, van der Waals heterostructure, Gibbs free energy,
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53 hydrogen evolution reaction, electrocatalyst
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60 ACS Paragon Plus Environment
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ACS Applied Materials & Interfaces Page 2 of 26
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3 ABSTRACT: Thermodynamic stable phase of molybdenum disulfide (MoS2) is evaluated as a
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6 promising and durable nonprecious-metal electrocatalyst toward the hydrogen evolution reaction
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8 (HER), however, its actual catalytic activity is restricted by the inert basal plane, low electronic
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10 conductivity, low density and using efficiency of edged atoms. Moreover, 2D/2D van der Waals
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(vdws) heterostructures (HS) with face-to-face contact can construct a highly coupled interface
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15 and are demonstrated to have immense potential for catalytic applications. In the present work, a
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17 2D/2D hetero-layered architecture of electrocatalyst, based on the alternately arrangement of ultra-
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small monolayer MoS2 nanosheets (approximately 5−10 nm) and ultrathin graphene (G) sheets is
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22 prepared with a facilely chemical process, which is named as MoS2/G HS. The unique structural
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24 characteristic of MoS2/G HS is in favor of accommodating more active sites as the centers of
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26 ad/desorption hydrogen, transferring and separating the charges at coupled interface to improve
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29 the electronic conductivity and durability. The density functional theory calculation results further
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31 confirm that the alternately arranged G layers and MoS2 monolayers, as well as the expanded
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33 interplanar distance of 1.104 nm for MoS2/G HS can exhibit a superior HER performance in both
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0.5 M H2SO4 and 1.0 M KOH.
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1. INTRODUCTION
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43 The hydrogen production via photo/electro-chemical water splitting are considered as efficient
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45 approaches to generate high energy density clean fuels and eliminate transportation costs caused
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from large-scale, centralized steam reforming.1−5 However, the sluggish kinetics or inferior
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50 stability of the HER for overwhelming majority electrocatalysts, as well as the high cost of noble
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52 metals, such as Pt and Pt derivatives, substantially hinder the large-scale application. Therefore, it
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54 is eager to exploit high-efficiency, long-term stability and inexpensive catalysts toward HER.
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3 Recently, Molybdenum disulfide (MoS2), as a typical two-dimensional layered material,
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6 constituted by the stacking S−Mo−S layers through weak van der Waals (vdws) forces, has been
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8 confirmed as a superior HER catalyst with thermoneutral hydrogen adsorption free energy,
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10 enhanced high corrosion resistance and stability in acidic media.6−27 However, the intrinsic 2H-
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MoS2 exhibits a trigonal prismatic structure and stable 2H phase with two main issues: lesser active
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15 sites on the edges and lower electron conductivity, which limit the catalytic activities for HER.
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17 For pristine 2H-MoS2, the HER catalytic activity is linearly proportional to the amount of edge
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atom active sites, but the lower conversion efficiency caused from only 25% edge atoms are
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22 covered by H2.7,12 In addition, the catalytic activity sites are distributed in the edge of MoS2 rather
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24 than the bottom, and more unsaturated marginal atoms need to be served as the active sites in
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26 MoS2.6−12 Therefore, in theory, synthesizing ultra-small size or single-layered MoS2 is an effective
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29 method to expose more edge active sites and enhance the catalytic performances.9 Moreover, about
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31 the active sites, the conventional strategies are increasing the edge atoms concentration of 2H-
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33 MoS2 or fine-tuning the sulfur vacancies, such as preparation amorphous phase,13−14 controlling
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the morphology (nanowire, dendrites, porous),3,15−17 and incorporating transition metal or
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38 nonmetal heteroatoms (Co, Ru, Mn, Ni, O, P).18−22 Despite striking achievements, many practical
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40 challenges still remain. Recently, the researchers adopted one novel strategy to expand the
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interlayer spacing of MoS2 to tune and modify the edge-terminated structure, and then calculate
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45 the influence of the electron structure induced by the expanded interlayer spacing through the
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47 density functional theory calculation (DFT).7,23 As a result, the expanded interlayer spacing of
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49 MoS2 can accommodate more active edge sites, and exhibit striking kinetic ability to heighten
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52 HER catalytic activity. For example, Gao et al. synthesized the edge-terminated and interlayer-
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54 enlarged (9.4 Å) features of MoS2 catalyst. Compared with the non-expanded MoS2, the expanded
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3 interlayer spacing can influence the electronic structure, which can be proved by the density of
