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Research Article

Ferrocene-induced switchable preparation of metal-nonmetal codoped tungsten nitride and carbide nanoarrays for electrocatalytic HER in alkaline and acid media

Jian Zhou1,§, Fanfan Wang2,§, Haiqing Wang1,§( ), Shuxian Hu2( ), Weijia Zhou1, Hong Liu1,3( )
Institute for Advanced Interdisciplinary Research (iAIR), School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China
Department of Physics, University of Science and Technology Beijing, Beijing 100083, China
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China

§ Jian Zhou, Fanfan Wang, and Haiqing Wang contributed equally to this work.

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Graphical Abstract

Metal and nonmetal codoped tungsten nitride and carbide nanoarrays were constructed successfully through switchable in situ gas-solid reaction for electrocatalytic hydrogen evolution reaction (HER).

Abstract

Transition metal nitride/carbide (TMN/C) have been actively explored as low-cost hydrogen evolution reaction (HER) electrocatalysts owing to their Pt-like physical and chemical properties. Unfortunately, pure TMN/C suffers from strong hydrogen adsorption and lacks active centers for water dissociation. Herein, we developed a switchable WO3-based in situ gas–solid reaction for preparing sophisticated Fe-N doped WC and Fe-C doped WN nanoarrays. Interestingly, the switch of codoping and phase can be effectively manipulated by regulating the amount of ferrocene. Resultant Fe-C-WN and Fe-N-WC exhibit robust electrocatalytic performance for HER in alkaline and acid electrolytes, respectively. The collective collaboration of morphological, phase and electronic effects are suggested to be responsible for the superior HER activity. The smallest |ΔGH*| value of Fe-N-WC indicates preferable hydrogen-evolving kinetics on the Fe-N-WC surface for HER under acid condition, while Fe-C-WN is suggested to be beneficial to the adsorption and dissociation of H2O for HER in alkaline electrolyte.

Keywords

gas–solid reactiontungsten nitride/carbidecodopingphase regulationhydrogen evolution

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References

[1]

Li, H. Y.; Chen, S. M.; Zhang, Y.; Zhang, Q. H.; Jia, X. F.; Zhang, Q.; Gu, L.; Sun, X. M.; Song, L.; Wang, X. Systematic design of superaerophobic nanotube-array electrode comprised of transition-metal sulfides for overall water splitting. Nat. Commun. 2018, 9, 2452.
Crossref Google Scholar
[2]

Li, H. Y.; Chen, S. M.; Jia, X. F.; Xu, B.; Lin, H. F.; Yang, H. Z.; Song, L.; Wang, X. Amorphous nickel-cobalt complexes hybridized with 1T-phase molybdenum disulfide via hydrazine-induced phase transformation for water splitting. Nat. Commun. 2017, 8, 15377.
Crossref Google Scholar
[3]

Han, N. N.; Yang, K. R.; Lu, Z. Y.; Li, Y. J.; Xu, W. W.; Gao, T. F.; Cai, Z.; Zhang, Y.; Batista, V. S.; Liu, W. et al. Nitrogen-doped tungsten carbide nanoarray as an efficient bifunctional electrocatalyst for water splitting in acid. Nat. Commun. 2018, 9, 924.
Crossref Google Scholar
[4]

Zhang, Z. C.; Liu, G. G.; Cui, X. Y.; Chen, B.; Zhu, Y. H.; Gong, Y.; Saleem, F.; Xi, S. B.; Du, Y. H.; Borgna, A. et al. Crystal phase and architecture engineering of lotus-thalamus-shaped Pt-Ni anisotropic superstructures for highly efficient electrochemical hydrogen evolution. Adv. Mater. 2018, 30, 1801741.
Crossref Google Scholar
[5]

Centi, G. Smart catalytic materials for energy transition. SmartMat 2020, 1, e1005.
Crossref Google Scholar
[6]

Wang, H. Q.; Xu, J. H.; Zhang, Q. B.; Hu, S. X.; Zhou, W. J.; Liu, H.; Wang, X. Super-hybrid transition metal sulfide nanoarrays of Co3S4 nanosheet/p-doped WS2 nanosheet/Co9S8 nanoparticle with Pt-like activities for robust all-pH hydrogen evolution. Adv. Funct. Mater. 2022, 32, 2112362.
Crossref Google Scholar
[7]

