AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Activating interfacial S sites of MoS2 boosts hydrogen evolution electrocatalysis

Shuo Geng1,2,§, Fenyang Tian2,§, Menggang Li2, Yequn Liu3, Jie Sheng1, Weiwei Yang1,2( ), Yongsheng Yu2( ), Yanglong Hou4( )
Laboratory for Space Environment and Physical Science, Research Center of Basic Space Science, Harbin Institute of Technology, Harbin 150001, China
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China
Analytical Instrumentation Center, State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
Beijing Key Laboratory for Magnetoelectric Materials and Devices (BKL-MMD), Beijing Innovation Center for Engineering Science and Advanced Technology (BIC-ESAT), School of Materials Science and Engineering, Peking University, Beijing 100871, China

§ Shuo Geng and Fenyang Tian contributed equally to this work.

Show Author Information

Graphical Abstract

Abstract

The hydrogen evolution reaction (HER) of molybdenum disulfide (MoS2) is limited in alkaline and acid solution because the active sites are on the finite edge with extended basal plane remaining inert. Herein, we activated the interfacial S sites by coupling with Ru nanoparticles on the inert basal plane of MoS2 nanosheets. The density functional theory (DFT) calculation and experimental results show that the interfacial S electronic structure was modulated. And the results of ∆GH* demonstrate that the adsorption of H on the MoS2 was also optimized. With the advantage of interfacial S sites activation, the Ru-MoS2 needs only overpotential of 110 and 98 mV to achieve 10 mA·cm–2 in both 0.5 M H2SO4 and 1 M KOH solution, respectively. This strategy paves a new way for activating the basal plane of other transition metal sulfide electrocatalysts for improving the HER performance.

Keywords

electronic structureinterfacial S sitesd-band centerhydrogen evolution reaction

References

1

Huang, Y. R.; Li, M. G.; Yang, W. W.; Yu, Y. S.; Hao, S. E. 3D ordered mesoporous cobalt ferrite phosphides for overall water splitting. Sci. China Mater. 2020, 63, 240–248.
Crossref Google Scholar
2

Centi, G. Smart catalytic materials for energy transition. SmartMat 2020, 1, e1005.
Crossref Google Scholar
3

Li, M. G.; Luo, M. C.; Xia, Z. H.; Yang, Y.; Huang, Y. R.; Wu, D.; Sun, Y. J.; Li, C. J.; Chao, Y. G.; Yang, W. X. et al. Modulating the surface segregation of PdCuRu nanocrystals for enhanced all-pH hydrogen evolution electrocatalysis. J. Mater. Chem. A 2019, 7, 20151–20157.
Crossref Google Scholar
4

Lu, K.; Liu, Y. Z.; Lin, F.; Cordova, I. A.; Gao, S. Y.; Li, B. M.; Peng, B.; Xu, H. P.; Kaelin, J.; Coliz, D. et al. LixNiO/Ni heterostructure with strong basic lattice oxygen enables electrocatalytic hydrogen evolution with Pt-like activity. J. Am. Chem. Soc. 2020, 142, 12613–12619.
Crossref Google Scholar
5

Ji, X. X.; Lin, Y. H.; Zeng, J.; Ren, Z. H.; Lin, Z. J.; Mu, Y. B.; Qiu, Y. J.; Yu, J. Graphene/MoS2/FeCoNi(OH)x and graphene/MoS2/FeCoNiPx multilayer-stacked vertical nanosheets on carbon fibers for highly efficient overall water splitting. Nat. Commun. 2021, 12, 1380.
Crossref Google Scholar
6

Yang, J.; Mohmad, A. R.; Wang, Y.; Fullon, R.; Song, X. J.; Zhao, F.; Bozkurt, I.; Augustin, M.; Santos, E. J. G.; Shin, H. S. et al. Ultrahigh-current-density niobium disulfide catalysts for hydrogen evolution. Nat. Mater. 2019, 18, 1309–1314.
Crossref Google Scholar
7

Greeley, J.; Jaramillo, T. F.; Bonde, J.; Chorkendorff, I.; Nørskov, J. K. Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat. Mater. 2006, 5, 909–913.
Crossref Google Scholar
8