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6 states (DOS). The shifted d band of −0.1 eV towards the Fermi level can strengthen the hydrogen
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8 adsorption and offer an increased hydrogen coverage on the edge sites.7 Beside the increased edges
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10 active sites for MoS2, improving the electrical conductivity is another effective way to enhance the
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HER catalytic activities, such as phase conversion reaction (from 2H-MoS2 to 1T-MoS2 or 1T’-
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15 MoS2),6,11,20−22 coating or loading heterostructure with highly conductive materials (graphene,
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17 carbon nanotube, porous carbon),6,24−25 and supported by highly conductive substrate (carbon fiber
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cloth, nickel foam).14,26−27 Thereinto, heterojunctions, especial the 2D/2D vdws heterojunctions,
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22 are proved to be indeed in favor of enhancing the HER catalytic activities by transferring and
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24 separating the charges at a highly coupled interface with strong electronic interactions, low
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26 interfacial resistance, and the abundance of exposed edges and defects.11,24,28−34 Theoretical
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29 prediction indicates that this heterojunctions structure can induce heterointerfacial charge transfer
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31 and enhance the thermodynamic stability, leading to the optimized Gibbs free energy of hydrogen
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33 adsorption (ΔGH*).11 However, due to the complicated and incommensurate synthetic method, the
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related experiments of 2D/2D vdw heterojunctions reports for HER are rare.
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38 Herein, self-assembly method via electrostatic attraction is executed to synthesize the intimate
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40 face-to-face contact of hetero-layered architectures, comprising polygonal ultras-mall MoS2
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nanosheets (approximatively 5−10 nm) and monolayer graphene layers (MoS2/G). The strong
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45 interaction at the interface of MoS2 and graphene, as well as the expanded interplanar distance of
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47 1.104 nm can not only ensure the as-synthesized MoS2/G HS possess an abundance of exposed
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49 edges and defects with catalytic active sites, but also boost its electronic conductivity with a short
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52 transport path for mass transfer and the wettability with the electrolyte. As a result, the MoS2/G
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54 HS exhibits an enhancement of HER catalytic activities with the overpotentials (η) at the current
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3 density j = 10 mA cm−2 and the Tafel slope are only 180 and 183 mV, 79 and 127 mV dec−1 in
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6 both 0.5 M H2SO4 and 1.0 M KOH solutions, respectively, superior to most HER catalysts reported
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8 previously. Moreover, the MoS2/G HS catalyst for HER exhibits outstanding long-term durability
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10 even being operated continuously at the current density of 20 mA cm−2 over 30 and 45 hours with
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a negligible current loss in both acidic and alkaline electrolytes, indicating the promising
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15 application in commercial electrolyzer.
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17 2. RESULTS AND DISCUSSION
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21 As illustrated in Scheme 1, the fabrication of MoS2/G HS involved three procedures and the
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23 details are described in Supporting Information. Firstly, positively charge
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25 polyethyleneimine/Graphene oxide (PEI/GO) was obtained by modifying the surface of GO with
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28 PEI, because an abundance of amine groups from PEI could combine with the negatively charged
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30 oxygenated functional groups (such as hydroxyl, carboxyl) on GO. Secondly, the MoS42− anions
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32 ionized from (NH4)2MoS4 were introduced and could easily combine and self-assemble with the
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amine groups in PEI/GO to form MoS42−/PEI/GO layers by electrostatic attraction. Thirdly, the
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37 MoS42−/PEI/GO layers were thermally treated in an electric furnace under H2/Ar flow at 450oC for
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39 2 h and then 750oC for another 2 h to remove the redundant PEI, convert the MoS42− anions to
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41 MoS2 and reduce the GO layers to G, and the final catalyst of MoS2/G HS with alternately stacked
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44 architecture were synthesized. The X-ray diffraction (XRD) pattern of MoS2/G HS catalysts
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46 ranged from 5 to 80o in Figure 1a shows that the diffraction peaks at 32.68o, 39.54o, 44.15o, 58.33o,
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48 and 60.14o, ascribed to the (100), (103), (006), (110), and (008) planes, are well matched with
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51 standard of hexagonal MoS2 (JCPDS card No. 37−1492). Noteworthily, another two obvious
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53 diffraction peaks in low-angle region at 7.99o and 16.98o, corresponding to the spacings of 11.04
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55 and 5.2 Å, belong to the expanded interplanar distance of MoS2 and the distance between G and
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3 MoS2 monolayers, respectively. Moreover, the approximate diploid relation of interplanar distance
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6 demonstrate that, during the self-assembly process via electrostatic attraction, the layer-by-layered
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8 architectures between monolayer MoS2 and G alternately arrangement results in an interlayer
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10 spacing expansion of MoS2 by the interlaminar G monolayer.
