Duan Yan, Lee Jun Yan, Xi Shibo, Sun Yuanmiao, Ge Jingjie, Ong Samuel Jun Hoong, Chen Yubo, Dou Shuo, Meng Fanxu, Diao Caozheng, Fisher Adrian C, Wang Xin, Scherer Günther G, Grimaud Alexis, Xu Zhichuan J
School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore.
Energy Research Institute @ NTU, ERI@N, Interdisciplinary Graduate School, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore.
Angew Chem Int Ed Engl. 2021 Mar 22;60(13):7418-7425. doi: 10.1002/anie.202015060. Epub 2021 Feb 18.
A rational design for oxygen evolution reaction (OER) catalysts is pivotal to the overall efficiency of water electrolysis. Much work has been devoted to understanding cation leaching and surface reconstruction of very active electrocatalysts, but little on intentionally promoting the surface in a controlled fashion. We now report controllable anodic leaching of Cr in CoCr O by activating the pristine material at high potential, which enables the transformation of inactive spinel CoCr O into a highly active catalyst. The depletion of Cr and consumption of lattice oxygen facilitate surface defects and oxygen vacancies, exposing Co species to reconstruct into active Co oxyhydroxides differ from CoOOH. A novel mechanism with the evolution of tetrahedrally coordinated surface cation into octahedral configuration via non-concerted proton-electron transfer is proposed. This work shows the importance of controlled anodic potential in modifying the surface chemistry of electrocatalysts.
合理设计析氧反应(OER)催化剂对于水电解的整体效率至关重要。许多工作致力于理解高活性电催化剂的阳离子浸出和表面重构,但很少有人致力于以可控方式有意地促进表面变化。我们现在报告,通过在高电位下活化原始材料,可实现CoCrO中Cr的可控阳极浸出,这能使惰性尖晶石CoCrO转变为高活性催化剂。Cr的耗尽和晶格氧的消耗促进了表面缺陷和氧空位的形成,使Co物种暴露出来并重构为不同于CoOOH的活性羟基氧化钴。提出了一种通过非协同质子 - 电子转移将四面体配位表面阳离子演化为八面体构型的新机制。这项工作表明了可控阳极电位在改变电催化剂表面化学性质方面的重要性。