The exploration of cost-effective, high-performance, and stable electrocatalysts for the hydrogen evolution reaction (HER) over wide pH range (0–14) is of paramount importance for future renewable energy conversion technologies. Regulation of electronic structure through doping vanadium atoms is a feasible construction strategy to enhance catalytic activities, electron transfer capability, and stability of the HER electrode. Herein, V-doped NiCoP nanosheets on carbon fiber paper (CFP) (denoted as Vx-NiCoP/CFP) were constructed by doping V modulation on NiCoP nanosheets on CFP and used for pH-universal HER. Benefiting from the abundant catalytic sites and optimized hydrogen binding thermodynamics, the resultant V15-NiCoP/CFP demonstrates a significantly improved HER catalytic activity, requiring overpotentials of 46.5, 52.4, and 85.3 mV to reach a current density of 10 mA·cm–2 in 1 mol·L–1 KOH, 0.5 mol·L–1 H2SO4, and 1 mol·L–1 phosphate buffer solution (PBS) electrolytes, respectively. This proposed cation-doping strategy provides a new inspiration to rationally enhance or design new-type nonprecious metal-based, highly efficient, and pH-universal electrocatalysts for various energy conversion systems.
F Qi, X Wang, B Zheng, Y Chen, B Yu, J Zhou, J He, P Li, W Zhang, Y Li. Self-assembled chrysanthemum-like microspheres constructed by few-layer ReSe2 nanosheets as a highly efficient and stable electrocatalyst for hydrogen evolution reaction. Electrochimica Acta, 2017, 224: 593–599 https://doi.org/10.1016/j.electacta.2016.12.097
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Z Yang, Y Lin, F X Jiao, J H Li, W F Wang, Y Q Gong, X F Jing. Morphology engineering of 3D nanostructure MMNS as bifunctional electrocatalysts towards high-efficient overall water splitting. Applied Surface Science, 2020, 502: 144147 https://doi.org/10.1016/j.apsusc.2019.144147
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X Wang, J He, B Yu, B Sun, D Yang, X Zhang, Q Zhang, W Zhang, L Gu, Y Chen. CoSe2 nanoparticles embedded MOF-derived Co-N-C nanoflake arrays as efficient and stable electrocatalyst for hydrogen evolution reaction. Applied Catalysis B: Environmental, 2019, 258: 117996 https://doi.org/10.1016/j.apcatb.2019.117996
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K Zhou, J He, X Wang, J Lin, Y Jing, W Zhang, Y Chen. Self-assembled CoSe2 nanocrystals embedded into carbon nanowires as highly efficient catalyst for hydrogen evolution reaction. Electrochimica Acta, 2017, 231: 626–631 https://doi.org/10.1016/j.electacta.2017.02.089
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Y Q Gong, Y Lin, Z Yang, F L Jiao, J H Li, W F Wang. High-performance bifunctional flower-like Mn-doped Cu7.2S4@NiS2@NiS/NF catalyst for overall water splitting. Applied Surface Science, 2019, 476: 840–849 https://doi.org/10.1016/j.apsusc.2019.01.167
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W Hou, J He, B Yu, Y Lu, W Zhang, Y Chen. One-pot synthesis of graphene-wrapped NiSe2-Ni0.85Se hollow microspheres as superior and stable electrocatalyst for hydrogen evolution reaction. Electrochimica Acta, 2018, 291: 242–248 https://doi.org/10.1016/j.electacta.2018.08.129
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S Gao, Y Zhang, Y Zhang, B Wang, S Yang. Modification of carbon nanotubes via birch reaction for enhanced HER catalyst by constructing pearl necklace-like NiCo2P2-CNT composite. Small, 2018, 14(51): 1804388 https://doi.org/10.1002/smll.201804388
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Y Lin, Z Yang, D L Cao, Y Q Gong. Electro-deposition of nickel-iron nanoparticles on flower-like MnCo2O4 nanowires as an efficient bifunctional electrocatalyst for overall water splitting. CrystEngComm, 2020, 22(8): 1425–1435 https://doi.org/10.1039/C9CE01921A
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Y Q Gong, Z Yang, Y Lin, J L Wang, H L Pan, Z F Xu. Hierarchical heterostructure NiCo2O4@CoMoO4/NF as an efficient bifunctional electrocatalyst for overall water splitting. Journal of Materials Chemistry. A, 2018, 6(35): 16950–16958 https://doi.org/10.1039/C8TA04325F
