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High-entropy alloys for accessing hydrogen economy via sustainable production of fuels and direct application in fuel cells

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Abstract

Heavy consumption of fossil fuels has raised concerns over the climate change and energy security in the past decades. In this review, hydrogen economy, as a clean and sustainable energy system, is receiving great attention. The success of future hydrogen economy strongly depends on the storage of renewable energy in hydrogen and hydrogen-rich chemicals through electrolyzers and conversion back to electricity via fuel cells. Electrocatalysts are at the heart of these critical technologies and great efforts have been devoted to preparing highly efficient nanomaterials. High-entropy alloys (HEAs), with their unique structural characteristics and intrinsic properties, have evolved to be one of the most popular catalysts for energy-related applications, especially those associated with hydrogen economy. Herein, recent advances regarding HEAs-based hydrogen economy are comprehensively reviewed. Attention is paid to the discussion of emerged HEAs as a new class of materials in hydrogen energy cycle, carbon-based hydrogen energy cycle, and nitrogen-based hydrogen energy cycle, covering the sustainable electrochemical synthesis of hydrogen and hydrogen-rich fuels and their direct application in fuel cells. Based on this overview, the challenges and promising directions are proposed to guide the development of HEAs research, aiming to achieve significant progress for further accessing hydrogen economy.

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摘要

在过去的几十年里，化石燃料的大量消耗引起了人们对气候变化和能源安全的担忧。氢经济作为一种清洁、可持续的能源体系受到学术界的高度重视。未来氢经济的实现很大程度上取决于可再生能源通过电解槽储存在氢和富氢化学品中，再通过燃料电池转换回电力。在这一能源转换路径中，高效纳米电催化剂是这些关键技术的核心。高熵合金以其独特的结构特征和内在性能，已成为能源领域特别是氢经济领域最受欢迎的催化剂之一。本文综述了近年来基于高熵合金的氢经济研究进展，重点讨论了氢能循环、碳基氢能循环、氮基氢能循环，涵盖了氢和富氢燃料的可持续电化学合成及其在燃料电池中的直接应用。在此基础上，提出了目前研究所面临的挑战和前景方向，以指导高熵合金催化剂的发展，以期进一步实现氢经济的重大进展。

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Fig. 1
Scheme 1
Fig. 2

Copyright 2020, Springer Nature. g Activities toward HER of FeCoPdIrPt, Pt/C, and pure CP electrodes; h chronopotentiometry curve for FeCoPdIrPt@GO; i amount of H2 during HER. Reproduced with permission from Ref. [59]. Copyright 2020, Springer Nature

Fig. 3

Reproduced with permission from Ref. [62]. Copyright 2021, Springer Nature

Fig. 4

Copyright 2020, American Chemical Society. c Comparative chronoamperometric responses in CO2 saturated electrolyte at different potentials (− 0.7, − 0.8 and − 0.9 V) for 1000 s with respective current density as inset; d bar diagram (with errors) for Faradaic efficiencies (FE) of their respective carbonaceous species and hydrogen gaseous products; e free energy diagram of CO2RR on AuAgPtPdCu HEA surface, and (inset) optimized structures of all intermediates on HEA surface, where gray, green, pink, yellow, blue, brown, red, and orange spheres represent Pt, Pd, Ag, Au, Cu, C, O, and H atoms, respectively. U is applied electrode potential. Reproduced with permission from Ref. [71]. Copyright 2020, American Chemical Society

Fig. 5

Reproduced with permission from Ref. [73]. Copyright 2009, Elsevier. c ECSA-normalized and d mass-normalized CVs of np-PtRuCuOsIr and PtC catalysts for methanol electro-oxidation in 0.5 mol·L−1 H2SO4 + 0.5 mol·L−1 CH3OH solution; e electrochemical CO-stripping curves of np-PtRuCuOsIr and PtC catalysts in 0.5 mol·L−1 H2SO4 solution. Reproduced with permission from Ref. [74]. Copyright 2015, Elsevier. f Peak values of mass activity and area activity; g PDOSs for key intermediates of MOR; h energetic pathway of alkaline MOR; i energetic pathway of CO poisoning. Reproduced with permission from Ref. [58]. Copyright 2020, Springer Nature

Fig. 6

Reproduced with permission from Ref. [75]. Copyright 2009, Elsevier

Fig. 7

Reproduced with permission from Ref. [76]. Copyright 2020, American Chemical Society. e ECSA values and mass activities of different alloys; f CVs recorded in N2-saturated 1.0 mol·L−1 KOH + 0.5 mol·L−1 ethanol solution at a scan rate of 50 mV·s−1; g LSV curve and power densities at different current densities; h comparison of power density with literature data; i surface models with and without doped atoms of Pd used for modeling ethanol catalysis, where navy blue, orange, light blue, and green balls represent Pd, Cu, Mo, and Ni atoms, and red, brown, and light pink balls represent O, C, and H atoms in ethanol molecule, respectively. Reproduced with permission from Ref. [77]. Copyright 2020, Wiley–VCH

Fig. 8

Reproduced with permission from Ref. [82]. Copyright 2020, Wiley–VCH. e Energetic distal pathway of NRR. Reproduced with permission from Ref. [83]. Copyright 2022, Elsevier

Fig. 9

Reproduced with permission from Ref. [88]. Copyright 2021, American Chemical Society

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Nos. U21A20332, 52103226, 52202275, 52203314 and 12204253), the Distinguished Young Scholars Fund of Jiangsu Province (No. BK20220061) and the Fellowship of China Postdoctoral Science Foundation (No. 2021M702382).

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  1. Qi-Yang Cheng and Meng-Fan Wang have contributed equally to this work.

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Nantong University, Nantong, 226019, China

    Qi-Yang Cheng, Si-Si Liu & Tao Qian

  2. Collaborative Innovation Center of Suzhou Nano Science and Technology, College of Energy, Soochow University, Suzhou, 215006, China

    Qi-Yang Cheng, Meng-Fan Wang, Jia-Jie Ni, Yan-Zheng He, Hao-Qing Ji, Si-Si Liu & Cheng-Lin Yan

  3. Light Industry Institute of Electrochemical Power Sources, Suzhou, 215600, China

    Tao Qian & Cheng-Lin Yan

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Cheng, QY., Wang, MF., Ni, JJ. et al. High-entropy alloys for accessing hydrogen economy via sustainable production of fuels and direct application in fuel cells. Rare Met. 42, 3553–3569 (2023). https://doi.org/10.1007/s12598-023-02343-8

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