Li Shiqi, Liu Weiwei, Shi Yi, Wang Tang, Liu Tianyang, Xue Xiang, Li Rui, Qiao Man, Wu Zhen-Yu, Zhang Wang
College of Materials Science and Engineering, College of Environment, Zhejiang University of Technology, Hangzhou 310014, China; Department of Chemistry, Institute of Innovative Material, Guangdong Provincial Key Laboratory of Sustainable Biomimetic Materials and Green Energy, Southern University of Science and Technology, Shenzhen 518055, China.
College of Materials Science and Engineering, College of Environment, Zhejiang University of Technology, Hangzhou 310014, China.
Sci Bull (Beijing). 2025 Jun 30;70(12):1976-1985. doi: 10.1016/j.scib.2025.04.037. Epub 2025 Apr 21.
Organic ligands in metal-organic frameworks (MOFs) play an indispensable role in the reconstruction and catalysis during the alkaline oxygen evolution reaction (OER). However, it is still a big challenge to maintain a high content of ligands in MOF-reconstructed OER electrocatalysts and to study the interaction between ligands and derived (oxy)hydroxides. Herein, a ligand-rich trimetallic amorphous electrocatalyst is fabricated through a two-step mechanochemical and electrochemical reconstruction strategy. Experimental and theoretical studies clearly reveal that the d-π interaction between delocalized π-electrons on the benzene ring of ligands and derived (oxy)hydroxides, can trigger the charge transfer from ligands to the active metal centers, thus optimizing the adsorption energy of the oxygen-containing intermediates and enhancing the OER performance. Moreover, an anion-exchange membrane water electrolyzer using such ligand-rich OER electrocatalyst can be operated steadily at 1.69 V and 55 °C under an industrial-level current density of 500 mA cm for over 200 h. This work provides novel insights into the role of organic ligands in alkaline OER electrocatalysis, with the potential to facilitate the production of green hydrogen at industrial-level current densities.
金属有机框架材料（MOFs）中的有机配体在碱性析氧反应（OER）的重构和催化过程中发挥着不可或缺的作用。然而，在MOF重构的OER电催化剂中保持高含量的配体以及研究配体与衍生的（氧）氢氧化物之间的相互作用仍然是一个巨大的挑战。在此，通过两步机械化学和电化学重构策略制备了一种富含配体的三金属非晶态电催化剂。实验和理论研究清楚地表明，配体苯环上离域π电子与衍生的（氧）氢氧化物之间的d-π相互作用可引发电荷从配体转移到活性金属中心，从而优化含氧中间体的吸附能并提高OER性能。此外，使用这种富含配体的OER电催化剂的阴离子交换膜水电解槽在500 mA cm的工业级电流密度下，可在1.69 V和55°C下稳定运行超过200小时。这项工作为有机配体在碱性OER电催化中的作用提供了新的见解，具有在工业级电流密度下促进绿色氢气生产的潜力。
