Cr掺杂CoFe2O4诱导羟基溢流促进析氧反应性能

doi:10.1016/S1872-2067(26)65231-X

催化学报 ›› 2026, Vol. 91: 232-240.DOI: 10.1016/S1872-2067(26)65231-X

Cr掺杂CoFe₂O₄诱导羟基溢流促进析氧反应性能

Muhammad Umair Ul Hassan^a^,^b^,¹, 王吉章^a^,¹, Rashid Mehmood^a^,^*(), Fazal Shah^a^,^b, 祁琨^a, 章福祥^a^,^*()

^a 中国科学院大连化学物理研究所, 能源催化转化全国重点实验室, 辽宁大连 116023
^b 中国科学院大学材料科学与光电子工程中心, 北京 100049

收稿日期:2026-03-12 接受日期:2026-05-25 出版日期:2026-12-18 发布日期:2026-10-13
通讯作者: ^*电子信箱: rashidm066@dicp.ac.cn (R. Mehmood),
fxzhang@dicp.ac.cn (章福祥).
作者简介:¹共同第一作者.
基金资助:
中国科学院战略性先导科技专项(XDB0600100);国家自然科学基金(22332005);国家自然科学基金(22302202);榆林清洁能源创新研究院能源革命科技项目(YIICE E411050316);催化国家重点实验室(2024SKL-A-016);中国博士后科学基金博士后奖学金项目(GZC20250056);辽宁省振兴人才计划(XLYC1807241);中国科学院大连化学物理研究所项目(I202439)

Chromium-doped CoFe₂O₄ for enhanced oxygen evolution via hydroxyl spillover

Muhammad Umair Ul Hassan^a^,^b^,¹, Jizhang Wang^a^,¹, Rashid Mehmood^a^,^*(), Fazal Shah^a^,^b, Kun Qi^a, Fuxiang Zhang^a^,^*()

^a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^b Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2026-03-12 Accepted:2026-05-25 Online:2026-12-18 Published:2026-10-13
About author:¹Contributed equally to this work.
Supported by:
Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0600100);National Natural Science Foundation of China(22332005);National Natural Science Foundation of China(22302202);Energy Revolution S&T Program of Yulin Innovation Institute of Clean Energy(YIICE E411050316);State Key Laboratory of Catalysis(2024SKL-A-016);Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(GZC20250056);F.Z. thanks the support from the Liaoning Revitalization Talents Program(XLYC1807241);DICP project(I202439)

摘要/Abstract

摘要：

开发高效、低成本且长期稳定的析氧反应(OER)催化剂对于推动实际水电解应用至关重要. 碱性水电解过程中, OER涉及多电子转移及多个含氧中间体的生成与转化, 其缓慢反应动力学严重限制制氢效率. 贵金属催化剂活性优异但稀缺昂贵, 制约了其大规模应用. 因此, 开发基于地壳丰产元素基的高性能非贵金属催化剂并深入理解其反应机制, 对于实现高效绿色制氢意义重大. 尖晶石型过渡金属氧化物具有组成可调、多价态及结构稳定性良好等特征, 其中CoFe₂O₄因Co/Fe活性中心间的协同作用而展现出较好的析氧潜力. 然而, 其本征活性及高电流密度下的反应动力学仍难以满足实际应用需求, 需通过合理的电子结构调控策略进一步提升催化性能.
基于此, 本文提出了一种通过掺杂调控电子结构并利用羟基溢流促进中间体转化的新策略, 并成功构筑了一种铬掺杂钴铁尖晶石电催化剂(Cr-CoFe₂O₄/IF), 实现了高电流密度条件下高效稳定析氧催化性能. 本文采用简单的水热法将Cr掺杂CoFe₂O₄直接生长于铁泡沫基底上, 构建了具有高效电子传输路径、紧密催化剂-基底接触和丰富活性位点的一体化电极结构. 电化学测试结果表明, 优化后的Cr-CoFe₂O₄/IF电极具有优异的催化活性, 在三电极体系中实现100和500 mA cm^-2电流密度分别仅需260和300 mV的过电位. 此外, 该电极能够在100 mA cm^-2条件下稳定运行超过400 h, 表现出较好的长期稳定性. X-射线光电子能谱和X-射线吸收光谱等结构表征结果表明, Cr掺杂未破坏CoFe₂O₄尖晶石晶体结构, 并且有效调控了Co/Fe活性中心的局域电子环境并诱导电子重新分布, 从而优化了含氧中间体的吸附和转化行为. 进一步结合密度泛函理论计算发现, Cr位点能够优先吸附OH物种, 降低关键反应步骤对应的吉布斯自由能变化, 从而改善析氧反应动力学. 此外, 计算结果还表明, 吸附于Cr位点的OH中间体能够通过掺杂介导的羟基溢流机制迁移至相邻Co/Fe活性位点, 加速关键O-O偶联过程并促进OOH中间体生成, 从而有效降低反应能垒. 原位衰减全反射表面增强红外吸收光谱测试进一步验证了OH及OOH中间体在反应过程中的形成与演变, 为提出的羟基溢流机制提供了直接的关键实验证据, 并支持了电子调控和界面中间体传输在增强催化性能方面的协同作用.
综上, 本工作不仅揭示了Cr掺杂对尖晶石氧化物局域反应环境和O-O偶联动力学的调控作用, 而且为设计高性能、低成本、地球丰富型OER电催化剂提供了新的理论依据和材料设计思路, 对推动实际碱性水电解制氢技术的发展具有重要意义.

