Oxygen-deficient MoOx/Ni3S2 heterostructure grown on nickel foam as efficient and durable self-supported electrocatalysts for hydrogen evolution reaction

Zihuan Yu, Haiqing Yan, Chaonan Wang, Zheng Wang, Huiqin Yao, Rong Liu, Cheng Li, Shulan Ma

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Front. Chem. Sci. Eng. ›› 2023, Vol. 17 ›› Issue (4) : 437-448. DOI: 10.1007/s11705-022-2228-1
RESEARCH ARTICLE
RESEARCH ARTICLE

Oxygen-deficient MoOx/Ni3S2 heterostructure grown on nickel foam as efficient and durable self-supported electrocatalysts for hydrogen evolution reaction

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Abstract

High-performance and ultra-durable electrocatalysts are vital for hydrogen evolution reaction (HER) during water splitting. Herein, by one-pot solvothermal method, MoOx/Ni3S2 spheres comprising Ni3S2 nanoparticles inside and oxygen-deficient amorphous MoOx outside in situ grow on Ni foam (NF), to assembly the heterostructure composites of MoOx/Ni3S2/NF. By adjusting volume ratio of the solvents of ethanol to water, the optimized MoOx/Ni3S2/NF-11 exhibits the best HER performance, requiring an extremely low overpotential of 76 mV to achieve the current density of 10 mA∙cm‒2 (η10 = 76 mV) and an ultra-small Tafel slope of 46 mV∙dec‒1 in 0.5 mol∙L‒1 H2SO4. More importantly, the catalyst shows prominent high catalytic stability for HER (> 100 h). The acid-resistant MoOx wraps the inside Ni3S2/NF to ensure the high stability of the catalyst under acidic conditions. Density functional theory calculations confirm that the existing oxygen vacancy and MoOx/Ni3S2 heterostructure are both beneficial to the reduced Gibbs free energy of hydrogen adsorption (|∆GH*|) over Mo sites, which act as main active sites. The heterostructure effectively decreases the formation energy of O vacancy, leading to surface reconstruction of the catalyst, further improving HER performance. The MoOx/Ni3S2/NF is promising to serve as a highly effective and durable electrocatalyst toward HER.

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Keywords

molybdenum oxides / oxygen vacancies / heterostructure / electrocatalysts / hydrogen evolution reaction

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Zihuan Yu, Haiqing Yan, Chaonan Wang, Zheng Wang, Huiqin Yao, Rong Liu, Cheng Li, Shulan Ma. Oxygen-deficient MoOx/Ni3S2 heterostructure grown on nickel foam as efficient and durable self-supported electrocatalysts for hydrogen evolution reaction. Front. Chem. Sci. Eng., 2023, 17(4): 437‒448 https://doi.org/10.1007/s11705-022-2228-1

