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

Phosphorus-induced electronic structure reformation of hollow NiCo2Se4 nanoneedle arrays enabling highly efficient and durable hydrogen evolution in all-pH media

Guojing Wang§, Yuzhuo Sun§, Yidan Zhao, Yang Zhang, Xiaohong Li, Louzhen Fan, Yunchao Li()
Key laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, China

§ Guojing Wang and Yuzhuo Sun contributed equally to this work.

Show Author Information

Graphical Abstract

View original image Download original image
P8.71-NiCo2Se4/CFP hollow nanoneedle arrays grown on carbon fiber paper were first synthesized, which exhibit an outstanding hydrogen evolution reaction (HER) performance and good durability in all-pH media due to the optimized electronic structure and the increased active sites induced by the P doping.

Abstract

With practical electrocatalytic hydrogen production frequently involving the splitting of water in various pH media, there is an urgent need but still a technical challenge to develop low-cost, highly active, and stable electrocatalysts for pH-universal hydrogen evolution reaction (HER). We report herein the adoption of a hydrothermal reaction combined with a post gas-phase doping strategy to fabricate P-doped NiCo2Se4 hollow nanoneedle arrays on carbon fiber paper (i.e., P-NiCo2Se4/CFP). Notably, the optimal arrays (P8.71-NiCo2Se4/CFP) can afford an outstanding pH-universal HER performance, with an overpotential as low as 33, 57, and 69 mV at 10 mA·cm−2 and corresponding Tafel slopes down to 52, 61, and 72 mV·dec−1 in acidic, alkaline, and neutral media, respectively, outperforming most state-of-the-art nonprecious catalysts and even the commercial Pt/C catalyst in both neutral and alkaline media at large current densities. Impressively, P8.71-NiCo2Se4/CFP also displays good durability toward long-time stability testing in harsh acidic and alkaline electrolytes. Experimental and theoretical studies further reveal that the doping of P atoms into NiCo2Se4 can simultaneously optimize its H* adsorption/desorption energy, water adsorption energy, and water dissociation energy by adjusting the local electronic states of various active sites, thus accelerating the rate-determining step of HER in different pH media to endow P-NiCo2Se4 with an outstanding pH-universal HER performance. This work provides atomic-level insights into the roles of active sites in various electrolysis environments, thereby shedding new light on the rational design of highly efficient pH-universal nonprecious catalysts for HER and beyond.

Keywords

P-doped NiCo2Se4 nanoarrayslocal electronic structurehydrogen evolution reaction (HER)pH-universal electrocatalysisdensity functional theory (DFT) calculation

Electronic Supplementary Material

Download File(s)
12274_2022_4534_MOESM1_ESM.pdf (3.7 MB)

References

1

Qi, J.; Zhang, W.; Cao, R. Solar-to-hydrogen energy conversion based on water splitting. Adv. Energy Mater. 2018, 8, 1701620.

Crossref Google Scholar
2

Turner, J. A. Sustainable hydrogen production. Science 2004, 305, 972–974.

Crossref Google Scholar
3

Shi, Y.; Zhou, Y.; Yang, D. R.; Xu, W. X.; Wang, C.; Wang, F. B.; Xu, J. J.; Xia, X. H.; Chen, H. Y. Energy level engineering of MoS2 by transition-metal doping for accelerating hydrogen evolution reaction. J. Am. Chem. Soc. 2017, 139, 15479–15485.

Crossref Google Scholar
4

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

Crossref Google Scholar
5

You, B.; Sun, Y. J. Innovative strategies for electrocatalytic water splitting. Acc. Chem. Res. 2018, 51, 1571–1580.

Crossref Google Scholar
6

Li, Y.; Luo, Z. Y.; Ge, J. J.; Liu, C. P.; Xing, W. Research progress in hydrogen evolution low noble/non-precious metal catalysts of water electrolysis. J. Electrochem. 2018, 24, 572–588.

Crossref Google Scholar
7

Carmo, M.; Fritz, D. L.; Mergel, J.; Stolten, D. A comprehensive review on PEM water electrolysis. Int. J. Hydrogen Energy 2013, 38, 4901–4934.