Kobayashi, D.; Kobayashi, H.; Wu, D. S.; Okazoe, S.; Kusada, K.; Yamamoto, T.; Toriyama, T.; Matsumura, S.; Kawaguchi, S.; Kubota, Y. et al. Significant enhancement of hydrogen evolution reaction activity by negatively charged Pt through light doping of W. J. Am. Chem. Soc. 2020, 142, 17250–17254.
Crossref Google Scholar
9

Li, M. G.; Zhao, Z. L.; Xia, Z. H.; Luo, M. C.; Zhang, Q. H.; Qin, Y. N.; Tao, L.; Yin, K.; Chao, Y. G.; Gu, L. et al. Exclusive strain effect boosts overall water splitting in PdCu/Ir core/shell nanocrystals. Angew. Chem., Int. Ed. 2021, 60, 8243–8250.
Crossref Google Scholar
10
Li, Y. L.; He, J. F.; Cheng, W. R.; Su, H.; Li, C. L.; Zhang, H.; Liu, M. H.; Zhou, W. L.; Chen, X.; Liu, Q. H. High mass-specific reactivity of a defect-enriched Ru electrocatalyst for hydrogen evolution in harsh alkaline and acidic media. Sci. China Mater., in press, DOI: 10.1007/s40843-020-1656-0.https://doi.org/10.1007/s40843-020-1656-0
Crossref
11

Zhang, Z. C.; Liu, G. G.; Cui, X. Y.; Gong, Y.; Yi, D.; Zhang, Q. H.; Zhu, C. Z.; Saleem, F.; Chen, B.; Lai, Z. C. et al. Evoking ordered vacancies in metallic nanostructures toward a vacated Barlow packing for high-performance hydrogen evolution. Sci. Adv. 2021, 7, eabd6647.
Crossref Google Scholar
12

Mahmood, J.; Li, F.; Jung, S. M.; Okyay, M. S.; Ahmad, I.; Kim, S. J.; Park, N.; Jeong, H. Y.; Baek, J. B. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction. Nat. Nanotechnol. 2017, 12, 441–446.
Crossref Google Scholar
13

Tian, F. Y.; Geng, S.; He, L.; Huang, Y. R.; Fauzi, A.; Yang, W. W.; Liu, Y. Q.; Yu, Y. S. Interface engineering: PSS-PPy wrapping amorphous Ni-Co-P for enhancing neutral-pH hydrogen evolution reaction performance. Chem. Eng. J. 2021, 417, 129232.
Crossref Google Scholar
14

Ma, B.; Yang, Z. C.; Chen, Y. T.; Yuan, Z. H. Nickel cobalt phosphide with three-dimensional nanostructure as a highly efficient electrocatalyst for hydrogen evolution reaction in both acidic and alkaline electrolytes. Nano Res. 2019, 12, 375–380.
Crossref Google Scholar
15

Su, J. Z.; Zhou, J. L.; Wang, L.; Liu, C.; Chen, Y. B. Synthesis and application of transition metal phosphides as electrocatalyst for water splitting. Sci. Bull. 2017, 62, 633–644.
Crossref Google Scholar
16

Jin, H. Y.; Guo, C. X.; Liu, X.; Liu, J. L.; Vasileff, A.; Jiao, Y.; Zheng, Y.; Qiao, S. Z. Emerging two-dimensional nanomaterials for electrocatalysis. Chem. Rev. 2018, 118, 6337–6408.
Crossref Google Scholar
17

Wang, H. Q.; Xu, Z. F.; Zhang, Z. F.; Hu, S. X.; Ma, M. J.; Zhang, Z. C.; Zhou, W. J.; Liu, H. Addressable surface engineering for N-doped WS2 nanosheet arrays with abundant active sites and the optimal local electronic structure for enhanced hydrogen evolution reaction. Nanoscale 2020, 12, 22541–22550.
Crossref Google Scholar
18

Geng, S.; Liu, Y. Q.; Yu, Y. S.; Yang, W. W.; Li, H. B. Engineering defects and adjusting electronic structure on S doped MoO2 nanosheets toward highly active hydrogen evolution reaction. Nano Res. 2020, 13, 121–126.
Crossref Google Scholar
19