Niu, S. W.; Fang, Y. Y.; Rao, D. W.; Liang, G. J.; Li, S. Y.; Cai, J. Y.; Liu, B.; Li, J. M.; Wang, G. M. Reversing the nucleophilicity of active sites in CoP2 enables exceptional hydrogen evolution catalysis. Small 2022, 18, 2106870.
Crossref Google Scholar
[8]

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
[9]

Wang, H. Q.; Zhang, W. J.; Zhang, X. W.; Hu, S. X.; Zhang, Z. C.; Zhou, W. J.; Liu, H. Multi-interface collaboration of graphene cross-linked NiS-NiS2-Ni3S4 polymorph foam towards robust hydrogen evolution in alkaline electrolyte. Nano Res. 2021, 14, 4857–4864.
Crossref Google Scholar
[10]

Liu, M. M.; Li, H. X.; Liu, S. J.; Wang, L. L.; Xie, L. B.; Zhuang, Z. C.; Sun, C.; Wang, J.; Tang, M.; Sun, S. J. et al. Tailoring activation sites of metastable distorted 1T′-phase MoS2 by Ni doping for enhanced hydrogen evolution. Nano Res. 2022, 15, 5946–5952.
Crossref Google Scholar
[11]

Li, X. P.; Huang, C.; Han, W. K.; Ouyang, T.; Liu, Z. Q. Transition metal-based electrocatalysts for overall water splitting. Chin. Chem. Lett. 2021, 32, 2597–2616.
Crossref Google Scholar
[12]

Ling, M.; Li, N.; Jiang, B. B.; Tu, R. Y.; Wu, T.; Guan, P. L.; Ye, Y.; Cheong, W. C. M.; Sun, K. A.; Liu, S. J. et al. Rationally engineered Co and N co-doped WS2 as bifunctional catalysts for pH-universal hydrogen evolution and oxidative dehydrogenation reactions. Nano Res. 2022, 15, 1993–2002.
Crossref Google Scholar
[13]

Ang, E. H.; Dinh, K. N.; Sun, X. L.; Huang, Y.; Yang, J.; Dong, Z. L.; Dong, X. C.; Huang, W.; Wang, Z. G.; Zhang, H. et al. Highly efficient and stable hydrogen production in all pH range by two-dimensional structured metal-doped tungsten semicarbides. Research 2019, 2019, 4029516.
Crossref Google Scholar
[14]

Wang, H. P.; Zhu, S.; Deng, J. W.; Zhang, W. C.; Feng, Y. Z.; Ma, J. M. Transition metal carbides in electrocatalytic oxygen evolution reaction. Chin. Chem. Lett. 2021, 32, 291–298.
Crossref Google Scholar
[15]

Zhang, B. W.; Li, C. J.; Hu, J.; Peng, D. D.; Huang, K.; Wu, J. S.; Chen, Z.; Huang, Y. Z. Cobalt tungsten phosphide with tunable W-doping as highly efficient electrocatalysts for hydrogen evolution reaction. Nano Res. 2021, 14, 4073–4078.
Crossref Google Scholar
[16]

Jin, H. Y.; Gu, Q. F.; Chen, B.; Tang, C.; Zheng, Y.; Zhang, H.; Jaroniec, M.; Qiao, S. Z. Molten salt-directed catalytic synthesis of 2D layered transition-metal nitrides for efficient hydrogen evolution. Chem 2020, 6, 2382–2394.
Crossref Google Scholar
[17]

Wang, H. Q.; Xu, X. B.; Ni, B.; Li, H. Y.; Bian, W.; Wang, X. 3D self-assembly of ultrafine molybdenum carbide confined in N-doped carbon nanosheets for efficient hydrogen production. Nanoscale 2017, 9, 15895–15900.
Crossref Google Scholar
[18]

Kundu, A.; Ma, J.; Carrete, J.; Madsen, G. K. H.; Li, W. Anomalously large lattice thermal conductivity in metallic tungsten carbide and its origin in the electronic structure. Mater. Today Phys. 2020, 13, 100214.
Crossref Google Scholar
[19]