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37 Scheme 1. Illustration of the synthesis of MoS2/G HS.
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40 Moreover, to uncover the effects of heterostructure of MoS2/G HS on the catalytic activity,
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42 another three samples, pure MoS2 micron particles (MoS2 MP), pure G, and mechanical mixture
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44 of MoS2 MP and G (MoS2/G MM), were also prepared and the synthesis processes were shown in
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47 Supporting Information. As shown in Figure 1a, all shark peaks of MoS2 MP are well assigned to
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49 normal 2H phase MoS2 (JCPDS card No. 37−1492), indicating the high crystalline purity. The
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51 structural models in Figure 1c-d directly show the corresponding distances of crystal plane varying
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54 from the 0.615 nm of pristine MoS2 MP to 1.104 nm of MoS2/G HS. Figure 1b shows the Raman
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56 spectrums of MoS2 MP with the typical feature peaks at 380.1 and 406.2 cm−1, corresponding to
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3 the E12g and A1g, respectively. For the MoS2/G HS in Figure 1b, the shifts of 4.9 cm−1 for A1g
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6 modes further confirm the diminished interlayer vdws force resulting from the expanded interlayer
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8 spacing of MoS2. In addition, the relatively low-intensity and broad peak width of the E12g and A1g
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10 modes in MoS2/G HS indicate the existing of more defects in MoS2 structures, which are in favor
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of HER catalytic activities (Figure 1b).35,36 Moreover, monolayer MoS2 is proved to accommodate
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15 more active sites and the Δk value (the peak separation between E12g and A1g modes) in Figure 1b
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17 is 21.3 cm−1 for MoS2/G HS, close to monolayer MoS2 (20.2−21.2 cm−1), suggesting the existence
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of single layer-like MoS2 in this heterostructure.37,38 Furthermore, the typical D and G bands are
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22 also detected at 1350.1 and 1590.9 cm−1 (Figure 1b). X-ray photoelectron spectra (XPS)
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24 measurement is performed to explore the valence states of MoS2/G HS. As shown in Figure S1a,
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26 the peaks located at 232.8 and 229.7 eV, assigned to the Mo 3d3/2 and 3d5/2, are the typical 2H
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29 phase MoS2 for MoS2/G HS.28,39 In addition, the high-resolution XPS spectra of S 2p core level
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31 (Figure S1b) for MoS2/G HS, the peaks at 162.6 and 163.8 eV are attributed to the binding energy
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33 of S 2p3/2 and S 2p1/2 region, respectively.28,39
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The crystal structures and morphologies of the MoS2/G HS and MoS2 MP were surveyed by the
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38 scanning electron microscope (SEM) and transmission electron microscope (TEM) measurements.
