文献类型：期刊文献

英文题名：Unraveling the intricate solvent-catalyst interplay in TS-1 catalyzed benzene hydroxylation: Experimental and molecular simulation insights

作者：Jiang, Yingdi[1];Zhan, Wanbin[1];Yang, Chao[2];Zhang, Jing[1];Xia, Changjiu[2];Qian, Gang[1];Duan, Xuezhi[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn & Low Carbon Technol, Shanghai 200237, Peoples R China;[2]Sinopec Res Inst Petr Proc, Beijing 100083, Peoples R China

年份：2026

卷号：92

起止页码：37

外文期刊名：CHINESE JOURNAL OF CHEMICAL ENGINEERING

收录：;EI(收录号：20261420410627);WOS:【SCI-EXPANDED(收录号:WOS:001833964600001)】；

基金：This work was supported by State Key Laboratory of Petroleum Molecular & Process Engineering (36800000-24-ZC0607-0110) , and the National Natural Science Foundation of China (22178101) .

语种：英文

外文关键词：Benzene; Hydroxylation; TS-1; Solvents; Molecular simulation

摘要：The direct hydroxylation of benzene with hydrogen peroxide (H2O2) over titanium silicalite-1 (TS-1) offers an environmentally benign route to phenol, though its efficiency is highly dependent on the solvent environment. By integrating experimental and theoretical approaches, this study reveals the underlying mechanism. Water uniquely boosts benzene conversion to 45.8% through synergistic effects. It serves as a proton-transfer mediator to lower the activation barrier (Delta G), enhances the electrophilicity of Ti-active sites via increased maximum electrostatic potential (ESPmax), and leverages the hydrophobic pores of TS-1 to enrich benzene near the active sites. However, this multifunctional enhancement also promotes over-oxidation, limiting phenol selectivity to 42.8%. In contrast, the organic solvents suppress consecutive oxidation and achieve high selectivity above 70% due to their larger HOMO-LUMO energy gaps (Egap). Yet they exhibit low activity owing to higher energy barriers, weaker electrophilicity, and competitive adsorption. This work further establishes quantitative correlations between catalytic performance and key descriptors such as Delta G, ESPmax, and Egap, providing a predictive framework for rational solvent selection in TS-1 catalysis. (c) 2025 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.