关键词: 水分解, 电催化, 非贵金属催化剂, 铬掺杂, 羟基溢流

Abstract:

Developing efficient, low-cost oxygen evolution reaction (OER) electrocatalysts capable of achieving high current densities is critical for advancing practical water electrolysis. Herein, we report a chromium-doped cobalt ferrite (i.e., Cr-CoFe₂O₄/IF) as an efficient OER electrocatalyst in alkaline media. The Cr-CoFe₂O₄/IF electrode exhibits overpotentials of 260 and 300 mV at current densities of 100 and 500 mA cm^-2, respectively, in a three-electrode system and maintains stable operation for more than 400 h, demonstrating its potential for practical application. Structural characterization demonstrates that Cr doping modulates the electronic structure of the Co/Fe active centers. Density functional theory calculations reveal that Cr incorporation introduces preferential hydroxyl adsorption sites, thereby decreasing the Gibbs free energy of the OER process. In particular, ^*OH species adsorbed on Cr sites can migrate to adjacent Co/Fe active sites through a dopant-mediated hydroxyl spillover pathway, which facilitates the formation of O-O coupling to lower the reaction energy barrier. This work establishes dopant-mediated hydroxyl spillover as an effective strategy for designing earth-abundant spinel oxides toward high-rate OER electrocatalysis.

Key words: Water splitting, Electrocatalyst, Non-noble-metal, Cr-doping, Hydroxyl spillover

Muhammad Umair Ul Hassan, 王吉章, Rashid Mehmood, Fazal Shah, 祁琨, 章福祥. Cr掺杂CoFe₂O₄诱导羟基溢流促进析氧反应性能[J]. 催化学报, 2026, 91: 232-240.

Muhammad Umair Ul Hassan, Jizhang Wang, Rashid Mehmood, Fazal Shah, Kun Qi, Fuxiang Zhang. Chromium-doped CoFe₂O₄ for enhanced oxygen evolution via hydroxyl spillover[J]. Chinese Journal of Catalysis, 2026, 91: 232-240.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65231-X

https://www.cjcatal.com/CN/Y2026/V91/I12/232

图/表 4

Fig. 1. Synthesis and structural characterization of Cr-CoFe2O4/IF. (a) Schematic illustration of the synthesis of Cr-CoFe2O4/IF. (b) XRD patterns of Cr-CoFe2O4/IF and control sample CoFe2O4/IF. (c) Raman spectra for Cr-CoFe2O4/IF and control sample. (d,e) HRTEM images of Cr-CoFe2O4/IF. (f) Elemental mapping images of Cr-CoFe2O4/IF.

Fig. 2. Electronic structure characterizations. (a) Co 2p XPS spectra of Cr-CoFe2O4/IF and control sample. (b) Co K-edge XANES spectra of Cr-CoFe2O4/IF and control sample. (c) Corresponding Co EXAFS spectra of both samples. (d) Fe 2p XPS spectra of Cr-CoFe2O4/IF and control sample. Fe K-edge XANES spectra of Cr-CoFe2O4/IF and control sample (e), and corresponding Fe EXAFS spectra (f). (g) Cr 2p XPS spectra of Cr-CoFe2O4/IF. Cr K-edge XANES spectra of Cr-CoFe2O4/IF and Cr2O3 reference sample (h), and corresponding Cr EXAFS spectra (i).

Fig. 3. Electrocatalytic OER performance of Cr-CoFe2O4/IF and control samples. (a) LSV curves of Cr-CoFe2O4/IF and control samples. (b) Overpotential comparison of Cr-CoFe2O4/IF at different current densities. (c) Comparison of overpotential of our catalyst with some state-of-the-art OER catalysts. (d) Tafel plots for Cr-CoFe2O4/IF and control samples. (e) EIS of Cr-CoFe2O4/IF and control samples. (f) ECSA normalized current density of Cr-CoFe2O4/IF and control samples. (g) Long term stability test of Cr-CoFe2O4/IF at a current density of 100 mA cm-2.

Fig. 4. DFT calculations. (a) Dopant-assisted OH spillover mechanism on Cr-CoFe2O4 during OER. (b) OER pathway without OH spillover on CoFe2O4. (c) Calculated free energy profiles of Cr-CoFe2O4 and CoFe2O4.

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Cr掺杂CoFe₂O₄诱导羟基溢流促进析氧反应性能

Chromium-doped CoFe₂O₄ for enhanced oxygen evolution via hydroxyl spillover

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