References

[1]
Zou X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting. Chemical Society Reviews, 2015, 44(15): 5148–5180
CrossRef Google scholar
[2]
Turner J A. Sustainable hydrogen production. Science, 2004, 305(5686): 972–974
CrossRef Google scholar
[3]
Holladay J D, Hu J, King D L, Wang Y. An overview of hydrogen production technologies. Catalysis Today, 2009, 139(4): 244–260
CrossRef Google scholar
[4]
Chen W F, Muckerman J T, Fujita E. Recent developments in transition metal carbides and nitrides as hydrogen evolution electrocatalysts. Chemical Communications, 2013, 49(79): 8896–8909
CrossRef Google scholar
[5]
Zhang J, Wang T, Liu P, Liao Z, Liu S, Zhuang X, Chen M, Zschech E, Feng X. Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics. Nature Communications, 2017, 8(1): 15437
CrossRef Google scholar
[6]
Stamenkovic V R, Mun B S, Arenz M, Mayrhofer K J J, Lucas C A, Wang G F, Ross P N, Markovic N M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nature Materials, 2007, 6(3): 241–247
CrossRef Google scholar
[7]
Wang K W, She X L, Chen S, Liu H L, Li D H, Wang Y, Zhang H W, Yang D J, Yao X D. Boosting hydrogen evolution via optimized hydrogen adsorption at the interface of CoP3 and Ni2P. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2018, 6(14): 5560–5565
CrossRef Google scholar
[8]
Lu W, Song Y, Dou M, Ji J, Wang F. Ni3S2@MoO3 core/shell arrays on Ni foam modified with ultrathin CdS layer as a superior electrocatalyst for hydrogen evolution reaction. Chemical Communications, 2018, 54(6): 646–649
CrossRef Google scholar
[9]
Wang X, Ma W, Ding C, Xu Z, Wang H, Zong X, Li C. Amorphous multi-elements electrocatalysts with tunable bifunctionality toward overall water splitting. ACS Catalysis, 2018, 8(11): 9926–9935
CrossRef Google scholar
[10]
Liang Q, Jin H, Wang Z, Xiong Y, Yuan S, Zeng X, He D, Mu S. Metal–organic frameworks derived reverse-encapsulation Co-NC@Mo2C complex for efficient overall water splitting. Nano Energy, 2019, 57: 746–752
CrossRef Google scholar
[11]
Li L, Zhang T, Yan J, Cai X, Liu S. P doped MoO3−x nanosheets as efficient and stable electrocatalysts for hydrogen evolution. Small, 2017, 13(25): 1700441
CrossRef Google scholar
[12]
Sinaim H, Ham D J, Lee J S, Phuruangrat A, Thongtem S, Thongtem T. Free-polymer controlling morphology of α-MoO3 nanobelts by a facile hydrothermal synthesis, their electrochemistry for hydrogen evolution reactions and optical properties. Journal of Alloys and Compounds, 2012, 516: 172–178
CrossRef Google scholar
[13]
Zhu Y H, Yao Y, Luo Z, Pan C Q, Yang J, Fang Y R, Deng H T, Liu C X, Tan Q, Liu F D, Guo Y. Nanostructured MoO3 for efficient energy and environmental catalysis. Molecules, 2020, 25(1): 26
[14]
Li J, Cheng Y, Zhang J, Fu J, Yan W, Xu Q. Confining Pd nanoparticles and atomically dispersed Pd into defective MoO3 nanosheet for enhancing electro- and photocatalytic hydrogen evolution performances. ACS Applied Materials & Interfaces, 2019, 11(31): 27798–27804
CrossRef Google scholar
[15]
Xue X, Zhang J, Saana I A, Sun J, Xu Q, Mu S. Rational inert-basal-plane activating design of ultrathin 1T′ phase MoS2 with a MoO3 heterostructure for enhancing hydrogen evolution performances. Nanoscale, 2018, 10(35): 16531–16538
CrossRef Google scholar
[16]
Liu P T, Zhu J Y, Zhang J Y, Xi P X, Tao K, Gao D Q, Xue D S. P dopants triggered new basal plane active sites and enlarged interlayer spacing in MoS2 nanosheets toward electrocatalytic hydrogen evolution. ACS Energy Letters, 2017, 2(4): 745–752
CrossRef Google scholar
[17]
Sadhanala H K, Harika V K, Penki T R, Aurbach D, Gedanken A. Ultrafine ruthenium oxide nanoparticles supported on molybdenum oxide nanosheets as highly efficient electrocatalyst for hydrogen evolution in acidic medium. ChemCatChem, 2019, 11(5): 1495–1502
CrossRef Google scholar
[18]
Lim K J H, Yilmaz G, Lim Y F, Ho G W. Multi-compositional hierarchical nanostructured Ni3S2@MoSx/NiO electrodes for enhanced electrocatalytic hydrogen generation and energy storage. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2018, 6(41): 20491–20499
CrossRef Google scholar
[19]
Kou T, Smart T, Yao B, Chen I, Thota D, Ping Y, Li Y. Theoretical and experimental insight into the effect of nitrogen doping on hydrogen evolution activity of Ni3S2 in alkaline medium. Advanced Energy Materials, 2018, 8(19): 1703538