Huang, H. J.; Yan, M. M.; Yang, C. Z.; He, H. Y.; Jiang, Q. G.; Yang, L.; Lu, Z. Y.; Sun, Z. Q.; Xu, X. T.; Bando, Y. et al. Graphene nanoarchitectonics: Recent advances in graphene-based electrocatalysts for hydrogen evolution reaction. Adv. Mater. 2019, 31, 1903415.
Crossref Google Scholar
20

Guo, Y. N.; Park, T.; Yi, J. W.; Henzie, J.; Kim, J.; Wang, Z. L.; Jiang, B.; Bando, Y.; Sugahara, Y.; Tang, J. et al. Nanoarchitectonics for transition-metal-sulfide-based electrocatalysts for water splitting. Adv. Mater. 2019, 31, 1807134.
Crossref Google Scholar
21

Ding, Q.; Song, B.; Xu, P.; Jin, S. Efficient electrocatalytic and photoelectrochemical hydrogen generation using MoS2 and related compounds. Chem 2016, 1, 699–726.
Crossref Google Scholar
22

Lei, L.; Huang, D. L.; Zeng, G. M.; Cheng, M.; Jiang, D. N.; Zhou, C. Y.; Chen, S.; Wang, W. J. A fantastic two-dimensional MoS2 material based on the inert basal planes activation: Electronic structure, synthesis strategies, catalytic active sites, catalytic and electronics properties. Coordin. Chem. Rev. 2019, 399, 213020.
Crossref Google Scholar
23

Hinnemann, B.; Moses, P. G.; Bonde, J.; Jørgensen, K. P.; Nielsen, J. H.; Horch, S.; Chorkendorff, I.; Nørskov, J. K. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J. Am. Chem. Soc. 2005, 127, 5308–5309.
Crossref Google Scholar
24

Jaramillo, T. F.; Jørgensen, K. P.; Bonde, J.; Nielsen, J. H.; Horch, S.; Chorkendorff, I. Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 2007, 317, 100–102.
Crossref Google Scholar
25

Tsai, C.; Chan, K. R.; Nørskov, J. K.; Abild-Pedersen, F. Theoretical insights into the hydrogen evolution activity of layered transition metal dichalcogenides. Surf. Sci. 2015, 640, 133–140.
Crossref Google Scholar
26

Kibsgaard, J.; Chen, Z. B.; Reinecke, B. N.; Jaramillo, T. F. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat. Mater. 2012, 11, 963–969.
Crossref Google Scholar
27

Xie, J. F.; Zhang, H.; Li, S.; Wang, R. X.; Sun, X.; Zhou, M.; Zhou, J. F.; Lou, X. W.; Xie, Y. Defect-rich MoS2 ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution. Adv. Mater. 2013, 25, 5807–5813.
Crossref Google Scholar
28

Sun, C.; Wang, P. P.; Wang, H.; Xu, C.; Zhu, J. T.; Liang, Y. X.; Su, Y.; Jiang, Y. N.; Wu, W. Q.; Fu, E. G. et al. Defect engineering of molybdenum disulfide through ion irradiation to boost hydrogen evolution reaction performance. Nano Res. 2019, 12, 1613–1618.
Crossref Google Scholar
29

Deng, J.; Li, H. B.; Wang, S. H.; Ding, D.; Chen, M. S.; Liu, C.; Tian, Z. Q.; Novoselov, K. S.; Ma, C.; Deng, D. H. et al. Multiscale structural and electronic control of molybdenum disulfide foam for highly efficient hydrogen production. Nat. Commun. 2017, 8, 14430.
Crossref Google Scholar
30

Li, H.; Tsai, C.; Koh, A. L.; Cai, L. L.; Contryman, A. W.; Fragapane, A. H.; Zhao, J. H.; Han, H. S.; Manoharan, H. C.; Abild-Pedersen, F. et al. Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies. Nat. Mater. 2016, 15, 48–53.
Crossref Google Scholar
31

Geng, S.; Yang, W. W.; Liu, Y. Q.; Yu, Y. S. Engineering sulfur vacancies in basal plane of MoS2 for enhanced hydrogen evolution reaction. J. Catal. 2020, 391, 91–97.
Crossref Google Scholar
32

