Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Graphical Abstract
Abstract
Keywords
Electronic Supplementary Material
References
Show full outline
Hide outline
Research Article

Self-supported CoMoS4 nanosheet array as an efficient catalyst for hydrogen evolution reaction at neutral pH

Xiang Ren1,§, Dan Wu1,§, Ruixiang Ge2, Xu Sun1, Hongmin Ma1, Tao Yan3, Yong Zhang1, Bin Du3, Qin Wei1(), Liang Chen2()
Key Laboratory of Interfacial Reaction & Sensing Analysis in Universities of ShandongSchool of Chemistry and Chemical EngineeringUniversity of JinanJinan250022China
Ningbo Institute of Materials Technology and EngineeringChinese Academy of SciencesNingbo315201China
School of Resources and EnvironmentUniversity of JinanJinan250022China

§ Xiang Ren and Dan Wu contributed equally to this work.

Show Author Information

Graphical Abstract

View original image Download original image

Abstract

Development of earth-abundant electrocatalysts, particularly for high-efficiency hydrogen evolution reaction (HER) under benign conditions, is highly desired, but still remains a serious challenge. Herein, we report a high-performance amorphous CoMoS4 nanosheet array on carbon cloth (CoMoS4 NS/CC), prepared by hydrothermal treatment of a Co(OH)F nanosheet array on a carbon cloth (Co(OH)F NS/CC) in (NH4)2MoS4 solution. As a three-dimensional HER electrode, CoMoS4 NS/CC exhibits remarkable activity in 1.0 M phosphate buffer saline (pH 7), only requiring an overpotential of 183 mV to drive a geometrical current density of 10 mA·cm–2. This overpotential is 140 mV lower than that for Co(OH)F NS/CC. Notably, this electrode also shows outstanding electrochemical durability and nearly 100% Faradaic efficiency. Density functional theory calculations suggest that CoMoS4 has a more favorable hydrogen adsorption free energy than Co(OH)F.

Keywords

CoMoS4 nanosheet arrayhydrogen evolution reactionanion exchange reactionneutral pHdensity functional theory

Electronic Supplementary Material

Download File(s)
12274_2017_1818_MOESM1_ESM.pdf (2.1 MB)

References

1

Tang, C.; Cheng, N. Y.; Pu, Z. H.; Xing, W.; Sun, X. P. NiSe nanowire film supported on nickel foam: An efficient and stable 3D bifunctional electrode for full water splitting. Angew. Chem., Int. Ed. 2015, 54, 9351-9355.

Crossref Google Scholar
2

Lewis, N. S.; Nocera, D. G. Powering the planet: Chemical challenges in solar energy utilization. Proc. Natl. Acad. Sci. USA 2006, 103, 15729-15735.

Crossref Google Scholar
3

Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; Mi, Q.; Santori, E. A.; Lewis, N. S. Solar water splitting cells. Chem. Rev. 2010, 110, 6446-6473.

Crossref Google Scholar
4

Wang, J. H.; Cui, W.; Liu, Q.; Xing, Z. C.; Asiri, A. M.; Sun, X. P. Recent progress in cobalt-based heterogeneous catalysts for electrochemical water splitting. Adv. Mater. 2016, 28, 215-230.

Crossref Google Scholar
5

Zou, X. X.; Zhang, Y. Noble metal-free hydrogen evolution catalysts for water splitting. Chem. Soc. Rev. 2015, 44, 5148-5180.

Crossref Google Scholar
6

Le Goff, A.; Artero, V.; Jousselme, B.; Tran, P. D.; Guillet, N.; Métayé, R.; Fihri, A.; Palacin, S.; Fontecave, M. From hydrogenases to noble metal-free catalytic nanomaterials for H2 production and uptake. Science 2009, 326, 1384-1387.

Crossref Google Scholar
7

Yang, N.; Tang, C.; Wang, K. Y.; Du, G.; Asiri, AM.; Sun, X. P. Iron-doped nickel disulfide nanoarray: A highly efficient and stable electrocatalyst for water splitting. Nano Res. 2016, 9, 3346-3354.

Crossref Google Scholar
8

Pu, Z. H.; Luo, Y. L.; Asiri, A. M.; Sun, X. P. Efficient electrochemical water splitting catalyzed by electrodeposited nickel diselenide nanoparticles based film. ACS Appl. Mater. Interfaces 2016, 8, 4718-4723.