CrossRef Google scholar
[20]
Feng L L, Yu G, Wu Y, Li G D, Li H, Sun Y, Asefa T, Chen W, Zou X. High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting. Journal of the American Chemical Society, 2015, 137(44): 14023–14026
CrossRef Google scholar
[21]
Chang Y H, Lin C T, Chen T Y, Hsu C L, Lee Y H, Zhang W, Wei K H, Li L J. Highly efficient electrocatalytic hydrogen production by MoSx grown on graphene-protected 3D Ni foams. Advanced Materials, 2013, 25(5): 756–760
CrossRef Google scholar
[22]
Tang C, Pu Z, Liu Q, Asiri A M, Luo Y, Sun X. Ni3S2 nanosheets array supported on Ni foam: a novel efficient three-dimensional hydrogen-evolving electrocatalyst in both neutral and basic solutions. International Journal of Hydrogen Energy, 2015, 40(14): 4727–4732
CrossRef Google scholar
[23]
Cao J, Zhou J, Zhang Y, Wang Y, Liu X. Dominating role of aligned MoS2/Ni3S2 nanoarrays supported on three-dimensional Ni foam with hydrophilic interface for highly enhanced hydrogen evolution reaction. ACS Applied Materials & Interfaces, 2018, 10(2): 1752–1760
CrossRef Google scholar
[24]
Yang Y, Yao H, Yu Z, Islam S M, He H, Yuan M, Yue Y, Xu K, Hao W, Sun G, Li H, Ma S, Zapol P, Kanatzidis M G. Hierarchical nanoassembly of MoS2/Co9S8/Ni3S2/Ni as a highly efficient electrocatalyst for overall water splitting in a wide pH range. Journal of the American Chemical Society, 2019, 141(26): 10417–10430
CrossRef Google scholar
[25]
Li T T, Zuo Y P, Lei X M, Li N, Liu J W, Han H Y. Regulating the oxidation degree of nickel foam: a smart strategy to controllably synthesize active Ni3S2 nanorod/nanowire arrays for high-performance supercapacitors. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(21): 8029–8040
CrossRef Google scholar
[26]
Tang T, Jiang W J, Niu S, Liu N, Luo H, Chen Y Y, Jin S F, Gao F, Wan L J, Hu J S. Electronic and morphological dual modulation of cobalt carbonate hydroxides by Mn doping toward highly efficient and stable bifunctional electrocatalysts for overall water splitting. Journal of the American Chemical Society, 2017, 139(24): 8320–8328
CrossRef Google scholar
[27]
He W, Wang C, Li H, Deng X, Xu X, Zhai T. Ultrathin and porous Ni3S2/CoNi2S4 3D-network structure for superhigh energy density asymmetric supercapacitors. Advanced Energy Materials, 2017, 7(21): 1700983
CrossRef Google scholar
[28]
Yang J, Zhang F J, Wang X, He D S, Wu G, Yang Q H, Hong X, Wu Y, Li Y D. Porous molybdenum phosphide nano-octahedrons derived from confined phosphorization in UIO-66 for efficient hydrogen evolution. Angewandte Chemie International Edition, 2016, 55(41): 12854–12858
CrossRef Google scholar
[29]
Weber T, Muijsers J C, Niemantsverdriet J W. Structure of amorphous MoS3. Journal of Physical Chemistry, 1995, 99(22): 9194–9200
CrossRef Google scholar
[30]
Li L D, Yan J Q, Wang T, Zhao Z J, Zhang J, Gong J L, Guan N J. Sub-10 nm rutile titanium dioxide nanoparticles for efficient visible-light-driven photocatalytic hydrogen production. Nature Communications, 2015, 6(1): 10
CrossRef Google scholar
[31]
Li J, Cheng Y, Zhang J, Fu J, Yan W, Xu Q. Confining Pd Nanoparticles and atomically dispersed Pd into defective MoO3 nanosheet for enhancing electro- and photocatalytic hydrogen evolution performances. ACS Applied Materials & Interfaces, 2019, 11(31): 27798–27804
CrossRef Google scholar
[32]
Kang Q, Cao J Y, Zhang Y J, Liu L Q, Xu H, Ye J H. Reduced TiO2 nanotube arrays for photoelectrochemical water splitting. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2013, 1(18): 5766–5774
CrossRef Google scholar
[33]
Yan J Q, Zhang Y X, Liu S Z, Wu G J, Li L D, Guan N J. Facile synthesis of an iron doped rutile TiO2 photocatalyst for enhanced visible-light-driven water oxidation. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2015, 3(43): 21434–21438
CrossRef Google scholar
[34]
Xie F, Wu H, Mou J, Lin D, Xu C, Wu C, Sun X. Ni3N@Ni-Ci nanoarray as a highly active and durable non-noble-metal electrocatalyst for water oxidation at near-neutral pH. Journal of Catalysis, 2017, 356: 165–172
CrossRef Google scholar
[35]
Zhou W, Wu X J, Cao X, Huang X, Tan C, Tian J, Liu H, Wang J, Zhang H. Ni3S2 nanorods/Ni foam composite electrode with low overpotential for electrocatalytic oxygen evolution. Energy & Environmental Science, 2013, 6(10): 2921
