Multidimensional In_(2)O_(3)/In_(2)S_(3) heterojunction with lattice distortion for CO_(2) photoconversion  

富含晶格畸变的多维In_(2)O_(3)/In_(2)S_(3)异质结调控用于光催化CO_(2)转化

作　　者：Jinman Yang Xingwang Zhu Qing Yu Minqiang He Wei Zhang Zhao Mo Junjie Yuan Yuanbin She Hui Xu Huaming Li 杨金曼;朱兴旺;于卿;贺敏强;张伟;莫曌;袁俊杰;佘远斌;许晖;李华明(江苏大学化学化工学院,能源研究院,江苏镇江212013;浙江工业大学化工学院,浙江杭州310014)

机构地区：[1]School of Chemistry and Chemical Engineering,Institute of Energy Research,Jiangsu University,Zhenjiang 212013,Jiangsu,China [2]College of Chemical Engineering,Zhejiang University of Technology,Hangzhou 310014,Zhejiang,China

出　　处：《Chinese Journal of Catalysis》2022年第5期1286-1294,共9页催化学报（英文）

基　　金：国家自然科学基金(22075113,22178152,22172066,51902138);江苏省自然科学(BK20190835);镇江市高新技术研究重点实验室(SS2018002);江苏省农业科技自主创新基金(CX(21)3067);国家自然基金重点项目(22138011);中国博士后基金(2021M691305);江苏省博士后基金(2021K079A).

摘　　要：Photocatalytic CO_(2)reduction to sustainably product of fuels is a potential route to achieve clean energy conversion.Unfortunately,the sluggish charge transport dynamics and poor CO_(2)activation performance result in a low CO_(2)conversion efficiency.Herein,we develop a multidimensional In_(2)O_(3)/In_(2)S_(3)(IO/IS)heterojunction with abundant lattice distortion structure and high concentration of oxygen defects.The close contact interfaces between the junction of the two phases ensure undisturbed transmission of electrons with high‐speed.The increased free electron concentration promotes the adsorption and activation of CO2 on the catalyst surface,leaving the key intermediate*COOH at a lower energy barrier.The perfect combination of the band matching oxide and sulfide effectively reduces the internal energy barrier of the CO2 reduction reaction.Furthermore,the lattice distortion structure not only provides additional active sites,but also optimizes the kinetics of the reaction through microstructural regulation.Remarkably,the optimal IO/IS heterojunction exhibits superior CO_(2)reduction performance with CO evolution rate of 12.22μmol g^(−1)h^(−1),achieving about 4 times compared to that of In_(2)O_(3)and In2S3,respectively.This work emphasizes the importance of tight interfaces of heterojunction in improving the performance of CO_(2)photoreduction,and provides an effective strategy for construction of heterojunction photocatalysts.利用光催化技术将CO_(2)进行有效转化是减少排放和实现可再生能源生产的理想途径之一.然而,较低的催化转化效率限制了其实际应用.因此,高效光催化剂的设计合成与改性是促进光催化CO_(2)还原技术发展的关键.在众多催化剂改性策略中,构建异质结构光催化体系是一种有效策略,不仅有利于提高载流子分离效率,还可以优化能级结构,同时改善光吸收.对于异质结材料,有效的界面接触对电子的动态行为起着重要作用,不仅可以为电子提供高速通道,还可以有效抑制光催化CO_(2)还原反应中光生载流子的复合.特别是载流子分离效率高和自由电子浓度增加,可有效促进CO_(2)分子的吸附和活化.此外,构建异质结也是缓解硫化物稳定性差的有效方法.值得注意的是,两种半导体在匹配过程中通常会形成大量的不饱和配位键和空位缺陷,在某种材料中甚至会发生晶格失配导致晶格畸变结构的形成.晶格畸变结构可以为催化反应提供额外的活性位点,并为反应进行提供温床.除光催化剂组成设计外,形貌的合理设计也对催化剂性能有较大影响,因为其不仅与光吸收能力和能带结构有关,而且在很大程度上影响着载流子的输运.近年来,中空结构材料因其独特的结构优势引起了光催化领域研究人员的广泛兴趣.内部空腔为光的多次反射和折射提供机会,进而提升光吸收和利用率.与本体结构相比,中空结构材料具有丰富的活性位点和较大的比表面积,能够为电子提供高速通道,因此,在表面催化反应中具有广阔的应用前景.特别是衍生的金属有机框架材料(MOFs)保留了原始材料的形貌结构,可以通过预先设计前驱体精确控制活性位点.因此,设计以MOFs为前驱体的中空结构催化剂有望提高光催化CO_(2)还原活性.本文通过简单的MOFs衍生策略和原位硫化法构筑了多维中空结构的In_(2)O_(3)/In_(2)S_(3)

关 键 词：PHOTOCATALYSIS CO2 conversion In2O3/In2S3 heterojunction Interface Lattice distortion 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]