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J Lin, J He, F Qi, B Zheng, X Wang, B Yu, K Zhou, W Zhang, Y Li, Y Chen. In-situ selenization of Co-based metal-organic frameworks as a highly efficient electrocatalyst for hydrogen evolution reaction. Electrochimica Acta, 2017, 247: 258–264 https://doi.org/10.1016/j.electacta.2017.06.179
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L Xiong, J Bi, L Wang, S Yang. Improving the electrocatalytic property of CoP for hydrogen evolution by constructing porous ternary CeO2-CoP-C hybrid nanostructure via ionic exchange of MOF. International Journal of Hydrogen Energy, 2018, 43(45): 20372–20381 https://doi.org/10.1016/j.ijhydene.2018.09.117
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Y Han, P Li, Z Tian, C Zhang, Y Ye, X Zhu, C Liang. Molybdenum-doped porous cobalt phosphide nanosheets for efficient alkaline hydrogen evolution. ACS Applied Energy Materials, 2019, 2(9): 6302–6310 https://doi.org/10.1021/acsaem.9b00924
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Z Wu, L Huang, H Liu, H Wang. Element-specific restructuring of anion- and cation-substituted cobalt phosphide nanoparticles under electrochemical water-splitting conditions. ACS Catalysis, 2019, 9(4): 2956–2961 https://doi.org/10.1021/acscatal.8b03835
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Y Q Gong, Z F Xu, H L Pan, Y Lin, Z Yang, J Wang. A 3D well-matched electrode pair of Ni-Co-S/Ni-Co-P nanoarrays grown on nickel foam as a high-performance electrocatalyst for water splitting. Journal of Materials Chemistry. A, 2018, 6(26): 12506–12514 https://doi.org/10.1039/C8TA03163K
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Y Pei, Y Cheng, J Chen, W Smith, P Dong, P M Ajayan, M Ye, J Shen. Recent developments of transition metal phosphides as catalysts in the energy conversion field. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2018, 6(46): 23220–23243 https://doi.org/10.1039/C8TA09454C
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C Du, L Yang, F Yang, G Cheng, W Luo. Nest-like NiCoP for highly efficient overall water splitting. ACS Catalysis, 2017, 7(6): 4131–4137 https://doi.org/10.1021/acscatal.7b00662
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Y Tan, H Wang, P Liu, Y Shen, C Cheng, A Hirata, T Fujita, Z Tang, M Chen. Versatile nanoporous bimetallic phosphides towards electrochemical water splitting. Energy & Environmental Science, 2016, 9(7): 2257–2261 https://doi.org/10.1039/C6EE01109H
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X D Wang, Y F Xu, H S Rao, W J Xu, H Y Chen, W X Zhang, D B Kuang, C Y Su. Novel porous molybdenum tungsten phosphide hybrid nanosheets on carbon cloth for efficient hydrogen evolution. Energy & Environmental Science, 2016, 9(4): 1468–1475 https://doi.org/10.1039/C5EE03801D
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W L Kwong, E Gracia Espino, C C Lee, R Sandstrom, T Wagberg, J Messinger. Cationic vacancy defects in iron phosphide: a promising route toward efficient and stable hydrogen evolution by electrochemical water splitting. ChemSusChem, 2017, 10(22): 4544–4551 https://doi.org/10.1002/cssc.201701565
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D J Rensel, J Kim, Y Bonita, J C Hicks. Investigating the multifunctional nature of bimetallic FeMoP catalysts using dehydration and hydrogenolysis reactions. Applied Catalysis A, General, 2016, 524: 85–93 https://doi.org/10.1016/j.apcata.2016.06.011
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R Zhang, X Wang, S Yu, T Wen, X Zhu, F Yang, X Sun, X Wang, W Hu. Ternary NiCo2Px nanowires as pH-universal electrocatalysts for highly efficient hydrogen evolution reaction. Advanced Materials, 2017, 29(9): 1605502 https://doi.org/10.1002/adma.201605502
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D Yang, W Hou, Y Lu, X Wang, W Zhang, Y Chen. Scalable synthesis of bimetallic phosphide decorated in carbon nanotube network as multifunctional electrocatalyst for water splitting. ACS Sustainable Chemistry & Engineering, 2019, 7(15): 13031–13040 https://doi.org/10.1021/acssuschemeng.9b02142
