The Enhancement of Selectivity and Activity for Two-Electron Oxygen Reduction Reaction by Tuned Oxygen Defects on Amorphous Hydroxide Catalysts

作     者：Junheng Huang Changle Fu Junxiang Chen Nangan Senthilkumar Xinxin Peng Zhenhai Wen 

作者机构：CAS Key Laboratory of Design and Assembly of Functional NanostructuresFujian Provincial Key Laboratory of NanomaterialsFujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouFujian 350002 University of the Chinese Academy of ScienceBeijing 100049 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2022年第4卷第2期

页      面：566-583页

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：the Natural Science Foundation of Fujian Province,China(grant no.2020J05079) the National Natural Science Foundation of China(grant nos.21875253,21701175,and 21703248) CAS-Commonwealth Scientific and Industrial Research Organization(CSIRO)Joint Research Projects(no.121835KYSB20200039) the Scientific Research and Equipment Development Project of CAS(no.YJKYYQ20190007) 

主　　题：amorphous hydroxide general preparation two-electron ORR on-site H_(2)O_(2)production three-OH-coordinated Cu sites 

摘      要：Amorphous catalysts,thanks to their uniquely coordinated unsaturated properties and abundance of defect sites,tend to possess higher activity and selectivity than their crystalline *** this work,we report a facile and general solventcontrolled precipitation method to prepare hybrids of graphene oxide(GO)supporting amorphous metal hydroxide[A-M(OH)_(x)/GO,M=Cu,Co,and Mn],which provides us with tangible materials to study the structure–performance relationship of various amorphous *** systematic investigation of A-Cu(OH)_(2)/GO by coupling ex situ/in situ characteristic techniques with electrochemical studies reveals that electrocatalytic activity and selectivity toward a two-electron oxygen reduction reaction(ORR)is highly dependent on the coordinated Cu catalytic sites and the disordered structure of A-Cu(OH)_(2).In situ X-ray absorption near-edge structure(XANES)and density functional theory(DFT)calculation verify that the degree of OH*poisoning(ΔG0 OH*)tuned by three-OH-coordinated Cu sites in amorphous structures plays a crucial role in selective catalysis of ORR for H_(2)O_(2) *** optimized A-Cu(OH)_(2)/GO shows superior activity and high selectivity(~95%)toward H_(2)O_(2),as demonstrated by a zinc–air battery capable of on-site H_(2)O_(2) production with a rate as high as 3401.5 mmol h^(−1) g^(−1).