Yan, H. J.; Tian, C. G.; Wang, L.; Wu, A. P.; Meng, M. C.; Zhao, L.; Fu, H. G. Phosphorus-modified tungsten nitride/reduced graphene oxide as a high-performance, non-noble-metal electrocatalyst for the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2015, 54, 6325–6329.
Crossref Google Scholar
[20]

Lv, C. C.; Wang, X. B.; Gao, L. J.; Wang, A. J.; Wang, S. F.; Wang, R. N.; Ning, X. K.; Li, Y. G.; Boukhvalov, D. W.; Huang, Z. P. et al. Triple functions of Ni(OH)2 on the surface of WN nanowires remarkably promoting electrocatalytic activity in full water splitting. ACS Catal. 2020, 10, 13323–13333.
Crossref Google Scholar
[21]

Li, H.; Hu, M. H.; Zhang, L. Y.; Huo, L. L.; Jing, P.; Liu, B. C.; Gao, R.; Zhang, J.; Liu, B. Hybridization of bimetallic molybdenum-tungsten carbide with nitrogen-doped carbon: A rational design of super active porous composite nanowires with tailored electronic structure for boosting hydrogen evolution catalysis. Adv. Funct. Mater. 2020, 30, 2003198.
Crossref Google Scholar
[22]
ZhangS. G.GaoG. H.ZhuH.CaiL. J.JiangX. D.LuS. L.DuanF.DongW. F.ChaiY.DuM. L. In situ interfacial engineering of nickel tungsten carbide janus structures for highly efficient overall water splittingSci. Bull.20206564065010.1016/j.scib.2020.02.003

Zhang, S. G.; Gao, G. H.; Zhu, H.; Cai, L. J.; Jiang, X. D.; Lu, S. L.; Duan, F.; Dong, W. F.; Chai, Y.; Du, M. L. In situ interfacial engineering of nickel tungsten carbide janus structures for highly efficient overall water splitting. Sci. Bull. 2020, 65, 640–650.
Crossref Google Scholar
[23]

Ma, M. J.; Xu, J. H.; Wang, H. Q.; Zhang, X. W.; Hu, S. X.; Zhou, W. J.; Liu, H. Multi-interfacial engineering of hierarchical CoNi2S4/WS2/Co9S8 hybrid frameworks for robust all-pH electrocatalytic hydrogen evolution. Appl. Catal. B:Environ. 2021, 297, 120455.
Crossref Google Scholar
[24]

Wang, H. Q.; Ma, M. J.; Li, J. J.; Zhang, Z. C.; Zhou, W. J.; Liu, H. Manipulating all-pH hydrogen evolution kinetics on metal sulfides through one-pot simultaneously derived multi-interface engineering and phosphorus doping. J. Mater. Chem. A 2021, 9, 25539–25546.
Crossref Google Scholar
[25]

Zhang, Z. F.; Wang, H. Q.; Ma, M. J.; Liu, H. L.; Zhang, Z. C.; Zhou, W. J.; Liu, H. Integrating NiMoO wafer as a heterogeneous ‘turbo’ for engineering robust Ru-based electrocatalyst for overall water splitting. Chem. Eng. J. 2021, 420, 127686.
Crossref Google Scholar
[26]

Wang, H. Q.; Zhang, X. W.; Wang, J. G.; Liu, H. L.; Hu, S. X.; Zhou, W. J.; Liu, H.; Wang, X. Puffing quaternary FexCoyNi1–x–yP nanoarray via kinetically controlled alkaline etching for robust overall water splitting. Sci. China Mater. 2020, 63, 1054–1064.
Crossref Google Scholar
[27]

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
[28]

Li, Y. H.; Wang, M. L.; Yi, Y. Y.; Lu, C.; Dou, S. X.; Sun, J. Y. Metallic transition metal dichalcogenides of group VIB: Preparation, stabilization, and energy applications. Small 2021, 17, 2005573.
Crossref Google Scholar
[29]

Ma, M. J.; Feng, Z. C.; Zhang, X. W.; Sun, C. Y.; Wang, H. Q.; Zhou, W. J.; Liu, H. Progress in the preparation and application of electrocatalysts based on microorganisms as intelligent templates. Acta Phys. Chim. Sin. 2022, 38, 2106003.
Crossref Google Scholar
[30]

