文献类型：期刊文献

英文题名：Optimizing Reaction Kinetics and Thermodynamics for Photocatalytic CO2 Reduction through Spin Polarization Manipulation

作者：Li, Mingyang[1];Wu, Shiqun[1];Liu, Dongni[1];Ye, Zhicheng[2];He, Chengxuan[1];Wang, Jinlong[1];Gu, Xiaoyi[1];Zhang, Zehan[1];Li, Huizi[1];Zhang, Jinlong[1]

机构：[1]East China Univ Sci & Technol, Shanghai Engn Res Ctr Multimedia Environm Catalysi, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem,Sch Che, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2024

卷号：14

期号：18

起止页码：14098

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20243917103810);WOS:【SCI-EXPANDED(收录号:WOS:001310125900001)】；

基金：This work was supported by the National Key R&D Program of China (2022YFE0107900), the National Natural Science Foundation of China (21972040, 21673073, 22202070), the Innovation Program of Shanghai Municipal Education Commission (2021-01-07-00-02-E00106), the Science and Technology Commission of Shanghai Municipality (22230780200, 20DZ2250400), the Project supported by Shanghai Municipal Science and Technology Major Project (2018SHZDZX03), the Postdoctoral Innovative Talent Support Program (BX20220107), the Shanghai Rising-Star Program (22YF1410200), and Fundamental Research Funds for the Central Universities (222201717003). Thanks to the Shanghai Synchrotron Radiation Facility (SSFR, beamline BL14W1) for providing beam time. The authors thank the Anhui Absorption Spectroscopy Analysis Instrument Co, Ltd. for XAFS measurements and analysis.

语种：英文

外文关键词：CO2 photoreduction; spin polarization; photocatalysis; Co vacancy; Co3O4

摘要：The intrinsic properties of electrons, "spin", significantly influence chemical reactions, particularly in catalysis, in terms of reaction rates and pathways. Notably, the effect of electron spin polarization (SP) has been demonstrated to significantly impact photocatalytic processes, yet the exact mechanism remains unclear. In this study, we achieved a controlled manipulation of the material's SP degree by strategically modulating the Co vacancies (V-Co) within Co3-x O-4 as corroborated by magnetic circular dichroism (MCD), positron annihilation spectroscopy, X-ray absorption fine structure (XAFS), and density functional theory (DFT) calculations. Carrier kinetic investigation reveals that the inherent SP of the material and external magnetic field augmented SP significantly enhances charge carrier mobility while attenuating the recombination of photoinduced carriers. Significantly, SP confers a thermodynamic benefit in CO2 reduction, favoring reactant adsorption and concurrently diminishing the free energy requisite for the rate-determining step. Remarkably, a CO production rate of 0.354 mu mol h(-1) (5 mg of catalyst) with 100% selectivity is achieved through manipulation of SP within Co3-x O-4 and applying an external magnetic field. This work reveals the mechanisms of SP effects on photocatalytic reactions, offering insights into the design of CO2 reduction photocatalysts.