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Non-noble metal-based bifunctional electrocatalysts for hydrogen production

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Abstract

Hydrogen is a promising candidate for clean and sustainable energy resources to substitute fossil fuels to mitigate global environmental issues. Electrochemical hydrogen production has been regarded as a viable and promising strategy. The overall water splitting is currently the predominant electrochemical hydrogen production method, which could be driven by renewable energy to achieve sustainable production. However, the current challenges are the intrinsically sluggish and energy-intensive oxygen evolution reduction (OER) at the anode and the expensive noble metal-based catalysts for overall water splitting, which limit the practical applications. Extensive efforts have been made to develop bifunctional non-noble metal-based electrocatalysts to boost hydrogen production efficiency and lower the cost. Meanwhile, alternative oxidation reactions with faster kinetics and less energy requirement than OER are being explored as the anodic reaction to couple with the hydrogen evolution reaction for energy-saving hydrogen production. In this review, the non-noble metal-based bifunctional electrocatalysts for overall water splitting, as well as other novel energy-saving hydrogen productions have been introduced and summarized. Current challenges and outlooks are commented on at the end of the article.

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摘要

氢气是清洁和可持续能源, 也是替代化石燃料从而缓解全球环境问题的最佳候选。电化学制氢被认为是一种可行且具备应用前景的重要策略。目前, 电化学催化水分解是目前最主要的电化学制氢方法, 该方法可以由可再生能源驱动从而实现可持续产氢过程。然而, 当前水分解催化制氢面临的挑战是阳极的析氧还原不仅动力学缓慢而且需要较高的过电势来驱动反应进行, 一般需要昂贵稀少的贵金属基催化剂来实现水分解制氢, 从而限制了大规模的工业应用前景。目前, 科学界已经进行了广泛的研究来开发双功能非贵金属基电催化剂用于水分解, 从而提高制氢效率并降低成本。与此同时, 作为与析氢反应耦合以实现高效节能制氢的阳极反应, 探索具有比析氧还原反应具有更快动力学和更少能量需求的替代氧化反应也成为了新的研究重点。在该综述中, 我们对于可用于整体水分解的非贵金属基双功能电催化剂进行了分类与总结, 并对其他新型可用于高效水分解制氢的替代氧化过程进行了介绍, 并在最后对当前的电化学制氢催化剂所面临的挑战和未来发展方向进行了全面的展望。

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Fig. 1

Reproduced with permission from Ref. [8]. Copyright 2019, Elsevier B.V. b Schematic illustration of integrated HER and biomass valorization. Reproduced with permission from Ref. [11]. Copyright 2016, American Chemical Society

Fig. 2

Reproduced with permission from Ref. [14]. Copyright 2015, the Author(s). g LSV curve of two-electrode setup with bifunctional catalysts for overall water splitting in 1 mol·L−1 NaOH and (inset) optical image of O2 and H2 bubble generated at FeOx/NF-Li anode and cathode, respectively; h chronoamperometry of water electrolysis at a cell voltage of 1.63 V for FeOx/NF-Li; i mechanism schematic illustration for OER and HER on FeOx/NF-Li. Reproduced with permission from Ref. [20]. Copyright 2020, American Chemical Society. j proposed mechanism of adaptive bifunctional amorphous CoFeO@BP electrocatalyst for overall water splitting. Reproduced with permission from Ref. [21]. Copyright 2020, Wiley–VCH GmbH

Fig. 3

Reproduced with permission from Ref. [31]. Copyright 2016, WILEY–VCH Verlag GmbH & Co. KGaA, Weinheim. b Schematic illustration of a general approach for metal phosphide@C for highly efficient overall water splitting. Reproduced with permission from Ref. [42]. Copyright 2020, American Chemical Society. c Schematic illustration of synthesis of CoNx@GDY NS/NF via an in-site growth strategy. Reproduced with permission from Ref. [44]. Copyright 2019, Elsevier Ltd

Fig. 4

Reproduced with permission from Ref. [48]. Copyright 2018, Elsevier B.V. b Current density of NixB/f-MWCNT and NixB as a function of scan rate, where surface-specific double-layer capacitance (Cdl) is shown in annotation; c EIS spectra of NixB/f-MWCNT and NixB recorded under the constant potential of 1.55 V (vs. RHE); d comparison of required voltage for overall water splitting at current density of 10 mA·cm−2 for NixB/f-MWCNT and other recently reported noble metal-free bifunctional catalysts. Reproduced with permission from Ref. [51]. Copyright 2019, Royal Society of Chemistry

Fig. 5

Reproduced with permission from Ref. [60]. Copyright 2018, the Authors. c LSV curves for UOR (0.33 M being 0.33 mol·L−1); d Tafel slopes for UOR; e LSV curves for HER; f Tafel slopes for HER. Urea splitting performance of NO and NFO in 1 mol·L−1 KOH solution with 0.33 mol·L−1 urea: g LSV curves; h chronopotentiometry curves at the current density of 10 mA·cm−2. Reproduced with permission from Ref. [72]. Copyright 2019, Royal Society of Chemistry

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Acknowledgments

This work was financially supported by the National Key R&D Program of China (No. 2021YFA1501101), the National Natural Science Foundation of China (No. NSFC 21771156) and the NSFC/RGC Joint Research Scheme Project (N_PolyU502/21).

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  1. Department of Applied Biology and Chemical Technology, the Hong Kong Polytechnic University, Hong Kong 999077, China

    Tong Wu, Ming-Zi Sun & Bo-Long Huang

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Wu, T., Sun, MZ. & Huang, BL. Non-noble metal-based bifunctional electrocatalysts for hydrogen production. Rare Met. 41, 2169–2183 (2022). https://doi.org/10.1007/s12598-021-01914-x

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