Crossref Google Scholar
9

Tian, J. Q.; Liu, Q.; Asiri, A. M.; Sun, X. P. Self-supported nanoporous cobalt phosphide nanowire arrays: An efficient 3D hydrogen-evolving cathode over the wide range of pH 0-14. J. Am. Chem. Soc. 2014, 136, 7587-7590.

Crossref Google Scholar
10

Tang, C.; Gan, L. F.; Zhang, R.; Lu, W. B.; Jiang, X. E.; Asiri, A. M.; Sun, X. P.; Wang, J.; Chen, L. Ternary FexCo1-xP nanowire array as a robust hydrogen evolution reaction electrocatalyst with Pt-like activity: Experimental and theoretical insight. Nano Lett. 2016, 16, 6617-6621.

Crossref Google Scholar
11

Losse, S.; Vos, J. G.; Rau, S. Catalytic hydrogen production at cobalt centres. Coord. Chem. Rev. 2010, 254, 2492-2504.

Crossref Google Scholar
12

Liu, T. T.; Ma, X.; Liu, D. N.; Hao, S.; Du, G.; Ma, Y. J.; Asiri, A. M.; Sun, X. P.; Chen, L. Mn doping of CoP nanosheets array: An efficient electrocatalyst for hydrogen evolution reaction with enhanced activity at all pH values. ACS Catal. 2017, 7, 98-102.

Crossref Google Scholar
13

Li, K. D.; Zhang, J. F.; Wu, R.; Yu, Y. F.; Zhang, B. Anchoring CoO domains on CoSe2 nanobelts as bifunctional electrocatalysts for overall water splitting in neutral media. Adv. Sci. 2016, 3, 1500426.

Crossref Google Scholar
14

Sun, Y. J.; Liu, C.; Grauer, D. C.; Yano, J.; Long, J. R.; Yang, P. D.; Chang, C. J. Electrodeposited cobalt-sulfide catalyst for electrochemical and photoelectrochemical hydrogen generation from water. J. Am. Chem. Soc. 2013, 135, 17699-17702.

Crossref Google Scholar
15

Merki, D.; Fierro, S.; Vrubel, H.; Hu, X. Amorphous molybdenum sulfide films as catalysts for electrochemical hydrogen production in water. Chem. Sci. 2011, 2, 1262-1267.

Crossref Google Scholar
16

Morales-Guio, C. G.; Hu, X. Amorphous molybdenum sulfides as hydrogen evolution catalysts. Acc. Chem. Res. 2014, 47, 2671-2681.

Crossref Google Scholar
17

Merki, D.; Vrubel, H.; Rovelli, L.; Fierro, S.; Hu, X. Fe, Co, and Ni ions promote the catalytic activity of amorphous molybdenum sulfide films for hydrogen evolution. Chem. Sci. 2012, 3, 2515-2525.

Crossref Google Scholar
18

Tian, J. Q.; Liu, Q.; Cheng, N. Y.; Asiri, A. M.; Sun, X. P. Self-supported Cu3P nanowire arrays as an integrated high-performance three-dimensional cathode for generating hydrogen from water. Angew. Chem., Int. Ed. 2014, 53, 9577-9581.

Crossref Google Scholar
19

Jiang, P.; Liu, Q.; Liang, Y. H.; Tian, J. Q.; Asiri, A. M.; Sun, X. A cost-Effective 3D hydrogen evolution cathode with high catalytic activity: FeP nanowire array as the active phase. Angew. Chem., Int. Ed. 2014, 53, 12855-12859.

Crossref Google Scholar
20

Xie, L. S.; Zhang, R.; Cui, L.; Liu, D. N.; Hao, S.; Ma, Y. J.; Du, G.; Asiri, A. M.; Sun, X. P. High-performance electrolytic oxygen evolution in neutral media catalyzed by a cobalt phosphate nanoarray. Angew. Chem., Int. Ed. 2017, 56, 1064-1068.

Crossref Google Scholar
21

Ren, X.; Ge, R. X.; Zhang, Y.; Liu, D. N.; Wu, D.; Sun, X.; Du B.; Wei, Q. Cobalt-borate nanowire array as a high-performance catalyst for oxygen evolution reaction in near-neutral media. J. Mater. Chem. A 2017, 5, 7291-7294.

Crossref Google Scholar
22

Ji, X. Q.; Cui, L.; Liu, D. N.; Hao, S.; Liu, J. Q.; Qu, F. L.; Ma, Y. J.; Du, G.; Asiri, A. M.; Sun, X. P. A nickel-borate nanoarray: A highly active 3D oxygen-evolving catalyst electrode operating in near-neutral water. Chem. Commun. 2017, 53, 3070-3073.