Liao, L. L.; Cheng, C.; Zhou, H. Q.; Qi, Y.; Li, D. Y.; Cai, F. M.; Yu, B.; Long, R.; Yu, F. Accelerating pH-universal hydrogen-evolving activity of a hierarchical hybrid of cobalt and dinickel phosphides by interfacial chemical bonds. Mater. Today Phys. 2022, 22, 100589.
Crossref Google Scholar
[31]

Gao, Z. Q.; Wang, C. Y.; Li, J. J.; Zhu, Y. T.; Zhang, Z. C.; Hu, W. P. Conductive metal–organic frameworks for electrocatalysis: Achievements, challenges, and opportunities. Acta Phys. Chim. Sin. 2021, 37, 2010025.
Crossref Google Scholar
[32]

Fu, H. C.; Wang, X. H.; Chen, X. H.; Zhang, Q.; Li, N. B.; Luo, H. Q. Interfacial engineering of Ni(OH)2 on W2C for remarkable alkaline hydrogen production. Appl. Catal. B:Environ. 2022, 301, 120818.
Crossref Google Scholar
[33]

Zhao, Y.; Kamiya, K.; Hashimoto, K.; Nakanishi, S. Hydrogen evolution by tungsten carbonitride nanoelectrocatalysts synthesized by the formation of a tungsten acid/polymer hybrid in situ. Angew. Chem., Int. Ed. 2013, 52, 13638–13641.
Crossref Google Scholar
[34]

Chen, Y. D.; Zheng, Y.; Yue, X.; Huang, S. M. Hydrogen evolution reaction in full pH range on nickel doped tungsten carbide nanocubes as efficient and durable non-precious metal electrocatalysts. Int. J. Hydrogen Energy 2020, 45, 8695–8702.
Crossref Google Scholar
[35]

Wu, A. P.; Gu, Y.; Yang, B. R.; Wu, H.; Yan, H. J.; Jiao, Y. Q.; Wang, D. X.; Tian, C. G.; Fu, H. G. Porous cobalt/tungsten nitride polyhedra as efficient bifunctional electrocatalysts for overall water splitting. J. Mater. Chem. A 2020, 8, 22938–22946.
Crossref Google Scholar
[36]

Xu, X. B.; Nosheen, F.; Wang, X. Ni-decorated molybdenum carbide hollow structure derived from carbon-coated metal–organic framework for electrocatalytic hydrogen evolution reaction. Chem. Mater. 2016, 28, 6313–6320.
Crossref Google Scholar
[37]

Li, Y. C.; Xia, L. L.; Fan, Y. M.; Wang, Q. Y.; Hu, M. Recent advances in autonomous synthesis of materials. ChemPhysMater 2022, 1, 77–85.
Crossref Google Scholar
[38]

Zhang, S. J.; Qin, Z. L.; Hou, Z. G.; Ye, J. J.; Xu, Z. B.; Qian, Y. T. Large-scale preparation of black phosphorus by molten salt method for energy storage. ChemPhysMater 2022, 1, 1–5.
Crossref Google Scholar
[39]

Cui, Y. L. S.; Tan, X.; Xiao, K. F.; Zhao, S. L.; Bedford, N. M.; Liu, Y. F.; Wang, Z. C.; Wu, K. H.; Pan, J.; Saputera, W. H. et al. Tungsten oxide/carbide surface heterojunction catalyst with high hydrogen evolution activity. ACS Energy Lett. 2020, 5, 3560–3568.
Crossref Google Scholar
[40]

Ma, F. H.; Wang, S. H.; Gong, X. Q.; Liu, X. L.; Wang, Z. Y.; Wang, P.; Liu, Y. Y.; Cheng, H. F.; Dai, Y.; Zheng, Z. K. et al. Highly efficient electrocatalytic hydrogen evolution coupled with upcycling of microplastics in seawater enabled via Ni3N/W5N4 janus nanostructures. Appl. Catal. B:Environ. 2022, 307, 121198.
Crossref Google Scholar
[41]

Zhang, Q.; Luo, F.; Long, X.; Yu, X. X.; Qu, K. G.; Yang, Z. H. N, P doped carbon nanotubes confined WN-Ni Mott–Schottky heterogeneous electrocatalyst for water splitting and rechargeable zinc–air batteries. Appl. Catal. B:Environ. 2021, 298, 120511.
Crossref Google Scholar
[42]