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40 The SEM image of MoS2/G HS in Figure 2a exhibits wrinkled sheet-like shape, similar to the
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characteristics of the pristine G sheets. In addition, there are no obvious nanosheets or particles
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45 anchored on the G, suggesting that the ultrathin MoS2 sheets and unique hetero-layered
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47 architectures features of MoS2/G HS (Figure 2a). TEM image in Figure S2a indicates that the every
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49 MoS2/G HS sheet is transparent to the electron beam, and abundant weeny nanosheets cover
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52 uniformly on the G sheets. Figure 2b shows that the polygon/irregular MoS2 nanosheets lie on the
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54 G sheets rather than stand vertically, indicating the electrostatic attraction from the opposite
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3 charges can lead to a strong vdws interfacial interaction and a tight face-to-face contact between
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6 MoS2 nanosheets and G layers. The TEM and high-resolution TEM (HRTEM) images indicate
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8 that the MoS2 sheets are high purity and crystallinity with the size of 5−10 nm (Figure 2c-d). The
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10 number of expanded interlayer spacing of MoS2 are marked by the yellow circles, indicating the
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MoS2 in MoS2/G HS is closed to less layers, which is consistent to the result of Raman
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15 measurement. Less layered MoS2 sheet is considered possessing more edge atoms, exposing more
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17 active sites and crystal defects, which are beneficial to HER performance. Previous report pointed
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that H2 annealing can enable good control of the defect formation while being scalable.8 When the
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22 MoS2 are annealed at > 600oC under H2 atmosphere, the large numbers of sulfur atoms strip from
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24 the MoS2 basal plane resulting in the formation of undercoordinated Mo regions and abundant
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26 sulfur vacancies.8 Accordingly, under the treated temperature of 750oC, the MoS2/G HS can
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29 generate more vacancies and active sites, which is beneficial to improve the HER catalytic
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31 activities. Moreover, the interplanar distances of MoS2/G HS lattice fringes are 0.271 and 1.104
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33 nm, corresponding to the normal planes (100) and the enlarged distance of crystal plane,
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respectively (Figure 2d). The expanded interlayer spacing can affect the electronic structure, which
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38 can boost the ability of hydrogen adsorption and increase the hydrogen coverage on the edge sites,
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40 thereby improving the HER catalytic performance of MoS2/G HS.7,23 As shown in Figure 2d, the
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clear lattice fringes of MoS2 (red lines) and G layers (blue lines) are alternately arranged, further
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45 confirming that the heterostructure of MoS2/G HS is successfully synthesized by a simple
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47 electrostatic attraction induced self-assembly method. For MoS2 MP, as shown in Figure S2b-c,
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49 the inferior morphology is completely different from the MoS2/G HS with a mass of uniformly
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52 fluffy lumpy aggregations observed, further confirming that the opposite charges between
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54 modified G and MoS42− can guide the growth orientation of MoS2 in MoS2/G HS. In order to
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3 survey the elemental composition of MoS2/G HS, energy dispersive X-ray spectrometry (EDX)
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6 mapping analysis (Figure S3) unambiguously confirms the uniform distributions of C, Mo, and S
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8 elements in local region of MoS2/G HS. In addition, EDX measurement are carried out to measure
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10 the existence of Mo and S in MoS2/G HS and the calculated atomic ratio of Mo/S is 1:1.75. (Figure
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S4a). Furthermore, the thermogravimetric analysis (TGA) measurement are taken to further
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15 analyze the MoS2 proportion in MoS2/G HS and the determined result is 82.1wt% by measured
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17 from 50 to 650oC in an air atmosphere (Figure S4b). N2 adsorption-desorption isotherms
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demonstrate that the Brunauer-Emmett-Teller (BET) surface area and the corresponding pore
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22 volume for MoS2/G HS, and MoS2 MP are 147.33 m2 g−1 and 16.26 cm3 g−1, 3.98 m2 g−1 and 20.95
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24 cm3 g−1, respectively (Figure S5a-d). The larger specific surface areas are caused by the ultrathin
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26 feature of the G sheets and small-sized MoS2 nanosheets, as well as the expanded interlayer
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29 spacing, which benefit to sufficiently expose electrochemically active sites and improve the HER
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31 catalytic property.
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Figure 1. (a) XRD patterns and (b) Raman spectra of MoS2/G HS and MoS2 MP. Structural models
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56 of (c) the pristine MoS2 MP and (d) expanded interplanar distance of MoS2/G HS.
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30 Figure 2. (a) SEM, (b) TEM, and (c-d) HRTEM images of MoS2/G HS.
