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In situ regulating intimately connected heterostructure by decomposition of solid solution oxides toward high-efficient water oxidation

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Abstract

Heterogeneous interfaces produced by inter-domain interactions on a nanoscale performs a crucial role in boosting the properties of an electrocatalyst toward oxygen evolution reaction (OER) process. Herein, a series of dual-phase electrodes with intimately connected heterointerfaces are prepared by in situ decomposing solid solution oxide of NixCoyFe100−x−yO, which grew on Ni foam massively via an ultrafast combustion approach. Particularly, with high-reaction kinetics caused by the reduction treatment at 450 °C, the less electronegative Fe and Co are more oxyphilic than Ni, which facilitated their co-exsolution and formation of CoFe2O4/NiO oxide with enriched oxygen vacancies. Benefiting from the nanoporous framework, heterojunction structure, and oxygen defects, the self-supporting electrodes present rapid charge/mass transmission and provide abundant active sites for OER. The optimized sample (R-SNCF4.5) shows low overpotentials of 226 and 324 mV at 10 and 100 mA·cm−2, a small Tafel slope (46.7 mV·dec−1), and excellent stability. The assembled R-SNCF4.5//Pt/C/NF electrolyzer demonstrates continuous electrolysis over 50 h at a current density of 10 mA·cm−2, under 1.51 V. Density functional theory (DFT) calculations verify that the strong electronic modulation plays a critical part in the CoFe2O4/NiO hybrid by lowering the energy barriers for the rate-determining steps, and Fe sites are the most active OER sites.

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摘要

由纳米尺度上结构域间相互作用产生的异质界面在提高电催化剂的析氧反应 (OER) 性能方面发挥了关键作用。本文通过原位分解NixCoyFe100-x-yO固溶体氧化物制备了一系列具有紧密连接异质界面的双相电极。其中NixCoyFe100-x-yO固溶体氧化物通过超快燃烧法在泡沫镍表面原位、大规模生长制备。尤其在450oC的还原处理条件下会引起快速反应动力学, 因此电负性较低的Fe和Co亲氧性更高, 促进了二者的共同溶出并形成具有富集氧空位的CoFe2O4/NiO双相电极。得益于纳米多孔框架、异质结结构和氧缺陷, 该系列自支撑电极在OER过程中呈现出快速的电荷/质量传输, 并提供了丰富的活性位点。优化后的样品 (R-SNCF4.5) 在10和100 mA·cm−2的电流密度下分别显示出226和324 mV的低过电位, 同时具有小的Tafel斜率 (46.7 mV· dec−1) 和优异的稳定性。组装的R-SNCF4.5//Pt/C/NF全解水体系在1.51 V电位下, 10 mA·cm−2的电流密度下可连续电解50小时不发生电压增加。密度泛函理论计算证实, 有效的电子调控可以降低OER过程中决速步能垒, 并在CoFe2O4/NiO异质电极中起关键作用。该密度泛函理论计算结果也验证了Fe位点是最活跃的OER催化活性位点。

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (No. 52101251) and the Natural Science Foundation of Hebei Province (Nos. E2020208069 and B2020208083).

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Authors and Affiliations

  1. Hebei Key Laboratory of Flexible Functional Materials/Hebei Key Laboratory of Material Near-Net Forming Technology, School of Materials Science and Engineering, Hebei University of Science and Technology, Shijiazhuang, 050018, China

    Shao-Fei Zhang, Xiao-Lu Yin, Jin Wang, Tian-Tian Li, Jin-Feng Sun, Yong-Qiang Meng, Jian-Jiang Wang & Dian-Long Wang

  2. Key Laboratory of Advanced Ceramics and Machining Technology/Ministry of Education, School of Materials Science and Engineering, Tianjin University, Tianjin, 300072, China

    Jian-Li Kang

  3. Electrochemical Engine Center, Department of Mechanical Engineering, Pennsylvania State University, University Park, PA, 16802, USA

    Kai-Qiang Qin

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  1. Shao-Fei Zhang
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Zhang, SF., Yin, XL., Wang, J. et al. In situ regulating intimately connected heterostructure by decomposition of solid solution oxides toward high-efficient water oxidation. Rare Met. 43, 1557–1569 (2024). https://doi.org/10.1007/s12598-023-02536-1

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