CrossRef Google scholar
[36]
Chia X, Sutrisnoh N A A, Pumera M. Tunable Pt-MoSx hybrid catalysts for hydrogen evolution. ACS Applied Materials & Interfaces, 2018, 10(10): 8702–8711
CrossRef Google scholar
[37]
Kuang P Y, Tong T, Fan K, Yu J G. In situ fabrication of Ni−Mo bimetal sulfide hybrid as an efficient electrocatalyst for hydrogen evolution over a wide pH range. ACS Catalysis, 2017, 7(9): 6179–6187
CrossRef Google scholar
[38]
Wang B, Huang H, Sun T, Yan P, Isimjan T T, Tian J, Yang X. Dissolution reconstruction of electron-transfer enhanced hierarchical NiSx−MoO2 nanosponges as a promising industrialized hydrogen evolution catalyst beyond Pt/C. Journal of Colloid and Interface Science, 2020, 567: 339–346
CrossRef Google scholar
[39]
Cheng Z, Abernathy H, Liu M L. Raman spectroscopy of nickel sulfide Ni3S2. Journal of Physical Chemistry C, 2007, 111(49): 17997–18000
CrossRef Google scholar
[40]
Li Z, Ma J, Zhang B, Song C, Wang D. Crystal phase- and morphology-controlled synthesis of MoO3 materials. CrystEngComm, 2017, 19(11): 1479–1485
CrossRef Google scholar
[41]
Qi K, Yu S S, Wang Q Y, Zhang W, Fan J C, Zheng W T, Cui X Q. Decoration of the inert basal plane of defect-rich MoS2 with Pd atoms for achieving Pt-similar HER activity. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(11): 4025–4031
CrossRef Google scholar
[42]
Huang H L, Huang J Y, Liu W P, Fang Y P, Liu Y. Ultradispersed and single-layered MoS2 nanoflakes strongly coupled with graphene: an optimized structure with high kinetics for the hydrogen evolution reaction. ACS Applied Materials & Interfaces, 2017, 9(45): 39380–39390
CrossRef Google scholar
[43]
Xiong J, Li J, Shi J W, Zhang X L, Suen N T, Liu Z, Huang Y J, Xu G X, Cai W W, Lei X R, Feng L, Yang Z, Huang L, Cheng H. In situ engineering of double-phase interface in Mo/Mo2C heteronanosheets for boosted hydrogen evolution reaction. ACS Energy Letters, 2018, 3(2): 341–348
CrossRef Google scholar
[44]
Manikandan A, Ilango P R, Chen C W, Wang Y C, Shih Y C, Lee L, Wang Z M M, Ko H, Chueh Y L. A superior dye adsorbent towards the hydrogen evolution reaction combining active sites and phase-engineering of (1T/2H) MoS2/MoO3 hybrid heterostructured nanoflowers. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2018, 6(31): 15320–15329
CrossRef Google scholar
[45]
Huang C, Pi C R, Zhang X M, Ding K, Qin P, Fu J J, Peng X, Gao B, Chu P K, Huo K F. In situ synthesis of MoP nanoflakes intercalated N-doped graphene nanobelts from MoO3-amine hybrid for high-efficient hydrogen evolution reaction. Small, 2018, 14(25): 7
CrossRef Google scholar
[46]
Wu H B, Xia B Y, Yu L, Yu X Y, Lou X W. Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal−organic frameworks for efficient hydrogen production. Nature Communications, 2015, 6(1): 8
CrossRef Google scholar
[47]
Chen X, Liu G, Zheng W, Feng W, Cao W, Hu W, Hu P. Vertical 2D MoO2/MoSe2 core-shell nanosheet arrays as high-performance electrocatalysts for hydrogen evolution reaction. Advanced Functional Materials, 2016, 26(46): 8537–8544
CrossRef Google scholar
[48]
Zhu L F, Liu L J, Huang G M, Zhao Q. Hydrogen evolution over N-doped CoS2 nanosheets enhanced by superaerophobicity and electronic modulation. Applied Surface Science, 2020, 504: 144490
CrossRef Google scholar
[49]
He L, Zhang W, Mo Q, Huang W, Yang L, Gao Q. Molybdenum carbide-oxide heterostructures: in situ surface reconfiguration toward efficient electrocatalytic hydrogen evolution. Angewandte Chemie International Edition, 2020, 59(9): 3544–3548
CrossRef Google scholar
[50]
Yilmaz G, Yang T, Du Y, Yu X, Feng Y, Shen L, Ho G. Stimulated electrocatalytic hydrogen evolution activity of MOF-derived MoS2 basal domains via charge injection through surface functionalization and heteroatom doping. Advancement of Science, 2019, 6(15): 1900140

Acknowledgements

Experimental work is supported by the National Natural Science Foundation of China (Grant No. 22176017), Scientific Research Project of the Ningxia Higher Education Department of China (Grant No. NGY2020034) and CAS “Light of West China Program (Grant No. XAB2020YW16)”.

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Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2228-1 and is accessible for authorized users.

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