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33 All the electrochemical measurements of MoS2/G HS, MoS2/G MM, MoS2 MP, G, and Pt/C are
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35 evaluated in 0.5 M H2SO4 and 1.0 M KOH solution after purging the electrolytes by N2 gas for 0.5
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h. Moreover, the three-electrode system is performed to survey the HER catalytic activities with
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40 the scan rate of 10 mV s−1. Figure 3a shows that the Pt/C electrode is still regarded as the best
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42 electrocatalytic HER catalyst. As expected in Figure 3a, the linear sweep voltammetry (LSV) curve
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shows that the magnitude of current density for MoS2/G HS has a sharp improvement with the
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47 increasing overpotentials. The MoS2/G HS exhibits a superior HER catalytic activities in 0.5 M
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49 H2SO4 solution with the onset overpotential of 52 mV versus (vs.) reversible hydrogen electrode
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51 (RHE), and the overpotentials of only 180 and 268 mV at the current density of 10 and 100 mA
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54 cm−2 (η10 = 180 mV and η100=268 mV), respectively. Such excellent HER catalytic activity
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56 outperforms the MoS2/G MM (η10 = 343 mV), MoS2 MP (η10 =383 mV), G (η10 = 423 mV) and
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3 most previously reported MoS2-based HER catalysts (Table S1), suggesting the hetero-layered
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6 architecture between the ultrathin G sheets and small-sized MoS2 monolayers is in favor of
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8 enhancing the HER activities. Moreover, it is noted that the HER activity for MoS2/G MM is
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10 superior than the MoS2 MP and G, confirming that the mechanical mixing can improve the MoS2
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performance to some extent due to the lager surface area and higher conductivity of G. To further
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15 demonstrate the catalytic performance of materials, the Tafel slope is fitted to η = a + b log j, where
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17 η, a, b, and j represent the corresponding overpotential, Tafel constant, Tafel slope, and current
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density, respectively.8,40 The Tafel slope of Pt/C electrode is 32 mV dec−1, which is in accord with
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22 the other reported values in acidic medium (Figure 3b). As displayed in Figure 3b-c, the MoS2/G
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24 HS electrode shows a slope value of 79 mV dec−1, which is lower than MoS2/G MM (136 mV
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26 dec−1), MoS2 MP (219 mV dec−1), G (318 mV dec−1) electrodes, signifying a superior catalytic
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29 ability of heterostructured MoS2/G. Generally, the HER processes of the rate determining step at
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31 25oC in acidic media has three steps: ion discharge (116 mV dec−1, the Volmer reaction),
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33 desorption (38 mV dec−1, the Heyrovsky reaction), and recombination (29 mV dec−1, the Tafel
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reaction), respectively.13,41 Therefore, the Tafel value reveals that the MoS2/G HS fits the Volmer-
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38 Heyrovsky mechanism under acidic conditions:13,41
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40 H3O+ + e− → Hads +H2O (Volmer reaction) (1)
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H3O+ + Hads + e− → H2 +H2O (Heyrovsky reaction) (2)
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45 To further investigate intrinsic catalytic activities and quantitative analysis active sites of
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47 catalysts, turnover frequency (TOF) is performed toward HER reaction. Assume that the oxidation
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49 and reduction are one-electron process, then all the charge in whole potential range can reflect the
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52 total quantity of active sites. Therefore, TOF (s−1) can be determine at different current densities
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54 or overpotentials after employing cyclic voltammetry (CV) cycling in pH = 7 phosphate buffer to
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30 Figure 3. (a) LSVs of MoS2/G HS, MoS2/G MM, MoS2 MP, G, and commercial Pt/C electrodes
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33 toward HER with a scan rate of 10 mV s−1, and (b) the corresponding Tafel plots, and (c) histogram
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35 of η10 and Tafel slope for various catalysts in 0.5 M H2SO4 solution. (d) LSVs of MoS2/G HS,
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37 MoS2/G MM, MoS2 MP, G, and commercial Pt/C electrodes toward HER with a scan rate of 10
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40 mV s−1, (e) the corresponding Tafel plots, and (f) histogram of η10 and Tafel slope of various
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42 catalysts in 1.0 M KOH solution. (g-i) LSVs of MoS2/G HS electrode before and after 1000 CV
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44 cycles, and the corresponding time-dependent current density curve under a static overpotential of
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206 and 226 mV over 30 and 45 h in 0.5 M H2SO4 and 1.0 M KOH solutions, respectively.