Yu, H. M.; Yang, X.; Xiao, X.; Chen, M.; Zhang, Q. H.; Huang, L.; Wu, J. B.; Li, T. Q.; Chen, S. M.; Song, L. et al. Atmospheric-pressure synthesis of 2D nitrogen-rich tungsten nitride. Adv. Mater. 2018, 30, 1805655.
Crossref Google Scholar
[43]

Zhu, Y. P.; Chen, G.; Zhong, Y. J.; Zhou, W.; Shao, Z. P. Rationally designed hierarchically structured tungsten nitride and nitrogen-rich graphene-like carbon nanocomposite as efficient hydrogen evolution electrocatalyst. Adv. Sci. 2018, 5, 1700603.
Crossref Google Scholar
[44]

Emin, S.; Altinkaya, C.; Semerci, A.; Okuyucu, H.; Yildiz, A.; Stefanov, P. Tungsten carbide electrocatalysts prepared from metallic tungsten nanoparticles for efficient hydrogen evolution. Appl. Catal. B:Environ. 2018, 236, 147–153.
Crossref Google Scholar
[45]

Zhao, B. H.; Sun, M. Y.; Chen, F. P.; Shi, Y. M.; Yu, Y. F.; Li, X. G.; Zhang, B. Unveiling the activity origin of iron nitride as catalytic material for efficient hydrogenation of CO2 to C2+ hydrocarbons. Angew. Chem., Int. Ed. 2021, 60, 4496–4500.
Crossref Google Scholar
[46]

Jin, Y.; Zhang, Z.; Yang, H.; Wang, P. T.; Shen, C. Q.; Cheng, T.; Huang, X. Q.; Shao, Q. Boosting hydrogen production with ultralow working voltage by selenium vacancy-enhanced ultrafine platinum-nickel nanowires. SmartMat 2022, 3, 130–141.
Crossref Google Scholar
[47]

Lu, T. Y.; Li, T. F.; Shi, D. S.; Sun, J. L.; Pang, H.; Xu, L.; Yang, J.; Tang, Y. W. In situ establishment of Co/MoS2 heterostructures onto inverse opal-structured N, S-doped carbon hollow nanospheres: Interfacial and architectural dual engineering for efficient hydrogen evolution reaction. SmartMat 2021, 2, 591–602.
Crossref Google Scholar
[48]

Jing, H. Y.; Zhu, P.; Zheng, X. B.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis. Adv. Powder Mater. 2022, 1, 100013.
Crossref Google Scholar
[49]

Nasiri, M. B.; Iranshahi, F. Comprehensive unified model and simulation approach for microstructure evolution. ChemPhysMater 2022, 1, 133–147.
Crossref Google Scholar
[50]

Liu, D. Y.; Zeng, Q.; Hu, C. Q.; Chen, D.; Liu, H.; Han, Y. S.; Xu, L.; Zhang, Q. B.; Yang, J. Light doping of tungsten into copper-platinum nanoalloys for boosting their electrocatalytic performance in methanol oxidation. Nano Res. Energy, 2022, 1, e9120017.
Crossref Google Scholar
[51]

Qi, D. F.; Lv, F.; Wei, T. R.; Jin, M. M.; Meng, G.; Zhang, S. S.; Liu, Q.; Liu, W. X.; Ma D.; Hamdy, M. S. et al. High-efficiency electrocatalytic NO reduction to NH3 by nanoporous VN. Nano Res. Energy, 2022, 1, e9120022.
Crossref Google Scholar
Nano Research
Volume 16 Issue 2,
February 2023
Pages 2085-2093
DOI: 10.1007/s12274-022-4901-6
Cite this article:
Zhou J, Wang F, Wang H, et al. Ferrocene-induced switchable preparation of metal-nonmetal codoped tungsten nitride and carbide nanoarrays for electrocatalytic HER in alkaline and acid media. Nano Research, 2023, 16(2): 2085-2093. https://doi.org/10.1007/s12274-022-4901-6
Topics:
Electrocatalysis Hydrogen evolution reaction

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Received: 23 June 2022
Revised: 11 August 2022
Accepted: 13 August 2022
Published: 02 September 2022
© Tsinghua University Press 2022
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