Spin engineering of single-site metal catalysts  

作　　者：Zichuang Li Ruguang Ma Qiangjian Ju Qian Liu Lijia Liu Yufang Zhu Minghui Yang Jiacheng Wang 

机构地区：[1]State Key Laboratory of High-Performance Ceramics and Superfine Microstructure,Shanghai Institute of Ceramics,Chinese Academy of Sciences,1295 Dingxi Road,Shanghai 200050,China [2]Center of Materials Science and Optoelectronics Engineering,University of Chinese Academy of Sciences,Beijing 100049,China [3]School of Materials Science and Engineering,Suzhou University of Science and Technology,99 Xuefu Road,Suzhou 215009,China [4]Department of Chemistry,Western University,1151 Richmond Street,London,ON N6A 5B7,Canada [5]Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences,1219 Zhongguan West Road,Ningbo 315201,China [6]Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials,College of Materials Science and Engineering,North China University of Science and Technology,Tangshan 063210,China

出　　处：《The Innovation》2022年第4期96-103,共8页创新（英文）

基　　金：support from the National Natural Science Foundation of China(grants 92163117,52072389,and 52172058);State Key Laboratory of ASIC&Sys-tem(grant 2020KF002);J.W.thanks the Program of Shanghai Academic Research Leader(grant 20XD1424300)for financial support.LL.acknowledges support from the Discovery Program of the Natural Sciences and Engineering Research Council of Canada(NSERC,grant DG RGPIN-2020-06675);Use of the Advanced Photon Source was supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences,under contract DE-AC02-06CH11357;Technical support from APS beamline scientists Dr.George E.Ster-binsky and Dr.Tianpin Wu,and from TLS beamline scientist Dr.Lo-Yueh Chang,is greatly appreciated.

摘　　要：Single-site metal atoms(SMAs)on supports are attracting extensive interest as new catalytic systems because of maximized atom utilization and superior performance.However,rational design of configuration-optimized SMAs with high activity from the perspectives of fundamental electron spin is highly challenging.Herein,N-coordinated Fe single atoms are successfully distributed over axial carbon micropores to form dangling-FeN4 centers(d-FeN4).This unique d-FeN4 demonstrates much higher intrinsic activity toward oxygen reduction reaction(ORR)in HClO4 than FeN4 without micropore underneath and commercial Pt/C.Both theoretical calculation and electronic structure characterization imply that d-FeN4 endows central Fe with medium spin(t2g 4 eg 1),which provides a spin channel for electron transition compared with FeN4 with low spin.This leads to the facile formation of the singlet state of oxygen-containing species from triplet oxygen during the ORR,thus showing faster kinetics than FeN4.This work provides an in-depth understanding of spin tuning on SMAs for advanced energy catalysis.

关 键 词：KINETICS attracting FASTER 

分 类 号：O64[理学—物理化学]