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49 calculate the voltammetric charges (Q) and then obtain number of active sites (n).42,43 Figure S6
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52 displays much higher TOF datas of MoS2/G HS than MoS2/G MM and MoS2 MP at different
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54 potentials. For example, when the value of TOF reaches to 1.0 s−1, the MoS2/G HS needs an
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56 overpotential of 266 mV, much smaller than the MoS2/G MM (484 mV) and MoS2 MP (657 mV),
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3 respectively, indicating this special layer-by-layered heterostructure can accommodate more
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6 exposed active sites and benefit to enhance the HER activities. The double-layer capacitance (Cdl),
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8 another vital element reflecting the activities of catalyst and effective surface area (ECSA), is
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10 evaluated by fitting the different scan rates of CV curves ranged from 0.25−0.35 V vs. RHE. The
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Cdl value of 33.3 mF cm−2 for MoS2/G HS is larger than the MoS2/G MM (28.4 mF cm−2) and
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15 MoS2 MP (0.2 mF cm−2), corresponding to lager active ECSA of heterostructured MoS2/G (Figure
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17 S7a-f). To evaluate the electronic conductivity of electrode/electrolyte interface, Electrochemical
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impedance spectroscopy (EIS) measurement is performed in acid solution toward HER. The
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22 Nyquist plots in Figure S8a displays that the charge-transfer resistance (Rct) values of MoS2/G HS
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24 at the overpotential of 300 mV is 1.5 Ω cm−2, lower than the MoS2/G MM (11.8 Ω cm−2) and MoS2
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26 MP (26.1 Ω cm−2), respectively. The decreased Rct for MoS2/G HS implies the enhancement of
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29 electronic conductivity caused by the expanded interlayer spacing and the alternately arranged
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31 layer-by-layered heterostructure between MoS2 and G.
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33 We next continue to investigate the HER activities of MoS2/G HS, MoS2/G MM, MoS2 MP, G,
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35
36
and Pt/C in 1.0 M KOH solution. LSVs in Figure 3d show that commercial Pt/C electrode has the
37
38 best HER activities with a near zero onset overpotential, while the G electrode exhibits the
39
40 ignorable HER performance with η10 =552 mV. To reach j = 10 mA cm−2, the overpotential of
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42
MoS2/G HS only requires 183 mV vs. RHE, superior to the MoS2/G MM (348 mV), MoS2 MP
43
44
45 (436 mV) and other previously reported MoS2-based catalysts in alkaline solution (Figure 3d and
46
47 Table S1). Tafel slope plots in Figure 3e-f show that the Tafel slop of MoS2/G HS is 127 mV dec−1,
48
49 which is proved to follow Volmer-Heyrovsky formalism and Heyrovsky reaction is the rate-
50
51
52 determining toward HER in 1.0 M KOH solution:41,42
53
54 H2O + e− → Hads + OH− (Volmer reaction) (3)
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13
1
2
3 Hads + H2O + e− → H2 + OH− (Heyrovsky reaction) (4)
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6 Furthermore, the Tafel slopes of MoS2/G MM, MoS2 MP, and G are 139, 312, and 302 mV dec−1
7
8 respectively, demonstrating the inferior intrinsic catalytic activities to HER (Figure 3e-f).
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10 Additionally, in order to further confirm the HER catalytic abilities of MoS2/G HS > MoS2/G MM
11
12
13
> MoS2 MP, the EIS in 1.0 M KOH solution is fitted with the Rct values of 1.7, 6.7, and 21.5 Ω
14
15 cm−2 for MoS2/G HS, MoS2/G MM, and MoS2 MP, respectively, suggesting the heterostructured
16
17 MoS2/G benefiting to the improvement of catalytic abilities and electronic conductivity (Figure
18
19
S8b).
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21
22 To investigate the durability during the HER process, a 1000th CV cycling test and long-term
23
24 stability are carried out. As shown in Figure 3g-h, the LSVs of the MoS2/G HS electrodes before
25
26 and after 1000 cycles sweeping from −0.35 to +0.2 V vs. RHE exhibits a negligible current change
27
28
29 both in acidic and alkaline solutions. Moreover, the long-term HER durability shows a
30
31 comparatively stable current ~ 20 mA cm−2 over 30 h during the potentiostatic measurement in
32
33 acidic solution (Figure 3i). Furthermore, the long-term stability > 45 h is detected at constant
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35
36
current density of 20−30 mA cm−2 in the given potential range with an inappreciable current loss
37
38 in 1.0 M KOH solution, indicating the superior stability of MoS2/G HS toward HER (Figure 3i).
39
40 The low-resolution SEM image MoS2/G HS after HER process for 10 h in Figure S9a shows that
41
42
the ultrathin nanosheets structure of MoS2/G HS are similar to the primary morphology after
43
44
45 multicycle stability test. Moreover, the HRTEM image exhibits that the stable crystallinity and the
46
47 same layer-by-layered architectures are still preserved, and the labeled interplanar lattice fringes
48
49 distances are 1.096 and 0.276 nm, corresponding to the lattice-expanded MoS2 and (100) planes,
50
51
52 respectively, further verifying the superior long-term stability (Figure S9b-c).