Crossref Google Scholar
8

Sun, X. W.; Xu, K. Q.; Fleischer, C.; Liu, X.; Grandcolas, M.; Strandbakke, R.; Bjørheim, T. S.; Norby, T.; Chatzitakis, A. Earth abundant electrocatalysts in proton exchange membrane electrolyzers. Catalysts 2018, 8, 657.

Crossref Google Scholar
9

Yu, Z. Y.; Duan, Y.; Feng, X. Y.; Yu, X. X.; Gao, M. R.; Yu, S. H. Clean and affordable hydrogen fuel from alkaline water splitting: Past, recent progress, and future prospects. Adv. Mater. 2021, 33, 2007100.

Crossref Google Scholar
10

Hu, C. L.; Zhang, L.; Gong, J. L. Recent progress made in the mechanism comprehension and design of electrocatalysts for alkaline water splitting. Energy Environ. Sci. 2019, 12, 2620–2645.

Crossref Google Scholar
11

Anantharaj, S.; Noda, S.; Jothi, V. R.; Yi, S.; Driess, M.; Menezes, P. W. Strategies and perspectives to catch the missing pieces in energy-efficient hydrogen evolution reaction in alkaline media. Angew. Chem., Int. Ed. 2021, 60, 18981–19006.

Crossref Google Scholar
12

Bennett, J. E. Electrodes for generation of hydrogen and oxygen from seawater. Int. J. Hydrogen Energy 1980, 5, 401–408.

Crossref Google Scholar
13

Dresp, S.; Dionigi, F.; Klingenhof, M.; Strasser, P. Direct electrolytic splitting of seawater: Opportunities and challenges. ACS Energy Lett. 2019, 4, 933–942.

Crossref Google Scholar
14

Yu, L.; Wu, L. B.; Song, S. W.; McElhenny, B.; Zhang, F. H.; Chen, S.; Ren, Z. F. Hydrogen generation from seawater electrolysis over a sandwich-like NiCoN|NixP|NiCoN microsheet arrays catalyst. ACS Energy Lett. 2020, 5, 2681–2689.

Crossref Google Scholar
15

Kibsgaard, J.; Chorkendorff, I. Considerations for the scaling-up of water splitting catalysts. Nat. Energy 2019, 4, 430–433.

Crossref Google Scholar
16

Gupta, S.; Patel, N.; Fernandes, R.; Kadrekar, R.; Dashora, A.; Yadav, A. K.; Bhattacharyya, D.; Jha, S. N.; Miotello, A.; Kothari, D. C. Co-Ni-B nanocatalyst for efficient hydrogen evolution reaction in wide pH range. Appl. Catal. B: Environ. 2016, 192, 126–133.

Crossref Google Scholar
17

Jin, H. Y.; Liu, X.; Vasileff, A.; Jiao, Y.; Zhao, Y. Q.; Zheng, Y.; Qiao, S. Z. Single-crystal nitrogen-rich two-dimensional Mo5N6 nanosheets for efficient and stable seawater splitting. ACS Nano 2018, 12, 12761–12769.

Crossref Google Scholar
18

Xu, H. T.; Wan, J.; Zhang, H. J.; Fang, L.; Liu, L.; Huang, Z. Y.; Li, J.; Gu, X.; Wang, Y. A new platinum-like efficient electrocatalyst for hydrogen evolution reaction at all pH: Single-crystal metallic interweaved V8C7 networks. Adv. Energy Mater. 2018, 8, 1800575.

Crossref Google Scholar
19

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 Catal. 2017, 7, 6179–6187.

Crossref Google Scholar
20

Staszak-Jirkovský, J.; Malliakas, C. D.; Lopes, P. P.; Danilovic, N.; Kota, S. S.; Chang, K. C.; Genorio, B.; Strmcnik, D.; Stamenkovic, V. R.; Kanatzidis, M. G. et al. Design of active and stable Co-Mo-Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction. Nat. Mater. 2016, 15, 197–203.

Crossref Google Scholar
21

Yu, J.; Zhang, M. L.; Liu, J. Y.; Chen, R. R.; Li, R. M.; Liu, Q.; Zhou, L. M.; Liu, P. L.; Wang, J. Heterogeneous NiSe2/Ni ultrafine nanoparticles embedded into an N, S-codoped carbon framework for pH-universal hydrogen evolution reaction. ACS Sustain. Chem. Eng. 2019, 7, 4119–4127.

