基于共价有机框架的单位点光(电)催化材料的研究进展

Review of covalent organic frameworks for single‐site photocatalysis and electrocatalysis

共价有机框架材料(COFs)是由有机单元通过共价键连接而成的晶态多孔有机聚合物.因其具有长程有序、高表面积和结构可预先设计等特点,为解决日益严重的环境和能源问题提供了新兴的材料平台,在光(电)催化领域得到广泛关注.负载型单位点催化剂具有最大的金属原子利用率和明确的活性中心,对提高原子利用效率、揭示催化反应机制和提升催化性能等具有重要意义,成为近年的科研前沿.基于单位点催化和COFs材料的独特优势,利用COFs材料作为支撑材料锚定高度分散的单位点,如单个金属离子、单原子、单个活性位点或金属团簇等,设计和制备基于COFs的单位点光(电)催化材料成为当前催化科学领域的研究热点之一.近年来,国内外研究人员在设计合成COFs基单位点光(电)催化材料方面取得诸多重要进展.本文综述了COFs基单位点光(电)催化材料的结构特点、设计原则、催化机理及其在光-电催化领域的应用.总结了COFs基单位点材料在光(电)催化应用方面的基本依据和适用光(电)催化的COFs材料的一般合成方法,讨论了COFs基单位点光(电)催化材料的设计原则及优缺点.概述了COFs基单位点光(电)催化材料在光催化分解水、光催化制备H_(2)O_(2)、光催化CO_(2)还原、光催化N_(2)还原、光催化降解污染物、光催化有机转化及电催化分解水、电催化CO_(2)还原、电催化产氧、氧还原和N_(2)还原等领域的最新研究进展,并着重介绍了催化机理.此外,介绍了COFs基单位点光(电)催化材料常用的先进原位表征技术,如原位红外和原位X射线光电子能谱,并对其他先进的原位技术如原位X射线吸收光谱和原位电子顺磁共振光谱等在COFs基单位点催化中的应用进行了展望.总结了理论计算在揭示COFs基单位点光(电)催化材料催化活性来源中的重要作用,并提出用于光催化和电催化的修饰策略.同时指出COFs基单位点材料在光(电)催化领域所面临的挑战和未来的发展机遇.综上,期望本文为COFs基单位点材料在光(电)催化领域的应用提供一些借鉴.

Covalent organic frameworks(COFs)represent a burgeoning category of highly tunable crystalline porous materials,which have garnered significant attention as promising platforms for designing novel photo‐and electrocatalysts.Single‐site catalysis holds paramount importance in revealing the catalytic reaction mechanism and enhancing catalytic performance because of the maximum utilization of metal atoms and presence of a definite active center.Given the distinct advantages of single‐site catalysts,such as single metal ions,single atoms,single active sites,and metal clusters,and COFs materials,there is a current surge of interest in using COFs materials as support materials to anchor highly dispersed single‐sites.Consequently,the design and preparation of COF‐based single‐site catalysts have emerged as a prominent research topic in the fields of photo‐and electrocatalysis,to address the pressing environmental and energy issues.This review provides an overview of the development of COF‐based single‐site photo‐and electrocatalysts.Advanced applications of COF‐based single‐site photo‐and electrocatalysts are comprehensively summarized and reviewed.Additionally,the review addresses the challenges faced by COF‐based single‐site photo‐and electrocatalysts and discusses their future development trends.We aim to provide new insights into the application of COF‐based single‐site materials in photo‐and electrocatalysis and further promote the development of catalytic science.