Geng, S.; Liu, H.; Yang, W. W.; Yu, Y. S. Activating the MoS2 basal plane by controllable fabrication of pores for an enhanced hydrogen evolution reaction. Chem. Eur. J. 2018, 24, 19075–19080.
Crossref Google Scholar
33

Voiry, D.; Salehi, M.; Silva, R.; Fujita, T.; Chen, M. W.; Asefa, T.; Shenoy, V. B.; Eda, G.; Chhowalla, M. Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Lett. 2013, 13, 6222–6227.
Crossref Google Scholar
34

Hong, M.; Shi, J. P.; Huan, Y. H.; Xie, Q.; Zhang, Y. F. Microscopic insights into the catalytic mechanisms of monolayer MoS2 and its heterostructures in hydrogen evolution reaction. Nano Res. 2019, 12, 2140–2149.
Crossref Google Scholar
35

Park, S.; Kim, C.; Park, S. O.; Oh, N. K.; Kim, U.; Lee, J.; Seo, J.; Yang, Y. J.; Lim, H. Y.; Kwak, S. K. et al. Phase engineering of transition metal dichalcogenides with unprecedentedly high phase purity, stability, and scalability via molten-metal-assisted intercalation. Adv. Mater. 2020, 32, 2001889.
Crossref Google Scholar
36

Kim, Y.; Jackson, D. H. K.; Lee, D.; Choi, M.; Kim, T. W.; Jeong, S. Y.; Chae, H. J.; Kim, H. W.; Park, N.; Chang, H. et al. In situ electrochemical activation of atomic layer deposition coated MoS2 basal planes for efficient hydrogen evolution reaction. Adv. Funct. Mater. 2017, 27, 1701825.
Crossref Google Scholar
37

Sun, K. A.; Zeng, L. Y.; Liu, S. H.; Zhao, L.; Zhu, H. Y.; Zhao, J. C.; Liu, Z.; Cao, D. W.; Hou, Y. C.; Liu, Y. Q. et al. Design of basal plane active MoS2 through one-step nitrogen and phosphorus co-doping as an efficient pH-universal electrocatalyst for hydrogen evolution. Nano Energy 2019, 58, 862–869.
Crossref Google Scholar
38

Chen, Z. Y.; Song, Y.; Cai, J. Y.; Zheng, X. S.; Han, D. D.; Wu, Y. S.; Zang, Y. P.; Niu, S. W.; Liu, Y.; Zhu, J. F. et al. Tailoring the d-band centers enables Co4N nanosheets to be highly active for hydrogen evolution catalysis. Angew. Chem., Int. Ed. 2018, 57, 5076–5080.
Crossref Google Scholar
39

Wang, L.; Li, Z. J.; Wang, K. X.; Dai, Q. Z.; Lei, C. J.; Yang, B.; Zhang, Q. H.; Lei, L. C.; Leung, M. K. H.; Hou, Y. Tuning d-band center of tungsten carbide via Mo doping for efficient hydrogen evolution and Zn-H2O cell over a wide pH range. Nano Energy 2020, 74, 104850.
Crossref Google Scholar
40

Duan, H. L.; Liu, W.; Guo, P.; Tang, F. M.; Yan, W. S.; Yao, T. Identifying the single active site in MoS2-based hydrogen evolution electrocatalyst by XAFS technique. Radiat. Phys. Chem. 2020, 175, 108151.
Crossref Google Scholar
41

Wang, X.; Zhang, Y. W.; Si, H. N.; Zhang, Q. H.; Wu, J.; Gao, L.; Wei, X. F.; Sun, Y.; Liao, Q. L.; Zhang, Z. et al. Single-atom vacancy defect to trigger high-efficiency hydrogen evolution of MoS2. J. Am. Chem. Soc. 2020, 142, 4298–4308.
Crossref Google Scholar
42

Zhang, X.; Zhou, F.; Zhang, S.; Liang, Y. Y.; Wang, R. H. Engineering MoS2 basal planes for hydrogen evolution via synergistic ruthenium doping and nanocarbon hybridization. Adv. Sci. 2019, 6, 1900090.
Crossref Google Scholar
43

Wei, S. T.; Cai, X. Q.; Xu, Y. C.; Shang, B.; Zhang, Q. H.; Gu, L.; Fan, X. F.; Zheng, L. R.; Hou, C. M.; Huang, H. H. et al. Iridium-triggered phase transition of MoS2 nanosheets boosts overall water splitting in alkaline media. ACS Energy Lett. 2019, 4, 368–374.
Crossref Google Scholar
44

