文献类型：期刊文献

英文题名：Insight into photocatalytic CO2 reduction on TiO2-supported Cu nanorods: a DFT study on the reaction mechanism and selectivity

作者：Liu, Ying[1,2];Zhang, Jinyang[1,2];Jin, Jiamin[1,2];Liu, Huihui[1,2];Ren, Guanhua[1,2];Hu, Peijun[1,2,3,4];Wang, Haifeng[1,2]

机构：[1]East China Univ Sci & Technol, Ctr Computat Chem, Sch Chem & Mol Engn, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[3]ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai 201210, Peoples R China;[4]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, North Ireland

年份：2025

卷号：27

期号：5

起止页码：2536

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001396456400001)】；

基金：This project was supported by the National Key Research and Development Program of China (2021YFA1500700), NSFC (22202069, 21873028), Special Support by the China Postdoctoral Science Foundation (in front of the website) (2022TQ0106), the China Postdoctoral Science Foundation Funded Project (2022M721141), and the Fundamental Research Funds for the Central Universities.

语种：英文

摘要：Photoreduction of CO2 into hydrocarbons is a potential strategy for reducing atmospheric CO2 and effectively utilizing carbon resources. Cu-deposited TiO2 photocatalysts stand out in this area due to their good photocatalytic activity and potential methanol selectivity. However, the underlying mechanism and factors controlling product selectivity remain less understood. Using first-principles calculations, this study systematically investigates the possible reaction network for CO2 photocatalytic reduction on TiO2 supported Cu-nanorods (nr-Cu/TiO2), driven by the surface-bound *H species generated via a Volmer-like process (H+ + e- + * -> *H). Our results reveal that the initial hydrogenation of CO2 on nr-Cu/TiO2 is energetically more favorable via the formate (HCOO) pathway than the carboxyl (COOH) route. Notably, HCOO undergoes further hydrogenation for effective C-O bond cleavage, with H2COOH identified as the key intermediate. Both CO (CO2 -> HCOO -> H2COOH -> H2CO -> CO) and CH3OH (CO2 -> HCOO -> H2COOH -> H2CO -> CH3OH) production share the H2CO intermediate, with CO formation proceeding via an unexpected "forth-back" mechanism. Energy profiles suggest that CH3OH formation is more favorable than CO formation. Additionally, excess photogenerated electrons were found to enhance CO2 activation and C-O bond cleavage to some extent but have minimal impact on other reaction steps. This study provides atomic-level insights into the CO2 photoreduction mechanism, offering potential guidance for improving product selectivity.