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Z Cai, A Wu, H Yan, Y Xiao, C Chen, C Tian, L Wang, R Wang, H Fu. Hierarchical whisker-on-sheet NiCoP with adjustable surface structure for efficient hydrogen evolution reaction. Nanoscale, 2018, 10(16): 7619–7629 https://doi.org/10.1039/C8NR01057A
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Y Li, X Tan, R K Hocking, X Bo, H Ren, B Johannessen, S C Smith, C Zhao. Implanting Ni-O-VOx sites into Cu-doped Ni for low-overpotential alkaline hydrogen evolution. Nature Communications, 2020, 11(1): 2720 https://doi.org/10.1038/s41467-020-16554-5
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Y Men, P Li, J Zhou, G Cheng, S Chen, W Luo. Tailoring the electronic structure of Co2P by N doping for boosting hydrogen evolution reaction at all pH Values. ACS Catalysis, 2019, 9(4): 3744–3752 https://doi.org/10.1021/acscatal.9b00407
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J Zhang, X Shang, H Ren, J Chi, H Fu, B Dong, C Liu, Y Chai. Modulation of inverse spinel Fe3O4 by phosphorus doping as an industrially promising electrocatalyst for hydrogen evolution. Advanced Materials, 2019, 31(52): 1905107 https://doi.org/10.1002/adma.201905107
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X Xiao, L Tao, M Li, X Lv, D Huang, X Jiang, H Pan, M Wang, Y Shen. Electronic modulation of transition metal phosphide via doping as efficient and pH-universal electrocatalysts for hydrogen evolution reaction. Chemical Science (Cambridge), 2018, 9(7): 1970–1975 https://doi.org/10.1039/C7SC04849A
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T Liu, C Fang, B Yu, Y You, H Niu, R Zhou, J Zhang, J Xu. Vanadium-doping in interlayer-expanded MoS2 nanosheets for the efficient electrocatalytic hydrogen evolution reaction. Inorganic Chemistry Frontiers, 2020, 7(13): 2497–2505 https://doi.org/10.1039/D0QI00135J
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R Zhu, F Chen, J Wang, Y Song, J Cheng, M Mao, H Ma, J Lu, Y Cheng. Multi-channel V-doped CoP hollow nanofibers as high-performance hydrogen evolution reaction electrocatalysts. Nanoscale, 2020, 12(16): 9144–9151 https://doi.org/10.1039/D0NR01595D
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X Zhang, F Zhou, W Pan, Y Liang, R Wang. General construction of molybdenum-based nanowire arrays for pH-universal hydrogen evolution electrocatalysis. Advanced Functional Materials, 2018, 28(43): 1804600 https://doi.org/10.1002/adfm.201804600
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X Zhang, X Zhang, H Xu, Z Wu, H Wang, Y Liang. Iron-doped cobalt monophosphide nanosheet/carbon nanotube hybrids as active and stable electrocatalysts for water splitting. Advanced Functional Materials, 2017, 27(24): 1606635 https://doi.org/10.1002/adfm.201606635
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L Sun, T Wang, L Zhang, Y Sun, K Xu, Z Dai, F Ma. Mace-like hierarchical MoS2/NiCo2S4 composites supported by carbon fiber paper: an efficient electrocatalyst for the hydrogen evolution reaction. Journal of Power Sources, 2018, 377: 142–150 https://doi.org/10.1016/j.jpowsour.2017.12.013
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C N Lv, L Zhang, X H Huang, Y X Zhu, X Zhang, J S Hu, S Y Lu. Double functionalization of N-doped carbon carved hollow nanocubes with mixed metal phosphides as efficient bifunctional catalysts for electrochemical overall water splitting. Nano Energy, 2019, 65: 103995 https://doi.org/10.1016/j.nanoen.2019.103995
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Y Lin, K Sun, S Liu, X Chen, Y Cheng, W C Cheong, Z Chen, L Zheng, J Zhang, X Li, Y Pan, C Chen. Construction of CoP/NiCoP nanotadpoles heterojunction interface for wide pH hydrogen evolution electrocatalysis and supercapacitor. Advanced Energy Materials, 2019, 9(36): 1901213 https://doi.org/10.1002/aenm.201901213
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S Liu, Q Liu, Y Lv, B Chen, Q Zhou, L Wang, Q Zheng, C Che, C Chen. Ru decorated with NiCoP: an efficient and durable hydrogen evolution reaction electrocatalyst in both acidic and alkaline conditions. Chemical Communications, 2017, 53(98): 13153–13156 https://doi.org/10.1039/C7CC08340H
