Selectivity control of photocatalytic CO_(2) reduction over ZnS-based nanocrystals:A comparison study on the role of ionic cocatalysts  

作　　者：Hong Pang Fumihiko Ichihara Xianguang Meng Lijuan Li Yuqi Xiao Wei Zhou Jinhua Ye 

机构地区：[1]Hebei Provincial Laboratory of Inorganic Nonmetallic Materials,College of Materials Science and Engineering,North China University of Science and Technology,Tangshan 063210,Hebei,China [2]International Center for Materials Nanoarchitectonics(WPI-MANA),National Institute for Materials Science(NIMS),Tsukuba 305-0044,Japan [3]Center for Green Research on Energy and Environmental Materials(GREEN),National Institute for Materials Science(NIMS),Tsukuba 305-0044,Japan [4]Department of Applied Physics,School of Science,Tianjin University,Tianjin 300072,China [5]Graduate School of Chemical Sciences and Engineering,Hokkaido University,Sapporo 060-0814,Japan

出　　处：《Journal of Energy Chemistry》2023年第11期391-398,I0009,共9页能源化学（英文版）

基　　金：financial support from the Tangshan Talent Funding Project(A202202007);the National Natural Science Foundation of China(21703065);the Natural Science Foundation of Hebei Province(B2018209267);the World Premier International Research Center Initiative(WPI Initiative)on Materials Nanoarchitectonics(MANA),the MEXT(Japan);the Photoexcitonix Project in Hokkaido University;the JSPS KAKENHI(Grant Number JP18H02065)。

摘　　要：Taking copper doped ZnS(ZnS:Cu)nanocrystals as the main body of photocatalyst,the influence of different base transition metal ions(M^(2+)=Ni^(2+),Co^(2+),Fe^(2+)and Cd^(2+))on photocatalytic CO_(2)reduction in inorganic reaction system is investigated.Confined single-atom Ni^(2+),Co^(2+),and Cd^(2+)sites were created via cation-exchange process and enhanced CO_(2)reduction,while Fe^(2+)suppressed the photocatalytic activity for both water and CO_(2)reduction.The modified ZnS:Cu photocatalysts(M/ZnS:Cu)demonstrated tunable product selectivity,with Ni^(2+)and Co^(2+)showing high selectivity for syngas production and Cd^(2+)displaying remarkable formate selectivity.DFT calculations indicated favorable H adsorption free energy on Ni^(2+)and Co^(2+)sites,promoting the hydrogen evolution reaction.The selectivity of CO_(2)reduction products was found to be sensitive to the initial intermediate adsorption states.*COOH formed on Ni^(2+)and Co^(2+)while*OCHO formed on Cd^(2+),favoring the production of CO and HCOOH as the main products,respectively.This work provides valuable insights for developing efficient solar-to-fuel platforms with controlled CO_(2)reduction selectivity.

关 键 词：CO_(2) reduction Photocatalysis Zns Ionic cocatalyst FORMATE Syngas DFT calculations 

分 类 号：O643.36[理学—物理化学] TB383.1[理学—化学]