Crossref Google Scholar
22

Zhang, R.; Wang, X. X.; Yu, S. J.; Wen, T.; Zhu, X. W.; Yang, F. X.; Sun, X. N.; Wang, X. K.; Hu, W. P. Ternary NiCo2Px nanowires as pH-universal electrocatalysts for highly efficient hydrogen evolution reaction. Adv. Mater. 2017, 29, 1605502.

Crossref Google Scholar
23

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
24

Jiao, Y. Q.; Yan, H. J.; Wang, R. H.; Wang, X. W.; Zhang, X. M.; Wu, A. P.; Tian, C. G.; Jiang, B. J.; Fu, H. G. Porous plate-like MoP assembly as an efficient pH-universal hydrogen evolution electrocatalyst. ACS Appl. Mater. Interfaces 2020, 12, 49596–49606.

Crossref Google Scholar
25

Cao, E. P.; Chen, Z. M.; Wu, H.; Yu, P.; Wang, Y.; Xiao, F.; Chen, S.; Du, S. C.; Xie, Y.; Wu, Y. Q. et al. Boron-induced electronic-structure reformation of CoP nanoparticles drives enhanced pH-universal hydrogen evolution. Angew. Chem., Int. Ed. 2020, 59, 4154–4160.

Crossref Google Scholar
26

Huang, J. J.; Wang, J. Y.; Xie, R. K.; Tian, Z. H.; Chai, G. L.; Zhang, Y. W.; Lai, F. L.; He, G. J.; Liu, C. T.; Liu, T. X. et al. A universal pH range and a highly efficient Mo2C-based electrocatalyst for the hydrogen evolution reaction. J. Mater. Chem. A 2020, 8, 19879–19886.

Crossref Google Scholar
27

Men, Y. N.; Li, P.; Zhou, J. H.; Cheng, G. Z.; Chen, S. L.; Luo, W. Tailoring the electronic structure of Co2P by N doping for boosting hydrogen evolution reaction at all pH values. ACS Catal. 2019, 9, 3744–3752.

Crossref Google Scholar
28

Luo, Y. T.; Tang, L.; Khan, U.; Yu, Q. M.; Cheng, H. M.; Zou, X. L.; Liu, B. L. Morphology and surface chemistry engineering toward pH-universal catalysts for hydrogen evolution at high current density. Nat. Commun. 2019, 10, 269.

Crossref Google Scholar
29

Geng, S.; Tian, F. Y.; Li, M. G.; Guo, X.; Yu, Y. S.; Yang, W. W.; Hou, Y. L. Hole-rich CoP nanosheets with an optimized d-band center for enhancing pH-universal hydrogen evolution electrocatalysis. J. Mater. Chem. A 2021, 9, 8561–8567.

Crossref Google Scholar
30

Gu, Y.; Wu, A. P.; Jiao, Y. Q.; Zheng, H. R.; Wang, X. Q.; Xie, Y.; Wang, L.; Tian, C. G.; Fu, H. G. Two-dimensional porous molybdenum phosphide/nitride heterojunction nanosheets for pH-universal hydrogen evolution reaction. Angew. Chem., Int. Ed. 2021, 60, 6673–6681.

Crossref Google Scholar
31

Kim, M.; Anjum, M. A. R.; Choi, M.; Jeong, H. Y.; Choi, S. H.; Park, N.; Lee, J. S. Covalent 0D–2D heterostructuring of Co9S8-MoS2 for enhanced hydrogen evolution in all pH electrolytes. Adv. Funct. Mater. 2020, 30, 2002536.

Crossref Google Scholar
32

Wu, A. P.; Gu, Y.; Xie, Y.; Yan, H. J.; Jiao, Y. Q.; Wang, D. X.; Tian, C. G. Interfacial engineering of MoS2/MoN heterostructures as efficient electrocatalyst for pH-universal hydrogen evolution reaction. J. Alloys Compd. 2021, 867, 159066.

