金属硫化物基异质结光催化剂:原理、影响、应用和原位表征  

Metal-sulfide-based heterojunction photocatalysts:Principles,impact,applications,and in-situ characterization

作　　者：张海波 王中辽 张金锋 代凯[1,2] Haibo Zhang;Zhongliao Wang;Jinfeng Zhang;Kai Dai(Key Laboratory of Green and Precise Synthetic Chemistry and Applications,Ministry of Education,Huaibei Normal University,Huaibei 235000,Anhui,China;Anhui Province Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation,School of Physics and Electronic Information,Huaibei Normal University,Huaibei 235000,Anhui,China)

机构地区：[1]淮北师范大学绿色和精准合成化学及应用教育部重点实验室,安徽淮北235000 [2]污染物敏感材料与环境修复安徽省重点实验室,安徽淮北235000

出　　处：《Chinese Journal of Catalysis》2023年第6期42-67,共26页催化学报（英文）

基　　金：国家自然科学基金(22278169,51973078);安徽省教育厅优秀科研创新团队(2022AH010028);安徽省教育厅重大项目(2022AH040068);安徽省教育委员会重点基金(2022AH050396).

摘　　要：金属硫化物的窄带隙使其具有吸收可见光和红外光的优势,因此可以用于开发高效的光催化剂.同时,金属硫化物具有出色的电荷分离、较强的光还原能力和低氧化还原能垒.然而,单一金属硫化物通常具有光吸收强度不高和电子-空穴快速复合的问题.在仅考虑光吸收范围时,应选择带隙较窄的光催化剂,但其氧化还原能力较低.此外,金属硫化物易发生光腐蚀.近年来,研究发现,在两种及以上光催化剂间构建异质结可以抑制单一催化剂载流子的复合,促使电子与空穴的分离;同时,异质结光催化剂也被证实可以提高光吸收和增加反应活性位点,是解决金属硫化物自身不足的重要措施.本文总结了金属硫化物用于光催化反应的优势和缺陷,讨论了构建异质结对单一金属硫化物的影响.不同的合成方法对于异质结光催化剂的形貌结构及性能具有重要影响,列举了一些金属硫化物异质结合成方法实例,例如水热合成法、离子交换法、静电纺丝法和原位光化学沉积法等.异质结光催化剂的种类可以根据电子转移机理分为肖特基结、typeⅡ型、Z型和S型异质结等.随后,概述了金属硫化物异质结在环境和能源领域的应用,比较了不同类型金属硫化物异质结的光催化活性.充分利用光生电子和空穴分别驱动氧化和还原反应,这不仅提高了光催化效率,而且拓宽了光催化剂的应用.此外,对异质结的电子转移机理进行了深入讨论,以往的表征手段通常只能间接证明异质结可以抑制电子空穴的复合,进而促进光催化活性,并未直接观察到电子转移路径.近年来,原位表征技术的快速发展弥补了异质结的证据不足,通过原位X射线光电子能谱、原位开尔文探针力显微镜和原位电子顺磁共振等表征手段可以观察到电子转移路径,并可利用原位红外监测反应过程中的中间产物和副产物的生成情况,逐步完Semiconductor photocatalysis is a new sustainable development technology that has demonstrated remarkable potential in the fields of energy-production and environmental-protection.However,a single photocatalyst usually does not possess both strong redox and fast charge-separation properties,greatly limiting photocatalysis efficiency.Heterojunction photocatalysts can perfectly solve this problem by providing multiple reactive sites and fast charge separation and migration,elevating photocatalytic efficiency to a new higher level.Metal sulfides are a family of compounds composed of metals and sulfur(e.g.,CdS,CuS,MoS_(2),In_(2)S_(3),ZnIn_(2)S_(4),and ZnxCd1–xS)that are preferred choices for heterojunction photocatalysts due to their narrow bandgaps,broad visible-light absorption ranges,and convenient preparation methods.This review article introduces the characteristics of metal sulfides,summarizes methods for their synthesis,and discusses various types of metal-sulfide-based heterojunctions.The use of such photocatalysts in energy and environmental-remediation applications is subsequently discussed.In addition,the roles of charge separation and transfer in heterojunction photocatalysts are demonstrated using in-situ characterization techniques.Finally,we discuss some application prospects and challenges concerning metal-sulfide-based heterojunction photocatalysts.

关 键 词：光催化 金属硫化物 异质结 电荷分离 应用 

分 类 号：O644.1[理学—物理化学] O643.36[理学—化学]