高校化学工程学报2025，Vol.39Issue(6)：1020-1033,14.DOI:10.3969/j.issn.1003-9015.2025.00.017
TS-1催化苯羟基化制苯酚过程中Ti活性位点的作用机制
The role of Ti active sites in TS-1 catalyzed benzene hydroxylation to phenol
摘要
Abstract
The role of different Ti active sites in TS-1 catalyzed hydroxylation of benzene with H2O2 to phenol was investigated by evaluating two tripodal structures(Tripodal(1I)and Tripodal(2I))and a defective Ti-Defect mod-el.Density functional theory(DFT)at the PBEO-D3(BJ)/genecp level was employed to analyze structural evolu-tion,atomic charge distribution,and Gibbs free energy changes during the reaction,as well as frontier molecular orbitals and electrostatic potential distributions at the reaction sites.This elucidated the reactant activation,inter-mediate evolution processes,and rate-controlling steps on different active sites.The results indicate that the rate-controlling step across all three Ti sites is the electrophilic substitution reaction between the Ti-peroxo(Ti—OOH)active species generated from the interaction of H2O2 with Ti sites and the benzene.Among the three sites,the Ti-Defect site exhibits the highest atomic charge on Ti,the smallest energy level of the lowest unoccupied molecular or-bital(LUMO),and the strongest surface electrostatic potential,leading to the lowest reaction energy barriers in both H2O2 dissociation and benzene electrophilic substitution steps.These findings provide theoretical insights for the design of high-performance TS-1 catalysts.关键词
苯羟基化/TS-1/活性位点/反应机理/分子模拟Key words
benzene hydroxylation/TS-1/active site/reaction mechanism/molecular simulation分类
化学化工引用本文复制引用
江英迪,詹万滨,杨焯,夏长久,钱刚,段学志,周兴贵..TS-1催化苯羟基化制苯酚过程中Ti活性位点的作用机制[J].高校化学工程学报,2025,39(6):1020-1033,14.基金项目
石油化工分子转化与反应工程全国重点实验室开放课题(36800000-24-ZC0607-0110) （36800000-24-ZC0607-0110）
国家自然科学基金(22178101). （22178101）
