文献类型：期刊文献

英文题名：Single-Atom High-Valent Fe(IV) for Promoted Photocatalytic Nitrogen Hydrogenation on Porous TiO2-SiO2

作者：Wu, Shiqun[1,2];Chen, Ziyu[1,2];Yue, Wenhui[1,2];Mine, Shinya[3];Toyao, Takashi[4,5];Matsuoka, Masaya[3];Xi, Xinguo[6];Wang, Lingzhi[1,2];Zhang, Jinlong[1,2,6]

机构：[1]East China Univ Sci & Technol, Shanghai Engn Res Ctr Multimedia Environm Catalys, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Joint Int Res Lab Precis Chem & Mol Engn, Sch Chem & Mol Engn,Feringa Nobel Prize Scientist, Shanghai 200237, Peoples R China;[3]Osaka Prefecture Univ, Dept Appl Chem, Sakai, Osaka 5998531, Japan;[4]Hokkaido Univ, Inst Catalysis, Sapporo, Hokkaido 0010021, Japan;[5]Kyoto Univ, Elements Strategy Initiat Catalysts & Batteries, Kyoto 6158520, Japan;[6]Yancheng Inst Technol, Sch Chem & Chem Engn, Yancheng 224051, Peoples R China

年份：2021

卷号：11

期号：7

起止页码：4362

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20211810303388);WOS:【SCI-EXPANDED(收录号:WOS:000637003700054)】；

基金：This work was supported by the National Natural Science Foundation of China (21972040 and 21673073), the Science and Technology Commission of Shanghai Municipality (18520710200 and 20DZ2250400), the Shanghai Pujiang Program (18PJD012), the PetroChina Innovation Foundation (2015D-5006-0402), the project supported by the Shanghai Municipal Science and Technology Major Project (no. 2018SHZDZX03), and the Program of Introducing Talents of Discipline to Universities (nos. B20031 and B16017). The X-ray absorption fine-structure (XAFS) measurements were performed under the approval of the JASRI (proposal no. 2019B1686). The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for the help on the characterization.

语种：英文

外文关键词：photofixation of nitrogen; water oxidation; high-valent Fe(IV); nitrogen hydrogenation; single-atom

摘要：Synergistic nitrogen reduction and water oxidation process is significant to the photocatalytic fixation of nitrogen. However, the coupling mechanism remains ambiguous and lacks study. Herein, we report enhanced photocatalytic nitrogen fixation on single-atom Fe-modified macro-/mesoporous TiO2-SiO2 (Fe-T-S), with a high ammonia generation rate of 32 mu mol g(-1) h(-1) without any sacrificial agent and cocatalysts. Experimental and theoretic calculation studies confirmed the formation of a photoinduced hole-trapping polaron on the Fe dopant, resulting in the high-valent Fe(IV) species. The single-atom Fe(IV) site is responsible for water oxidation and helps promote N-2 hydrogenation on neighboring oxygen vacancy. This study explicitly unravels the key to achieve the coupling between photocatalytic N-2 hydrogenation and water oxidation through a doping strategy and provides significant guidance for the rational design of photocatalysts for ammonia synthesis.