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32 Figure 4. (a-d) Contact angle of water droplets on the surface and electrical conductivity of MoS2
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34 MP, MoS2/G MM, and MoS2/G HS, respectively. (e) Hydrogen adsorption free energy diagram at
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36
an external potential URHE = 0 V for pristine MoS2 MP and MoS2/G HS. The top view of (f) the
37
38
39 optimized supercell and (g) the edge models of MoS2/G HS. Structures of 2 hydrogen atoms
40
41 adsorbed on edges of (h) pristine MoS2 MP and (i) MoS2/G HS. Carbon is brown, molybdenum is
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43 purple, sulfur is yellow, hydrogen is white, respectively.
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45
46 The first-class HER catalytic ability and excellent durability for MoS2/G HS are relevant to the
47
48
following factors: i) the ultrathin G sheets and monolayer MoS2 with ultras-mall size can expose
49
50
51 more unsaturated edge atoms and abundant defects, resulting in more edge active sites contacting
52
53 with the electrolyte and thereby improving the using efficiency of edge atoms and enhancing of
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55 HER performance; ii) the expanded interplanar distance of 1.104 nm benefits to ad/desorb
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15
1
2
3 hydrogen, and the high crystallinity with the discorded lattice fringes, as well as the larger BET of
4
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6 hetero-layered architectures MoS2/G HS can accommodate more active sites, thereby ensuring the
7
8 catalytic ability and the long-term stability; iii) the MoS2/G HS can effectively restrain the
9
10 aggregation of MoS2 nanosheets, facilitating the exposure of edge atoms and numerous defects;
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12
13
iV) the heterostructured MoS2/G can improve the wettability when exposure to electrolyte, which
14
15 benefits to electrolyte infiltration and more available active sites participating the catalytic
16
17 activities. The wettability measurement in Figure 4a-c are performed and the contact angle
18
19
between water and MoS2/G HS is 82.4o, which smaller than the MoS2/G MM (99.8o) and MoS2
20
21
22 MP (106.7o), suggesting the superior hydrophily of the MoS2/G HS; V) the 2D/2D alternately
23
24 arranged layer-by-layers between ultrathin MoS2 and G can form the face-to-face contact
25
26 heterostructures, which influence the electronic states and electrical conductivity. The
27
28
29 heterostructured MoS2/G are favor of transferring and separating the charges at coupled interface
30
31 and improving the electronic conductivity. The electrical conductivities of the MoS2/G HS,
32
33 MoS2/G MM and MoS2 MP were measured through the four-point probe technique. The MoS2/G
34
35
36
HS exhibits an enhancement electrical conductivity of 59.98 S cm−1, which is more than 1.893×103
37
38 and 1.926×105 times higher than those of MoS2/G MM and MoS2 MP (3.114 ×10−4 and 3.168×10−2
39
40 S cm−1), respectively (Figure 4d). Such high electrical conductivity can efficiently reduce the
41
42
additional voltage drop and facilitate the improvement of the catalytic efficiency.