Crossref Google Scholar
23

Ma, M.; Qu, F. L.; Ji, X. Q.; Liu, D. N.; Hao, S.; Du, G.; Asiri, A. M.; Yao, Y. D.; Chen, L.; Sun, X. P. Bimetallic nickel-substituted cobalt-borate nanowire array: An earth-abundant water oxidation electrocatalyst with superior activity and durability at near neutral pH. Small 2017, 13, 1700394.

Crossref Google Scholar
24

Ge, R. X.; Ren, X.; Qu, F. L.; Liu, D. N.; Ma, M.; Hao, S.; Du, G.; Asiri, A. M.; Chen, L.; Sun, X. P. Three-dimensional nickel-borate nanosheets array for efficient oxygen evolution at near-neutral pH. Chem. -Eur. J. 2017, 23, 6959-6963.

Crossref Google Scholar
25

Zhu, G. L.; Ge, R. X.; Qu, F. L.; Du, G.; Asiri, A. M.; Yao, Y. D.; Sun, X. P. In situ surface derivation of an Fe-Co-Bi layer on an Fe-doped Co3O4 nanoarray for eficient water oxidation electrocatalysis under near-neutral conditions. J. Mater. Chem. A 2017, 5, 6388-6392.

Crossref Google Scholar
26

Zhang, R.; Tang, C.; Kong, R. M.; Du, G.; Asiri, A. M.; Chen, L.; Sun, X. P. Al-doped CoP nanoarray: A durable water-splitting electrocatalyst with superhigh activity. Nanoscale 2017, 9, 4793-4800.

Crossref Google Scholar
27

Sun, X.; Guo, Y. Q.; Wu, C. Z.; Xie, Y. The hydric effect in inorganic nanomaterials for nanoelectronics and energy applications. Adv. Mater. 2015, 27, 3850-3867.

Crossref Google Scholar
28

Bi, W. T.; Hu, Z. P.; Li, X. G.; Wu, C. Z.; Wu, J. C.; Wu, Y. B.; Xie, Y. Metallic mesocrystal nanosheets of vanadium nitride for high-performance all-solid-state pseudocapacitors. Nano Res. 2015, 8, 193-200.

Crossref Google Scholar
29

Xu, R.; Wu, R.; Shi, Y. M.; Zhang, J. F.; Zhang, B. Ni3Se2 nanoforest/Ni foam as a hydrophilic, metallic, and self-supported bifunctional electrocatalyst for both H2 and O2 generations. Nano Energy 2016, 24, 103-110.

Crossref Google Scholar
30

Shi, Y. M.; Zhang, B. Recent advances in transition metal phosphide nanomaterials: Synthesis and applications in hydrogen evolution reaction. Chem. Soc. Rev. 2016, 45, 1529-1541.

Crossref Google Scholar
31

Wu, R.; Zhang, J. F.; Shi, Y. M.; Liu, D. L.; Zhang, B. Metallic WO2-carbon mesoporous nanowires as highly efficient electrocatalysts for hydrogen evolution reaction. J. Am. Chem. Soc. 2015, 137, 6983-6986.

Crossref Google Scholar
32

Xia, X. H.; Zhu, C. R.; Luo, J. S.; Zeng, Z. Y.; Guan, C.; Ng, C. F.; Zhang, H.; Fan, H. J. Synthesis of free-standing metal sulfide nanoarrays via anion exchange reaction and their electrochemical energy storage application. Small 2014, 10, 766-773.

Crossref Google Scholar
33

Wang, H.; Zhuo, S. F.; Liang, Y.; Han, X. L.; Zhang, B. General self-template synthesis of transition-metal oxide and chalcogenide mesoporous nanotubes with enhanced electrochemical performances. Angew. Chem., Int. Ed. 2016, 55, 9055-9059.

Crossref Google Scholar
34

Zhu, L. P.; Wen, Z.; Mei, W. M.; Li, Y. G.; Ye, Z. Z. Porous CoO nanostructure arrays converted from rhombic Co(OH)F and needle-like Co(CO3)0.5(OH)·0.11H2O and their electrochemical properties. J. Phys. Chem. C 2013, 117, 20465-20473.

Crossref Google Scholar
35

Jiang, J.; Liu, J. P.; Huang, X. T.; Li, Y. Y.; Ding, R.M.; Ji, X. X.; Hu, Y. Y.; Chi, Q. B.; Zhu, Z. H. General synthesis of large-scale arrays of one-dimensional nanostructured Co3O4 directly on heterogeneous substrates. Cryst. Growth Des. 2010, 10, 70-75.