Crossref Google Scholar
33

Xie, J. F.; Xie, Y. Transition metal nitrides for electrocatalytic energy conversion: Opportunities and challenges. Chem. -Eur. J. 2016, 22, 3588–3598.

Crossref Google Scholar
34

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. Nat. Commun. 2015, 6, 6512.

Crossref Google Scholar
35

Yao, M. Q.; Wang, B. J.; Sun, B. L.; Luo, L. F.; Chen, Y. J.; Wang, J. W.; Wang, N.; Komarneni, S.; Niu, X. B.; Hu, W. C. Rational design of self-supported Cu@WC core-shell mesoporous nanowires for pH-universal hydrogen evolution reaction. Appl. Catal. B: Environ. 2021, 280, 119451.

Crossref Google Scholar
36

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
37

Shen, Y.; Zhou, Y. F.; Wang, D.; Wu, X.; Li, J.; Xi, J. Y. Nickel-copper alloy encapsulated in graphitic carbon shells as electrocatalysts for hydrogen evolution reaction. Adv. Energy Mater. 2018, 8, 1701759.

Crossref Google Scholar
38

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
39

Mou, H. Y.; Xue, Z. M.; Zhang, B. L.; Lan, X.; Mu, T. C. Deep eutectic solvent strategy to form defect-rich N, S, and O tridoped carbon/Co9S8 hybrid materials for a pH-universal hydrogen evolution reaction. J. Mater. Chem. A 2021, 9, 2099–2103.

Crossref Google Scholar
40

Hafner, J. Ab-initio simulations of materials using VASP: Density-functional theory and beyond. J. Comput. Chem. 2008, 29, 2044–2078.

Crossref Google Scholar
41

Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. Phys. Rev. B 1992, 46, 6671–6687.

Crossref Google Scholar
42

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.

Crossref Google Scholar
43

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
44

Li, Y.; Gao, Y. G.; Yang, S.; Wu, C. Q.; Tan, Y. W. Anion-modulated nickel-based nanoheterostructures as high performance electrocatalysts for hydrogen evolution reaction. J. Mater. Chem. A 2020, 8, 12013–12027.

Crossref Google Scholar
45

Xin, Y. M.; Kan, X.; Gan, L. Y.; Zhang, Z. H. Heterogeneous bimetallic phosphide/sulfide nanocomposite for efficient solar-energy-driven overall water splitting. ACS Nano 2017, 11, 10303–10312.

Crossref Google Scholar
46

Hou, Y.; Qiu, M.; Zhang, T.; Zhuang, X. D.; Kim, C. S.; Yuan, C.; Feng, X. L. Ternary porous cobalt phosphoselenide nanosheets: An efficient electrocatalyst for electrocatalytic and photoelectrochemical water splitting. Adv. Mater. 2017, 29, 1701589.

Crossref Google Scholar
47

Wu, J.; Chen, T.; Zhu, C. Y.; Du, J. J.; Huang, L. S.; Yan, J.; Cai, D. M.; Guan, C.; Pan, C. X. Rational construction of a WS2/CoS2 heterostructure electrocatalyst for efficient hydrogen evolution at all pH values. ACS Sustainable Chem. Eng. 2020, 8, 4474–4480.

Crossref Google Scholar
48

McCrory, C. C. L.; Jung, S.; Peters, J. C.; Jaramillo, T. F. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J. Am. Chem. Soc. 2013, 135, 16977–16987.

Crossref Google Scholar
49

Subbaraman, R.; Tripkovic, D.; Strmcnik, D.; Chang, K. C.; Uchimura, M.; Paulikas, A. P.; Stamenkovic, V.; Markovic, N. M. Enhancing hydrogen evolution activity in water splitting by tailoring Li+-Ni(OH)2-Pt interfaces. Science 2011, 334, 1256–1260.

Crossref Google Scholar
50

Zhou, K. L.; Wang, Z. L.; Han, C. B.; Ke, X. X.; Wang, C. H.; Jin, Y. H.; Zhang, Q. Q.; Liu, J. B.; Wang, H.; Yan, H. Platinum single-atom catalyst coupled with transition metal/metal oxide heterostructure for accelerating alkaline hydrogen evolution reaction. Nat. Commun. 2021, 12, 3783.