43
44
45 Density functional theory (DFT) calculations were further performed to demonstrate the HER
46
47 activity of the non-expanded MoS2 and the interlayer-expanded MoS2/G HS by the typical three-
48
49 state diagram (Figure 4e-i). Figure 4f-g show the top view of the optimized supercell and the edge
50
51
52 models of MoS2/G HS. When 2 hydrogen atoms adsorbed on edges of the pristine MoS2 MP and
53
54 MoS2/G HS, the optimized structures are shown in Figure 4h-i. The ΔGH* process has been proved
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59
16
1
2
3 to be a good factor to evaluate the HER activity, including those MoS2 based materials,44 with a
4
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6 ΔGH* close to zero yielding the optimal electrochemical HER performance:
7
8 ΔGH*=ΔEH*+ΔEZPE−TΔSH (5)
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10 ΔEH*=E(edge+H) −E(edge) −1/2E(H2) (6)
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12
13
where ΔEH* is the adsorption energies of hydrogen atoms on the edges, E(edge+H) is the total
14
15 energy of the edges adsorbed with a hydrogen atom, E(edge) and E(H2) are the total energies of
16
17 the edge and hydrogen molecule, respectively. ΔEZPE is the zero point energy difference of
18
19
adsorbed hydrogen atom and a half of a gas phase hydrogen molecule, which is calculated to be
20
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22 0.04 eV. ΔSH is the entropy difference of adsorbed hydrogen atom and a half of a gas phase
23
24 hydrogen molecule at standard state and thus TΔSH is calculated to be −0.18 eV. Thus
25
26 ΔGH*=ΔEH*+ΔEZPE−TΔSH= ΔEH*+0.22 eV (7)
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29 The hydrogen adsorption coverage H = 0.5ML is reported to obtain optimal HER activity on 2H-
30
31 MoS2 edges.44 As shown in Figure 4e, the ΔGH* of non-expanded MoS2 (0.615 nm) is −0.72 eV,
32
33 while the heterostructured MoS2/G with the expanded interplanar distance of 1.104 nm is also
34
35
36
calculated and the more preferable ΔGH* is −0.28 eV, indicating the heterostructured MoS2/G has
37
38 the fast hydrogen release and the appropriate hydrogen adsorption process.
39
40 3. CONCLUSIONS
41
42
43
44 In summary, we successfully synthesize the ultra-small size monolayer (approximately 5−10 nm)
45
46 MoS2 nanosheets covered on the ultrathin G sheets to form the intimate face-to-face hetero-layered
47
48 architectures via electrostatic attraction and self-assembly method. Compared to MoS2/G MM,
49
50
51 MoS2 MP, and G catalysts, the as-synthesized heterostructured MoS2/G is demonstrated to be favor
52
53 of interacting at the interface of MoS2 and graphene, and the unique architectures can lead to more
54
55 atom edges active sites and defects, the improvement using efficiency of edge atoms, as well as
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17
1
2
3 the enhancement electronic conductivity. The DFT calculation results further confirm that the
4
5
6 alternately arranged G layers and MoS2 monolayers, as well as the expanded interplanar distance
7
8 of 1.104 nm for MoS2/G HS are beneficial to improve the HER performance. Therefore, the
9
10 MoS2/G HS exhibits superior HER ability with the overpotentials at j = 10 and 100 mA cm−2 are
11
12
13
only 180 and 263 mV, as well as the Tafel slope is 79 mV dec−1 in 0.5 M H2SO4 solution,
14
15 respectively. Moreover, the overpotential and Tafel slope are 183 mV and 127 mV dec−1 in 1.0 M
16
17 KOH solution. In addition, the outstanding long-term stability for MoS2/G HS in acidic and
18
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alkaline electrolytes all surpass 30 and 45 h at 20 mA cm−2 with a negligible current loss,
20
21
22 respectively. Thus, the cost-effective synthetic method in our work can further extend to produce
23
24 other 2D/2D layered materials to enhance the catalytic ability and broaden their applications, such
25
26 as energy storage, physical electronics, photonic devices.
27
28
29
30 ASSOCIATED CONTENT
31
32
33 Supporting Information Available: Experimental details and additional Figure S1–S9 and Table
34
35 S1. Experimental details, XPS spectra, TEM and SEM results, Element mapping images, EDS
36
37 image and TG curve, Nitrogen adsorption and desorption isotherms and the corresponding pore-
38
39
40 size distribution curves, TOF curves, Cdl and the corresponding fitted curves, Nyquist plots,
41
42 performances with comparisons are described in the text.
43
44
45 AUTHOR INFORMATION
46
47
Corresponding Author
48
49
50 *E-mail: zhaogy810525@gmail.com
51
52
53 *E-mail: znqmww@163.com
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55
56 *E-mail: pengbo.lyu@umontpellier.fr
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59
18
1
2
3 Notes
4
5
6
7
The authors declare no competing financial interest.
8
9
10 ACKNOWLEDGMENT
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12
13 This work was supported by the National Natural Science Foundation of China (Nos. 21776052),
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15 the Natural Science Foundation of Heilongjiang Province (Nos. QC2016010) and the Fundamental
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17
18
Research Funds for the Central Universities (Nos. HIT. IBRSEM. A. 201407).
19
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10 Chorkendorff, I.; Nørskov, J. K. Biomimetic Hydrogen Evolution: MoS2 Nanoparticles as
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