Aerobic oxidation of toluene and benzyl alcohol to benzaldehyde using a visible light-responsive titanium-oxide cluster

被引：31

作者：

Wu, Wenli ^{[1
]}

Zhang, Guanyun ^{[2
]}

Zhang, Jian ^{[3
]}

Wang, Guo ^{[4
]}

Tung, Chen-Ho ^{[2
]}

Wang, Yifeng ^{[2
,3
]}

机构：

[1] Qilu Univ Technol, Shandong Acad Sci, Sch Pharmaceut Sci, Jinan 250014, Peoples R China

[2] Shandong Univ, Sch Chem & Chem Engn, Key Lab Colloid & Interface Sci, Minist Educ, Jinan 250100, Peoples R China

[3] Shandong Univ, State Key Lab Crystal Mat, Jinan 250100, Peoples R China

[4] Capital Normal Univ, Dept Chem, Beijing, Peoples R China

来源：

CHEMICAL ENGINEERING JOURNAL | 2021年 / 404卷

基金：

中国国家自然科学基金;

关键词：

Titanium-oxide cluster; Selective oxidation; Visible light; Photocatalysis; Br--association; C-H BONDS; PHOTOCATALYTIC ACTIVATION; TIO2; PHOTOCATALYSIS; MOLECULAR-OXYGEN; BINDING MODES; NANOPARTICLES; DEGRADATION; DIOXIDE; DYES; SIZE;

D O I：

10.1016/j.cej.2020.126433

中图分类号：

X [环境科学、安全科学];

学科分类号：

08 ; 0830 ;

摘要：

Photocatalytic selective oxidation using sunlight and O-2 can serve as a green and cost-effective method for the transformation of organic raw materials to value-added products. Here, we report a [Ti6O8(OH2)(20)](8+) cluster modified with Br- (denoted as Ti6B) triggers the selective conversion of toluene and benzyl alcohol to benzaldehyde under visible light irradiation with high efficiency. The absorption edge of Ti6B in MeCN solution is ca. 500 nm. The conversion of toluene, operated under non-solvent conditions, reached 4.7% with ca. 80% selectivity. The yield of benzaldehyde from benzyl alcohol reached 96%. Common substituents could be tolerated. ESR analyses indicate superoxide is directly involved in the reactions. The results of O-17 NMR, IR and small angle scattering indicate Ti6B is the true photocatalyst. Mechanistic studies suggest Br- binds to Ti4+ at the Ti-oxo core of Ti6B and the photo-driven electronic transition is from HOMO comprised of Br2p to LUMO + 1 comprised of Ti3d orbitals.

引用

页数：10

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