锐钛矿TiO<sub>2</sub>可见光催化选择有氧氧化巯基化合物到二硫化物

引用本文: 许辉, 石继龙, 吕少帅, 郎贤军. 锐钛矿TiO₂可见光催化选择有氧氧化巯基化合物到二硫化物[J]. 催化学报, 2020, 41(10): 1468-1473. doi: 10.1016/S1872-2067(20)63640-3 shu

Citation: Hui Xu, Ji-Long Shi, Shaoshuai Lyu, Xianjun Lang. Visible-light photocatalytic selective aerobic oxidation of thiols to disulfides on anatase TiO₂[J]. Chinese Journal of Catalysis, 2020, 41(10): 1468-1473. doi: 10.1016/S1872-2067(20)63640-3 shu

锐钛矿TiO₂可见光催化选择有氧氧化巯基化合物到二硫化物

a 武汉大学化学与分子科学学院索维奇国际分子科学研究中心, 湖北武汉 430072;
b 南开大学先进能源材料化学教育部重点实验室, 天津 300071
基金项目:
国家自然科学基金（21773173，21503086）；中央高校基本科研业务费专项资金（2042018kf0212）；高等学校学科创新引智计划（B12015）；武汉大学引进人才启动基金.

摘要: 二硫化物独特的化学性质使其在生物分子结构改性、药物传输、工业原材料生产中有重要的应用，因而它的合成和研究一直备受关注.在报道的众多合成方法中，最主流的仍然是硫酚的氧化合成.鉴于传统的合成条件严苛、不利于环境保护，以O₂/空气为氧化剂的光催化实现二硫化物的合成已经成为热点研究.在已报道的光催化剂中，TiO₂因为具有化学性质稳定、高效廉价、易回收等优点，在非均相光催化体系中倍受关注.但其缺陷是只能在紫外光区响应激发，这在很大程度上限制了它的应用.本文通过底物巯基化合物与TiO₂表面络合的方式吸收可见光，使其光响应拓展到可见光区.
本文以O₂为氧化剂，巯基化合物与锐钛矿TiO₂络合，可见光高效催化选择氧化生成二硫化物.同时优化了反应条件，如不同波长LED光源、不同类型TiO₂及TiO₂用量，确定硫酚（0.6mmol）、O₂（0.1MPa）、绿光LED（520nm）、CH₃CN（1mL）、锐钛矿TiO₂（30mg，ST-01）为反应最优条件.通过紫外-可见光吸收光谱、透射电镜、比表面积、核磁和高分辨质谱等方法对光催化剂和产物进行表征.结果表明，该反应体系对硫酚（包括杂环、多环硫酚）具有普适性，反应效率高，产率> 90%.其中含吸电子基团的底物比含供电子基团的底物更利于反应进行；同时官能团空间效应对反应速率有一定影响.反应对各类官能团具有很好的兼容性.对于硫醇类底物，需要有机碱三乙胺（TEA）参与才能完成转化.另外，当反应有TEA参与时，可在很短的时间内（< 5min）生成不对称的二硫化物，且产率极高（> 92%）.当底物与二氧化钛的表面络合物吸收可见光后，激发产生的电子通过底物的S原子直接注入到TiO₂的导带，得到含硫自由基和超氧自由基两个活性体.含硫自由基与底物分子作用形成对称的二硫化物，进而在TEA协助下生成不对称二硫化物，而超氧自由基则最终转化成H₂O₂.整个过程中TiO₂的作用至关重要，包括：与巯基化合物络合，完成电子传输，促进超氧自由基形成等.该反应体系简单高效，具有很高的原子经济性，符合绿色化学理念.

关键词:

English

Visible-light photocatalytic selective aerobic oxidation of thiols to disulfides on anatase TiO₂

a Sauvage Center for Molecular Sciences, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China;
b Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education), Nankai University, Tianjin 300071, China
Received Date: 23 February 2020
Revised Date: 26 March 2020
Fund Project:
This work was supported by the National Natural Science Foundation of China (21773173, 21503086), the Fundamental Research Funds for the Central Universities (2042018kf0212), the 111 project (B12015), and the Start-Up Fund of Wuhan University.

Abstract: This work presents the visible-light photocatalytic selective oxidation of thiols to disulfides with molecular oxygen (O₂) on anatase TiO₂. The high specific surface area of anatase TiO₂ proved to be especially critical in conferring high photocatalytic activity. Herein, surface complexation between thiol and TiO₂ gives rise to photocatalytic activity under irradiation with 520 nm green light-emitting diodes (LEDs), resulting in excellent reaction activity, substrate scope, and functional group tolerance. The transformation was extremely efficient for the selective oxidation of various thiols, particularly with substrates bearing electron-withdrawing groups (reaction times of less than 10 min). To date, the longest wavelength of visible light that this system can utilize is 520 nm by the surface complex of substrate-TiO₂. Importantly, O₂ was found to act as the electron and proton acceptor, rather than to incorporate into the substrates. Our findings regarding this surface complex-based photocatalytic system can allow one to understand the interaction between the conduction band electrons and O₂.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

锐钛矿TiO₂可见光催化选择有氧氧化巯基化合物到二硫化物

English

Visible-light photocatalytic selective aerobic oxidation of thiols to disulfides on anatase TiO₂

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锐钛矿TiO2可见光催化选择有氧氧化巯基化合物到二硫化物

English

Visible-light photocatalytic selective aerobic oxidation of thiols to disulfides on anatase TiO2

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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中国化学会秘书处

锐钛矿TiO₂可见光催化选择有氧氧化巯基化合物到二硫化物

Visible-light photocatalytic selective aerobic oxidation of thiols to disulfides on anatase TiO₂

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs