自牺牲型金属有机框架衍生In_(2)S_(3)多级孔结构纳米材料强化光催化性能  

Self-sacrificing MOF-derived hierarchical porous In_(2)S_(3) nanostructures with enhanced photocatalytic performance

作　　者：杨婷婷 王彬 朱剑豪[2] 夏杰祥[1] 李华明[1] Tingting Yang;Bin Wang;Paul KChu;Jiexiang Xia;Huaming Li(School of Chemistry and Chemical Engineering,Institute for Energy Research,Jiangsu University,Zhenjiang 212013,Jiangsu,China;Department of Physics,Department of Materials Science and Engineering,and Department of Biomedical Engineering,City University of Hong Kong,Tat Chee Avenue,Kowloon,Hong Kong,China)

机构地区：[1]江苏大学化学化工学院,能源研究院,江苏镇江212013 [2]香港城市大学物理系,材料科学与工程系,生物医学工程系,中国香港

出　　处：《Chinese Journal of Catalysis》2024年第4期204-213,共10页催化学报（英文）

基　　金：国家自然科学基金(22108106);国家自然科学基金(22108108);中国博士后科学基金(2022M721380);香港城市大学捐赠研究补助金(DON-RMG 9229021)。

摘　　要：半导体基光催化是减少对化石燃料的依赖和解决环境污染问题的有前景的策略之一.在光催化有机污染物降解领域,硫化物材料备受关注.其中,In_(2)S_(3)催化剂因展现较好的催化活性及经济可行性,而被认为是光催化降解的理想催化剂之一.然而,采用传统煅烧法制备的In_(2)S_(3)催化剂由于比表面积小,暴露的活性位点有限,进而限制了其催化活性的进一步提升.因此,制备具有较大比表面积和多活性位点的In_(2)S_(3)基催化剂,对于推动光催化降解有机污染物领域的发展具有重要的意义.本文通过构建分级多孔结构的光催化剂,以增强材料的光吸收性能并优化光生载流子的迁移和分离,从而提升光催化降解有机污染物的性能.利用In基金属有机骨架(MOFs)作为自我牺牲模板,通过硫化制备了包括空心纳米管、微管、中空球和十二面体在内的多种分级In_(2)S_(3)光催化剂.分级多孔结构不仅增强了入射光的多次折射和反射,还提供了更大的表面积,从而提高了光生载流子的光利用率和相分离效率.实验结果表明,这些材料的光催化效率远高于块状和商用In_(2)S_(3).通过X射线光电子能谱、X射线衍射等手段验证了不同形貌分级多孔In_(2)S_(3)材料的成功制备.紫外-可见漫反射光谱结果表明,所有催化剂均可吸收部分可见光,结合莫特肖特基曲线和XPS价带谱结果,说明催化剂的导带、价带位置均满足光催化降解有机污染物的要求.光致发光光谱、光电流强度曲线和电化学阻抗曲线等研究表明,分级多孔结构有效促进了光生载流子的分离和迁移.光催化降解罗丹明B(RhB)和四环素(TC)性能评价结果表明,与块状和商用In_(2)S_(3)相比,具有分级多孔结构的In_(2)S_(3)材料表现出更好的光催化降解活性.其中,空心In_(2)S_(3)纳米管(HNTs)具有最佳的光催化性能,在光照1.5和2 h后,In_(2)S_(3)-HNT可以去除约50%的TC和Fabrication of porous hierarchical structures is an effective method to improve the photo-absorption capability of photocatalysts by enhancing the photogenerated charge separation and transfer.In-based metal-organic frameworks(MOFs)are utilized as self-sacrificial templates to synthesize various hierarchical In_(2)S_(3) photocatalysts including hollow nanotubes/microtubes/spheres and dodecahedrons by the sulfidation process.The porous hierarchical structures improve multiple refraction and reflection of the incident light,provide larger surface areas,and increase the light utilization and phase separation efficiency of the photogenerated carriers.As a result,the photocatalytic efficiency is much higher than that of the bulk and commercial In_(2)S_(3).In particular,the hollow In_(2)S_(3) nanotubes(HNTs)have the best photocatalytic properties boosting degradation rates of organic pollutants that are 135.6 and 446.9 times than those of the bulk and commercial-grade In_(2)S_(3),respectively.Theoretical calculations,optical/electrical characterization,and free radical trapping experiments reveal that under the condition of light,the photogenerated electron hole pairs produced in In_(2)S_(3)-HNT can effectively separate due to its hierarchical porous structure.So,the In_(2)S_(3)-HNT can accumulate more reactive oxygen radicals.This novel self-sacrificial template method has large potential in the design and fabrication of hierarchical high-efficiency photocatalysts.

关 键 词：硫化铟 金属有机框架 形貌调控 光催化 污染物降解 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学] TB383.1[一般工业技术—材料科学与工程]