Engineering d-band states of(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)material for photocatalytic syngas production  

作　　者：Peng Liu Baopeng Yang Ziyi Xiao Shengyao Wang Shimiao Wu Min Liu Gen Chen Xiaohe Liu Renzhi Ma Ning Zhang 

机构地区：[1]School of Materials Science and Engineering,Central South University,Changsha 410083,Hunan,China [2]School of Physical Science and Electronics,Central South University,Changsha 410083,Hunan,China [3]College of Science,Huazhong Agricultural University,Wuhan 430070,Hubei,China [4]School of Chemical Engineering,Zhengzhou University,Zhengzhou 450001,Henan,China [5]International Center for Materials Nanoarchitectonics(MANA),National Institute for Materials Science(NIMS),1-1 Namiki,Tsukuba,Ibaraki 305-0044,Japan

出　　处：《Journal of Energy Chemistry》2023年第4期365-372,共8页能源化学（英文版）

基　　金：the financial support from the National Natural Science Foundation of China(22072183);the Natural Science Foundation of Hunan Province,China(2022JJ30690);supported in part by the High Performance Computing Center of Central South University。

摘　　要：The d-band states of catalytic materials participate in adsorbing reactive intermediate species and determine the catalytic behaviors in CO_(2)reduction reactions.However,surface d-band states relating to the photocatalytic CO_(2)reduction reactions behaviors are rarely concerned.Herein,a slightly amount of Cd^(2+)is decorated on the surface of(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)material(Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4))to tune the surface d-band states for improved CO_(2)+2reduction reactions.The Cd/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)is fabricated via the facile ions-exchange method to make that slightly Zn2+is substituted by Cd^(2+).The Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)exhibits much enhanced photocatalytic activity in CO_(2)reduction reactions to produce CO and water splitting to produce H_(2).Physical characterizations show that the energy band structure is not changed obviously.Density functional theory reveals that Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)possesses a closer shift of d-band center to Fermi level than(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4),suggesting easier adsorption of CO_(2)reduction reactive intermediates after Cd^(2+)decoration.Further calculations confirm that a relatively reduced adsorption Gibbs energy of reactive intermediates in CO_(2)reduction reaction is required on Zn atoms in Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)material,benefiting the photocatalytic CO_(2)reduction reactions.This work engineers surface d-band states by surface Cd^(2+)decoration,which gives an effective strategy to design highly efficient photocatalysts for syngas production.

关 键 词：Photocatalysisd-band state Density functional theory Sulfide semiconductor Surface modification 

分 类 号：X701[环境科学与工程—环境工程] O644.1[理学—物理化学] O643.36[理学—化学]