光催化苯制苯酚的研究进展  

Research progress on the heterogeneous photocatalytic selective oxidation of benzene to phenol

作　　者：Mengistu Tulu Gonfa 申升 陈浪[1] 胡彪 周威 白张君 区泽堂 尹双凤[1] Mengistu Tulu Gonfa;Sheng Shen;Lang Chen;Biao Hu;Wei Zhou;Zhang‐Jun Bai;Chak‐Tong Au;Shuang‐Feng Yin(Advanced Catalytic Engineering Research Center of the Ministry of Education,State Key Laboratory of Chemo/Biosensing and Chemometrics,College of Chemistry and Chemical Engineering,Hunan University,Changsha 410082,Hunan,China;College of Chemical Engineering,Fuzhou University,Fuzhou 350002,Fujian,China)

机构地区：[1]湖南大学化学化工学院,化学/生物传感与化学计量学国家重点实验室,教育部高级催化工程研究中心,湖南长沙410082 [2]福州大学化工学院,福建福州350002

出　　处：《Chinese Journal of Catalysis》2023年第6期16-41,共26页催化学报（英文）

基　　金：国家自然科学基金(22008059,21938002,21725602,21975069).

摘　　要：苯酚作为一种重要的有机化学品,广泛用于制造树脂、合成橡胶、染料和药品等行业.然而,传统的苯酚生产方法——联苯法存在着许多问题,如反应条件苛刻和产物纯度低等,这些问题严重制约了苯酚的工业化生产应用.因此,开发一种高效、绿色的苯酚制备方法十分必要.目前,苯一步法制苯酚反应备受关注,然而,实现该反应难度很大.首先,苯分子的C(sp2)-H键活化在化学反应中比较稳定,难以高效活化.其次,相比惰性反应物苯,产物苯酚分子本身更易氧化,使反应的选择性调控成为挑战.光催化选择性氧化苯制苯酚具有反应条件温和、选择性高和产物纯度高等优点,是一种很有工业应用前景的苯酚制备方法.本文系统总结了近年来多相光催化氧化苯制苯酚的研究进展,包括从光催化剂设计原则、改性策略、反应机理分析、影响反应动力学的因素、反应器设计和光催化剂失活机制等方面.首先,单原子、层状双氢氧化物和金属簇构成的光催化剂具有高效催化作用和良好的反应选择性.其次,在光催化反应过程中,光催化剂的设计和合成是非常关键的,可以通过调节光催化剂的组成和结构来提高反应效率和选择性.此外,基于原位表征和密度泛函理论计算的机理研究也为光催化反应的优化提供了重要的理论基础.此外,介绍了光催化反应器的设计原理和操作要点,以及光催化剂失活的原因和解决方案.在未来的研究中,可以考虑更多的应用新材料和新技术来设计和制备高效催化剂.还可以利用先进的表征和理论计算方法更深入地研究光催化反应的机理,并探索更多的反应条件和催化剂组合,以提高光催化反应的效率和选择性.在实际应用中,光催化反应器的设计和操作也需要进一步完善,以确保光催化反应的稳定性和可控性.随着对光催化反应机理和催化剂设计的深入理解,相信�Phenol is important for the manufacture of phenolic chemicals.The current cumene process for phenol production requires harsh conditions and suffers from unwanted side products.Nowadays,the one step conversion of benzene to phenol has received much attention.However,because of the obscurity in benzene C(sp2)–H bond activation and the easy oxidation of phenol,the direct oxidation of benzene to phenol is challenging.As an alternative,the photocatalytic selective oxidation of benzene into phenol under mild conditions is considered promising.In this review,we systematically summarize the recent advance of heterogeneous photocatalytic oxidation of benzene,including those of design principles and various modification strategies,mechanistic understanding determined based on in situ characterization and density functional theory calculation,factors affecting kinetics of the reaction,reactor design and photocatalyst deactivation.It is envisaged that photocatalysts made up of single atoms,layered double hydroxides,and metal clusters are good candidates.At the end of this article,the perspective of catalyst design and strategies for the exploration of reaction mechanism are discussed,emphasizing on the use of state-of-the-art techniques.Moreover,the design of photocatalytic reactors for the realization of the photocatalytic process is considered.

关 键 词：苯 苯酚 直接氧化 光催化剂 光反应器 

分 类 号：TQ243.12[化学工程—有机化工] TQ426