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Y Qi, L Zhang, L Sun, G Chen, Q Luo, H Xin, J Peng, Y Li, F Ma. Sulfur doping enhanced desorption of intermediates on NiCoP for efficient alkaline hydrogen evolution. Nanoscale, 2020, 12(3): 1985–1993 https://doi.org/10.1039/C9NR08583A
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R Boppella, J Tan, W Yang, J Moon. Homologous CoP/NiCoP heterostructure on N-doped carbon for highly efficient and pH-universal hydrogen evolution electrocatalysis. Advanced Functional Materials, 2018, 29(6): 1807976 https://doi.org/10.1002/adfm.201807976
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Y Yang, H Yao, Z Yu, S M Islam, H He, M Yuan, Y Yue, K Xu, W Hao, G Sun, H Li, S Ma, P Zapol, M G Kanatzidis. 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 https://doi.org/10.1021/jacs.9b04492
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L Xiong, B Wang, H Cai, T Yang, L Wang, S Yang. Neighboring effect induced by V and Cr doping in FeCoP nanoarrays for the hydrogen evolution reaction with Pt-like performance. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2020, 8(3): 1184–1192 https://doi.org/10.1039/C9TA12562K
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W Li, G Cheng, M Sun, Z Wu, G Liu, D Su, B Lan, S Mai, L Chen, L Yu. C-CoP hollow microporous nanocages based on phosphating regulation: a high-performance bifunctional electrocatalyst for overall water splitting. Nanoscale, 2019, 11(36): 17084–17092 https://doi.org/10.1039/C9NR05061B
41
Y Yan, J Lin, J Cao, S Guo, X Zheng, J Feng, J Qi. Activating and optimizing the activity of NiCoP nanosheets for electrocatalytic alkaline water splitting through the V doping effect enhanced by P vacancies. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2019, 7(42): 24486–24492 https://doi.org/10.1039/C9TA09283H
42
Y Luo, L Tang, U Khan, Q Yu, H M Cheng, X Zou, B Liu. Morphology and surface chemistry engineering toward pH-universal catalysts for hydrogen evolution at high current density. Nature Communications, 2019, 10(1): 269 https://doi.org/10.1038/s41467-018-07792-9
43
H Li, X Qian, C Xu, S Huang, C Zhu, X Jiang, L Shao, L Hou. Hierarchical porous Co9S8/nitrogen-doped carbon@MoS2 polyhedrons as pH universal electrocatalysts for highly efficient hydrogen evolution reaction. ACS Applied Materials & Interfaceserfaces, 2017, 9(34): 28394–28405 https://doi.org/10.1021/acsami.7b06384
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E Hu, Y Feng, J Nai, D Zhao, Y Hu, X W Lou. Construction of hierarchical Ni-Co-P hollow nanobricks with oriented nanosheets for efficient overall water splitting. Energy & Environmental Science, 2018, 11(4): 872–880 https://doi.org/10.1039/C8EE00076J
45
A Han, H Chen, H Zhang, Z Sun, P Du. Ternary metal phosphide nanosheets as a highly efficient electrocatalyst for water reduction to hydrogen over a wide pH range from 0 to 14. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2016, 4(26): 10195–10202 https://doi.org/10.1039/C6TA02297A
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X Zhang, S Zhu, L Xia, C Si, F Qu, F Qu. Ni(OH)2-Fe2P hybrid nanoarray for alkaline hydrogen evolution reaction with superior activity. Chemical Communications, 2018, 54(10): 1201–1204 https://doi.org/10.1039/C7CC07342A
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J Liu, Y Zheng, Y Jiao, Z Wang, Z Lu, A Vasileff, S Z Qiao. NiO as a bifunctional promoter for RuO2 toward superior overall water splitting. Small, 2018, 14(16): 1704073 https://doi.org/10.1002/smll.201704073
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Z Zhuang, Y Wang, C Q Xu, S Liu, C Chen, Q Peng, Z Zhuang, H Xiao, Y Pan, S Lu, R Yu, W C Cheong, X Cao, K Wu, K Sun, Y Wang, D Wang, J Li, Y Li. Three-dimensional open nano-netcage electrocatalysts for efficient pH-universal overall water splitting. Nature Communications, 2019, 10(1): 4875 https://doi.org/10.1038/s41467-019-12885-0
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Y Zhu, G Chen, X Xu, G Yang, M Liu, Z Shao. Enhancing electrocatalytic activity for hydrogen evolution by strongly coupled molybdenum nitride@nitrogen-doped carbon porous nano-octahedrons. ACS Catalysis, 2017, 7(5): 3540–3547 https://doi.org/10.1021/acscatal.7b00120