Mechanism investigation of A-site doping on modulating electronic band structure and photocatalytic performance towards CO_(2) reduction of LaFeO_(3) perovskite  

作　　者：Chi Cao Jinshuo Li Yang Hu Lin Zhang Wensheng Yang 

机构地区：[1]State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,College of Chemistry,Jilin University,Changchun 130012,China [2]Engineering Research Center for Nanomaterials,Henan University,Kaifeng 475004,China

出　　处：《Nano Research》2024年第5期3733-3744,共12页纳米研究（英文版）

基　　金：supported by the National Natural Science Foundation of China(No.21773089).

摘　　要：Three kinds of metal atoms with different valence electronic configurations,Bi(6s^(2)6p^(3)),Y(4d^(1)5s^(2)),and Ce(4f^(1)5d^(1)6s^(2)),were selected to investigate the effect of A-site(La^(3+))doping on electronic band structure,photoelectric properties,and photocatalytic performance of LaFeO_(3) perovskite.It was identified that the Bi doped LaFeO_(3) presented significantly improved photocatalytic activity towards the reduction of CO_(2),while the Y or Ce doped LaFeO_(3) displayed decreased photocatalytic activity compared to the pristine LaFeO_(3).It was revealed that doping of all the three metal atoms resulted in narrowed band gap and thus extended light absorption of LaFeO_(3) by lowering its conduction band minimum(CBM).The recombination rate and mobility of the charge carriers were represented by the relative effective mass(D)between holes and electrons for pristine and A-site doped LaFeO_(3).The doping of Bi resulted in increased D value,attributed to the Bi 6s electron states at the valence band maximum(VBM),and thus promoted separation and transfer of the charge carriers and improved photocatalytic activity of LaFeO_(3).In contrast,the doping of Ce resulted in significantly decreased D value,induced by the highly localized Ce 4f hole states at the CBM,and thus higher recombination rate of the charge carriers and decreased photocatalytic activity of LaFeO_(3).Furthermore,the Y doped LaFeO_(3) with a slightly decreased D value presented slightly increased recombination rate of the charge carriers and thus decreased photocatalytic activity.Such a work provides new insights into the A-site doping in LaFeO_(3) perovskite,which should be helpful for optimizing the electronic band structure and activity of perovskite-type photocatalysts at atomic level.

关 键 词：A-site doping electronic band structure charge carrier behavior photocatalytic CO_(2)reduction perovskite-type photocatalytsts 

分 类 号：O61[理学—无机化学]