文献类型：期刊文献

英文题名：Engineering Spatially Adjacent Redox Sites with Synergistic Spin Polarization Effect to Boost Photocatalytic CO2 Methanation

作者：Li, Mingyang[1];Wu, Shiqun[1];Liu, Dongni[1];Ye, Zhicheng[1];Wang, Lijie[1];Kan, Miao[1];Ye, Ziwei[1];Khan, Mazhar[1];Zhang, Jinlong[1,2]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Shanghai Engn Res Ctr Multimedia Environm Catalysi, Sch Chem & Mol Engn,Key Lab Adv Mat,Joint Int Res, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Engn Res Ctr Multimedia Environm Catalysi, Shanghai 200237, Peoples R China

年份：2024

卷号：146

期号：22

起止页码：15538

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20242216167735);WOS:【SCI-EXPANDED(收录号:WOS:001228932800001)】；

基金：This work was supported by the National Key R&D Program of China Program of China (2022YFE0107900, 2022YFB3803600), the National Natural Science Foundation of China (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, 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. We thank the Anhui Absorption Spectroscopy Analysis Instrument Co, Ltd. for XAFS measurements and analysis.

语种：英文

外文关键词：Carbon dioxide - Cobalt - Manganese - Redox reactions

摘要：The integration of oxidation and reduction half-reactions to amplify their synergy presents a considerable challenge in CO2 photoconversion. Addressing this challenge requires the construction of spatially adjacent redox sites while suppressing charge recombination at these sites. This study introduces an innovative approach that utilizes spatial synergy to enable synergistic redox reactions within atomic proximity and employs spin polarization to inhibit charge recombination. We incorporate Mn into Co3O4 as a catalyst, in which Mn sites tend to enrich holes as water activation sites, while adjacent Co sites preferentially capture electrons to activate CO2, forming a spatial synergy. The direct H transfer from H2O at Mn sites facilitates the formation of *COOH on adjacent Co sites with remarkably favorable thermodynamic energy. Notably, the incorporation of Mn induces spin polarization in the system, significantly suppressing the recombination of photogenerated charges at redox sites. This effect is further enhanced by applying an external magnetic field. By synergizing spatial synergy and spin polarization, Mn/Co3O4 exhibits a CH4 production rate of 23.4 mu mol g(-1) h(-1) from CO2 photoreduction, showcasing a 28.8 times enhancement over Co3O4. This study first introduces spin polarization to address charge recombination issues at spatially adjacent redox sites, offering novel insights for synergistic redox photocatalytic systems.