Zhuang, Z. C.; Li, Y.; Li, Z. L.; Lv, F.; Lang, Z. Q.; Zhao, K. N.; Zhou, L.; Moskaleva, L.; Guo, S. J.; Mai, L. MoB/g-C3N4 interface materials as a Schottky catalyst to boost hydrogen evolution. Angew. Chem., Int. Ed. 2018, 57, 496–500.
Crossref Google Scholar
45

Liu, X. Y.; Liu, H.; Wang, Y. J.; Yang, W. W.; Yu, Y. S. Nitrogen-rich g-C3N4@AgPd Mott-Schottky heterojunction boosts photocatalytic hydrogen production from water and tandem reduction of NO3− and NO2−. J. Colloid Interface Sci. 2021, 581, 619–626.
Crossref Google Scholar
46

He, R.; Hua, J.; Zhang, A. Q.; Wang, C. H.; Peng, J. Y.; Chen, W. J.; Zeng, J. Molybdenum disulfide-black phosphorus hybrid nanosheets as a superior catalyst for electrochemical hydrogen evolution. Nano Lett. 2017, 17, 4311–4316.
Crossref Google Scholar
47

Zhang, H.; Li, H. Y.; Akram, B.; Wang, X. Fabrication of NiFe layered double hydroxide with well-defined laminar superstructure as highly efficient oxygen evolution electrocatalysts. Nano Res. 2019, 12, 1327–1331.
Crossref Google Scholar
48

Bolar, S.; Shit, S.; Kumar, J. S.; Murmu, N. C.; Ganesh, R. S.; Inokawa, H.; Kuila, T. Optimization of active surface area of flower like MoS2 using V-doping towards enhanced hydrogen evolution reaction in acidic and basic medium. Appl. Catal. B Environ. 2019, 254, 432–442.
Crossref Google Scholar
49

Zhou, Y. Y.; Xie, Z. Y.; Jiang, J. X.; Wang, J.; Song, X. Y.; He, Q.; Ding, W.; Wei, Z. D. Lattice-confined Ru clusters with high CO tolerance and activity for the hydrogen oxidation reaction. Nat. Catal. 2020, 3, 454–462.
Crossref Google Scholar
50

LaRue, J.; Krejčí, O.; Yu, L.; Beye, M.; Ng, M. L.; Öberg, H.; Xin, H.; Mercurio, G.; Moeller S.; Turner, J. J. et al. Real-time elucidation of catalytic pathways in CO hydrogenation on Ru. J. Phys. Chem. Lett. 2017, 8, 3820–3825.
Crossref Google Scholar
51

Ni, J.; Ran, H. Y.; Lin, J. X.; Wang, X. Y.; Lin, B. Y.; Jiang, L. L. Investigation on deactivation of K-promoted Ru catalyst for ammonia synthesis by CO formation. ChemistrySelect 2020, 5, 6639–6645.
Crossref Google Scholar
52

Fang, Z. W.; Peng, L. L.; Qian, Y. M.; Zhang, X.; Xie, Y. J.; Cha, J. J.; Yu, G. H. Dual tuning of Ni-Co-A (A = P, Se, O) nanosheets by anion substitution and holey engineering for efficient hydrogen evolution. J. Am. Chem. Soc. 2018, 140, 5241–5247.
Crossref Google Scholar
Nano Research
Volume 15 Issue 3,
March 2022
Pages 1809-1816
DOI: 10.1007/s12274-021-3755-7
Cite this article:
Geng S, Tian F, Li M, et al. Activating interfacial S sites of MoS2 boosts hydrogen evolution electrocatalysis. Nano Research, 2022, 15(3): 1809-1816. https://doi.org/10.1007/s12274-021-3755-7
Topics:
Hydrogen evolution reaction
Part of a topical collection:
The winners of “Top Papers Award” in 2022

1326

Views

112

Crossref

133

Web of Science

116

Scopus

8

CSCD

Altmetrics
Received: 13 May 2021
Revised: 13 July 2021
Accepted: 17 July 2021
Published: 02 August 2021
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
Return