Engineering spin-dependent catalysts:chiral covalent organic frameworks with tunable electroactivity for electrochemical oxygen evolution  

作　　者：Ziping Li Yueyuan Xiao Chao Jiang Bang Hou Yan Liu Yong Cui 

机构地区：[1]School of Chemistry and Chemical Engineering,Frontiers Science Center for Transformative Molecules and State Key Laboratory of Metal Matrix Composites,Shanghai Jiao Tong University,Shanghai 200240,China

出　　处：《National Science Review》2024年第9期23-32,共10页国家科学评论（英文版）

基　　金：supported by the National Key R&D Program of China(2021YFA1200402,2022YFA1503302,2021YFA1200302,and 2021YFA1501501);the National Natural Science Foundation of China(22225111 and 22331007);the Key Project of Basic Research of Shanghai(21JC1401700 and 22JC1402000);the Shenzhen Science and Technology Program(CJG JZD20210408091800002).

摘　　要：The chiral-induced spin selectivity(CISS)effect offers promising prospects for spintronics,yet designing chiral materials that enable efficient spin-polarized electron transport remains challenging.Here,we report the utility of covalent organic frameworks(COFs)in manipulating electron spin for spin-dependent catalysis via CISS.This enables us to design and synthesize three three-dimensional chiral COFs(CCOFs)with tunable electroactivity and spin-electron conductivity through imine condensations of enantiopure 1,1′-binaphthol-derived tetraaldehyde and tetraamines derived from 1,4-benzenediamine,pyrene,or tetrathiafulvalene skeletons.The CISS effect of CCOFs is verified by magnetic conductive atomic force microscopy.Compared with their achiral analogs,these CCOFs serve as efficient spin filters,reducing the overpotential of oxygen evolution and improving the Tafel slope.Particularly,the diarylamine-based CCOF showed a low overpotential of 430 mV(vs reversible hydrogen electrode)at 10 mA cm^(-2)with long-term stability comparable to the commercial RuO_(2).This enhanced spin-dependent OER activity stems from its excellent redox-activity,good electron conductivity and effective suppression effect on the formation of H_(2)O_(2)byproducts.

关 键 词：3D chiral COF spin-dependent catalysts CISS electrochemical oxygen evolution 

分 类 号：O64[理学—物理化学]