Long Yanju, Jiang Pingping, Liao Peisen, Yang Chenyu, Li Suisheng, Xian Jiahui, Sun Yamei, Liu Qinghua, Li Guangqin
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, Lehn Institute of Functional Materials, Institute of Green Chemistry and Molecular Engineering, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China.
BYD Auto Industry Company Limited, Shenzhen, 518083, China.
Small. 2024 Nov;20(46):e2403991. doi: 10.1002/smll.202403991. Epub 2024 Aug 13.
Acquiring a highly efficient electrocatalyst capable of sustaining prolonged operation under high current density is of paramount importance for the process of electrocatalytic water splitting. Herein, Fe-doped phosphide (Fe-NiP) derived from the NiFc metal-organic framework (NiFc-MOF) (Fc: 1,1'-ferrocene dicarboxylate) shows high catalytic activity for overall water splitting (OWS). Fe-NiP||Fe-NiP exhibits a low voltage of 1.72 V for OWS at 0.5 A cm and permits stable operation for 2700 h in 1.0 m KOH. Remarkably, Fe-NiP||Fe-NiP can sustain robust water splitting at an extra-large current density of 1 A cm for 1170 h even in alkaline seawater. Theoretical calculations confirm that Fe doping simultaneously reduces the reaction barriers of coupling and desorption (O→OOH, OOH→O ) in the oxygen evolution reaction (OER) and regulates the adsorption strength of the intermediates (HO, H) in the hydrogen evolution reaction (HER), enabling Fe-NiP to possess excellent dual functional activity. This study offers a valuable reference for the advancement of highly durable electrocatalysts through the regulation derived from coordination frameworks, with significant implications for industrial applications and energy conversion technologies.
获得一种能够在高电流密度下持续长时间运行的高效电催化剂对于电催化水分解过程至关重要。在此，源自NiFc金属有机框架（NiFc-MOF）（Fc：1,1'-二茂铁二甲酸酯）的铁掺杂磷化物（Fe-NiP）对全水分解（OWS）表现出高催化活性。Fe-NiP||Fe-NiP在0.5 A cm下对OWS的电压为1.72 V，并在1.0 m KOH中可稳定运行2700小时。值得注意的是，即使在碱性海水中，Fe-NiP||Fe-NiP在1 A cm的超大电流密度下也能持续强劲的水分解1170小时。理论计算证实，铁掺杂同时降低了析氧反应（OER）中耦合和解吸（O→OOH，OOH→O）的反应势垒，并调节了析氢反应（HER）中中间体（HO，H）的吸附强度，使Fe-NiP具有优异的双功能活性。本研究为通过源自配位框架的调控来推进高耐久性电催化剂提供了有价值的参考，对工业应用和能量转换技术具有重要意义。