Crossref Google Scholar
51

Kucernak, A. R. J.; Sundaram, V. N. N. Nickel phosphide: The effect of phosphorus content on hydrogen evolution activity and corrosion resistance in acidic medium. J. Mater. Chem. A 2014, 2, 17435–17445.

Crossref Google Scholar
52

Zhang, G.; Feng, Y. S.; Lu, W. T.; He, D.; Wang, C. Y.; Li, Y. K.; Wang, X. Y.; Cao, F. F. Enhanced catalysis of electrochemical overall water splitting in alkaline media by Fe doping in Ni3S2 nanosheet arrays. ACS Catal. 2018, 8, 5431–5441.

Crossref Google Scholar
53

Zheng, Y. R.; Wu, P.; Gao, M. R.; Zhang, X. L.; Gao, F. Y.; Ju, H. X.; Wu, R.; Gao, Q.; You, R.; Huang, W. X. et al. Doping-induced structural phase transition in cobalt diselenide enables enhanced hydrogen evolution catalysis. Nat. Commun. 2018, 9, 2533.

Crossref Google Scholar
54

Chen, G. B.; Wang, T.; Zhang, J.; Liu, P.; Sun, H. J.; Zhuang, X. D.; Chen, M. W.; Feng, X. L. Accelerated hydrogen evolution kinetics on NiFe-layered double hydroxide electrocatalysts by tailoring water dissociation active sites. Adv. Mater. 2018, 30, 1706279.

Crossref Google Scholar
55

Dong, J.; Zhang, F. Q.; Yang, Y.; Zhang, Y. B.; He, H. L.; Huang, X. F.; Fan, X. J.; Zhang, X. M. (003)-facet-exposed Ni3S2 nanoporous thin films on nickel foil for efficient water splitting. Appl. Catal. B: Environ. 2019, 243, 693–702.

Crossref Google Scholar
56

Hammer, B.; Norskov, J. K. Why gold is the noblest of all the metals. Nature 1995, 376, 238–240.

Crossref Google Scholar
57

Wang, J.; Li, X. Z.; Wei, B.; Sun, R.; Yu, W.; Hoh, H. Y.; Xu, H. M.; Li, J.; Ge, X. B.; Chen, Z. X. et al. Activating basal planes of NiPS3 for hydrogen evolution by nonmetal heteroatom doping. Adv. Funct. Mater. 2020, 30, 1908708.

Crossref Google Scholar
58

Shi, Y.; Ma, Z. R.; Xiao, Y. Y.; Yin, Y. C.; Huang, W. M.; Huang, Z. C.; Zheng, Y. Z.; Mu, F. Y.; Huang, R.; Shi, G. Y. et al. Electronic metal-support interaction modulates single-atom platinum catalysis for hydrogen evolution reaction. Nat. Commun. 2021, 12, 3021.

Crossref Google Scholar
59

Zhang, H. B.; Ma, Z. J.; Duan, J. J.; Liu, H. M.; Liu, G. G.; Wang, T.; Chang, K.; Li, M.; Shi, L.; Meng, X. G. et al. Active sites implanted carbon cages in core-shell architecture: Highly active and durable electrocatalyst for hydrogen evolution reaction. ACS Nano 2016, 10, 684–694.

Crossref Google Scholar
60

Yin, J.; Jin, J.; Zhang, H.; Lu, M.; Peng, Y.; Huang, B. L.; Xi, P. X.; Yan, C. H. Atomic arrangement in metal-doped NiS2 boosts the hydrogen evolution reaction in alkaline media. Angew. Chem., Int. Ed. 2019, 58, 18676–18682.

Crossref Google Scholar
Nano Research
Volume 15 Issue 10,
October 2022
Pages 8771-8782
DOI: 10.1007/s12274-022-4534-9
Cite this article:
Wang G, Sun Y, Zhao Y, et al. Phosphorus-induced electronic structure reformation of hollow NiCo2Se4 nanoneedle arrays enabling highly efficient and durable hydrogen evolution in all-pH media. Nano Research, 2022, 15(10): 8771-8782. https://doi.org/10.1007/s12274-022-4534-9
Topics:
Electrocatalysis Hydrogen evolution reaction
Metrics & Citations  
Article History
Copyright
Return