Regulating^(*)COOH intermediate via amino alkylation engineering for exceptionally effective photocatalytic CO_(2) reduction  

作　　者：Chengcheng Chen Qiaoyu Zhang Fangting Liu Zhengguo Zhang Qiong Liu Xiaoming Fang 

机构地区：[1]Key Laboratory of Enhanced Heat Transfer and Energy Conservation,The Ministry of Education,School of Chemistry and Chemical Engineering,South China University of Technology,Guangzhou 510640,Guangdong,China [2]Guangdong Provincial Key Laboratory of Chemical Measurement and Emergency Test Technology(China),Institute of Analysis,Guangdong Academy of Sciences(China National Analytical Center,Guangzhou),Guangzhou 510070,Guangdong,China [3]Guangdong Engineering Technology Research Center of Efficient Heat Storage and Application,South China University of Technology,Guangzhou 510640,Guangdong,China [4]Guangdong Provincial Key Laboratory of Fuel Cell Technology,South China University of Technology,Guangzhou 510640,Guangdong,China

出　　处：《Journal of Energy Chemistry》2024年第5期282-291,共10页能源化学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(22309032);the Guangdong Basic and Applied Basic Research Foundation(2022A1515011737);the Science and Technology Program of Guangzhou(2023A04J1395);the GDAS’Project of Science and Technology Development(2021GDASYL-20210102010)。

摘　　要：Photocatalytic reduction of CO_(2) into fuel represents a promising approach for achieving carbon neutrality,while realizing high selectivity in this process is challenging due to uncontrollable reaction intermediate and retarded desorption of target products.Engineering the interface microenvironment of catalysts has been proposed as a strategy to exert a significant influence on reaction outcomes,yet it remains a significant challenge.In this study,amino alkylation was successfully integrated into the melem unit of polymeric carbon nitrides(PCN),which could efficiently drive the photocatalytic CO_(2) reduction.Experimental characterization and theoretical calculations revealed that the introduction of amino alkylation lowers the energy barrier for CO_(2) reduction into^(*)COOH intermediate,transforming the adsorption of^(*)COOH intermediate from the endothermic to an exothermic process.Notably,the as-prepared materials demonstrated outstanding performance in photocatalytic CO_(2) reduction,yielding CO_(2)at a rate of 152.8μmol h^(-1) with a high selectivity of 95.4%and a quantum efficiency of 6.6%.

关 键 词：Polymeric carbonnitride Regulate intermediate Photocatalytic CO_(2)reduction Amino alkylation ^(*)COOH adsorption 

分 类 号：X701[环境科学与工程—环境工程] O643.36[理学—物理化学] O644.1[理学—化学]