Crossref Google Scholar
36

Kresse, G.; Furthmuller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 1996, 6, 15-50.

Crossref Google Scholar
37

Kresse, G.; Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169-11186.

Crossref Google Scholar
38

Kresse, G.; Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germaniu. Phys. Rev. B 1994, 49, 14251-14269.

Crossref Google Scholar
39

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple[Phys. Rev. Lett. 77, 3865 (1996)]. Phys. Rev. Lett. 1997, 78, 1396.

Crossref Google Scholar
40

Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758-1775.

Crossref Google Scholar
41

Blochl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953-17979.

Crossref Google Scholar
42

Monkhorst, H. J.; Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 1976, 13, 5188-5192.

Crossref Google Scholar
43

Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 2006, 27, 1787-1799.

Crossref Google Scholar
44

Nøskov, J. K.; Bligaard, T.; Logadottir, A.; Kitchin, J. R.; Chen, J. G.; Pandelov, S.; Stimming, U. Trends in the exchange current for hydrogen evolutio. J. Electrochem. Soc. 2005, 152, J23-J26.

Crossref Google Scholar
45

Sivanantham, A.; Ganesan, P.; Shanmugam, S. Hierarchical NiCo2S4 nanowire arrays supported on Ni foam: An efficient and durable bifunctional electrocatalyst for oxygen and hydrogen evolution reactions. Adv. Funct. Mater. 2016, 26, 4661-4672.

Crossref Google Scholar
46

Gu, D.; Jia, C. -J.; Weidenthaler, C.; Bongard, H. -J.; Spliethoff, B.; Schmidt, W.; Schüth, F. Highly ordered mesoporous cobalt-containing oxides: Structure, catalytic properties, and active sites in oxidation of carbon monoxide. J. Am. Chem. Soc. 2015, 137, 11407-11418.

Crossref Google Scholar
47

Martin-Aranda, R. M.; Portela, M. F.; Madeira, L. M.; Freire, F.; Oliveira, M. Effect of alkali metal promoters on nickel molybdate catalysts and its relevance to the selective oxidation of butane. Appl. Catal. A: Gen. 1995, 127, 201-217.

Crossref Google Scholar
48

Ozkar, S.; Ozin, G. A.; Prokopowicz, R. A. Photooxidation of hexacarbonylmolybdenum(0) in sodium zeolite Y to yield redox-interconvertible molybdenum(Ⅵ) oxide and molybdenum(Ⅳ) oxide monomers. Chem. Mater. 1992, 4, 1380-1388.

Crossref Google Scholar
49

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
50

Xing, Z. C.; Liu, Q.; Asiri, A. M.; Sun, X. P. Closely interconnected network of molybdenum phosphide nanoparticles: A highly efficient electrocatalyst for generating hydrogen from water. Adv. Mater. 2014, 26, 5702-5707.

Crossref Google Scholar
51

Zou, X. X.; Huang, X. X.; Goswami, A.; Silva, R.; Sathe, B. R.; Mikmeková, E.; Asefa, T. Cobalt-embedded nitrogen-rich carbon nanotubes efficiently catalyze hydrogen evolution reaction at all pH values. Angew. Chem., Int. Ed. 2014, 53, 4372-4376.

Crossref Google Scholar
52

Gu, H. H.; Huang, Y. P.; Zuo, L. Z.; Fan, W.; Liu, T. X. Electrospun carbon nanofiber@CoS2 core/sheath hybrid as an efficient all-pH hydrogen evolution electrocatalyst. Inorg. Chem. Front. 2016, 3, 1280-1288.

Crossref Google Scholar
53

Tran, P. D.; Chiam, S. Y.; Boix, P. P.; Ren, Y.; Pramana, S. S.; Fize, J.; Artero V.; Barber, J. Novel cobalt/nickel-tungsten-sulfide catalysts for electrocatalytic hydrogen generation from water. Energy Environ. Sci. 2013, 6, 2452-2459.

Crossref Google Scholar
54

Shin, S.; Jin, Z. Y.; Kwon, D. H.; Bose, R.; Min, Y. -S. High turnover frequency of hydrogen evolution reaction on amorphous MoS2 thin film directly grown by atomic layer deposition. Langmuir 2015, 31, 1196-1201.

Crossref Google Scholar
55

Xu, Y. F.; Gao, M. R.; Zheng, Y. R.; Jiang, J.; Yu, S. H. Nickel/nickel(Ⅱ) oxide nanoparticles anchored onto cobalt(Ⅳ) diselenide nanobelts for the electrochemical production of hydrogen. Angew. Chem., Int. Ed. 2013, 52, 8546-8550.

Crossref Google Scholar
56

Lu, X. Y.; Zhao, C. Electrodeposition of hierarchically structured three-dimensional nickel-iron electrodes for efficient oxygen evolution at high current densities. Nat. Commun. 2015, 6, 6616.

Crossref Google Scholar
57

Wang, J. M.; Ma, X.; Qu, F. L.; Asiri, A. M.; Sun, X. P. Fe-doped Ni2P nanosheet array for high-efficiency electrochemical water oxidation. Inorg. Chem. 2017, 56, 1041-1044.

Crossref Google Scholar
58

Jiang, J.; Gao, M. R.; Sheng, W. C.; Yan, Y. S. Hollow chevrel-phase NiMo3S4 for hydrogen evolution in alkaline electrolytes. Angew. Chem., Int. Ed. 2016, 55, 15240-15245.

Crossref Google Scholar
59

Yan, X. D.; Tian, L. H.; He, M.; Chen, X. B. Three-dimensional crystalline/amorphous Co/Co3O4 core/shell nanosheets as efficient electrocatalysts for the hydrogen evolution reaction. Nano Lett. 2015, 15, 6015-6021.

Crossref Google Scholar
60

Chen, W.; Wang, H. T.; Li, Y. Z.; Liu, Y. Y.; Sun, J.; Lee, S. H.; Lee, J. -S.; Cui, Y. In situ electrochemical oxidation tuning of transition metal disulfides to oxides for enhanced water oxidation. ACS Cent. Sci. 2015, 1, 244-251.

Crossref Google Scholar
61

Karunadasa, H. I.; Chang, C. J.; Long, J. R. A molecular molybdenum-oxo catalyst for generating hydrogen from water. Nature 2010, 464, 1329-1333.

Crossref Google Scholar
62

Ren, X.; Wang, W. Y.; Ge, R. X.; Hao, S.; Qu, F. L.; Du, G.; Asiri, A. M.; Wei, Q.; Chen, L.; Sun, X. P. An amorphous FeMoS4 nanorod array toward efficient hydrogen evolution electrocatalysis under neutral conditions. Chem. Commun. 2017, 53, 9000-9003.

Crossref Google Scholar
63

Li, H. M.; Qian, X.; Zhu, C. L.; Jiang, X. C.; Shao, L.; Hou, L. X. Template synthesis of CoSe2/Co3Se4 nanotubes: Tuning of their crystal structures for photovoltaics and hydrogen evolution in alkaline medium. J. Mater. Chem. A 2017, 5, 4513-4526.

Crossref Google Scholar
64

Wang, W. Y.; Yang, L.; Qu, F. L.; Liu, Z. A.; Du, G.; Asiri, A. M.; Yao, Y. D.; Chen L.; Sun X. P. A self-supported NiMoS4 nanoarray as an efficient 3D cathode for the alkaline hydrogen evolution reaction. J Mater. Chem. A 2017, 5, 16585-16589.

Crossref Google Scholar
65

Shao, L.; Qian, X.; Wang, X. Y.; Li, H. M.; Yan, R. C.; Hou, L. X. Low-cost and highly efficient CoMoS4/NiMoS4-based electrocatalysts for hydrogen evolution reactions over a wide pH range. Electrochim. Acta 2016, 213, 236-243.

Crossref Google Scholar
66

Yu, L.; Xia, B. Y.; Wang, X.; Lou, X. W. General formation of M-MoS3 (M = Co, Ni) hollow structures with enhanced electrocatalytic activity for hydrogen evolution. Adv. Mater. 2016, 28, 92-97.

Crossref Google Scholar
Nano Research
Volume 11 Issue 4,
April 2018
Pages 2024-2033
DOI: 10.1007/s12274-017-1818-6
Cite this article:
Ren X, Wu D, Ge R, et al. Self-supported CoMoS4 nanosheet array as an efficient catalyst for hydrogen evolution reaction at neutral pH. Nano Research, 2018, 11(4): 2024-2033. https://doi.org/10.1007/s12274-017-1818-6
Part of a topical collection:
The winners of “Top Papers Award” in 2019
Metrics & Citations  
Article History
Copyright
Return