Photocatalytic C-H Bond Activation of Toluene on Rutile TiO2(110)

Li, Fangliang1,2; Wang, Binli3; Chen, Xiao1,2; Zeng, Weiwang3; Sun, Rulin4; Liu, Xinlu4; Ren, Zefeng3; Yang, Xueming1,2,3; Fan, Hongjun3; Guo, Qing1,2

2022-07-28

10.1021/acs.jpcc.2c02474

Journal of Physical Chemistry C   Impact Factor & Quartile

1932-7447

1932-7455

The activation of sp(3) C-H bond over photoactive TiO2 catalysts has emerged as a promising means to realize the functionalization of hydrocarbons under mild conditions. However, a fundamental understanding of the microscopic mechanism is still unclear. In this work, we have systematically investigated the photochemistry of toluene on rutile (R)-TiO2(110) with temperature-programmed desorption (TPD) and density functional theory (DFT). The TPD results demonstrate that UV light (355 nm) efficiently facilitates the methyl C-H bond activation of toluene at 100 K, forming the stable C6H5CH2 group intermediate adsorbed on five-coordinated Ti4+ sites (Ti-5c) until around room temperature (similar to 300 K). Further DFT calculations suggest that the photocatalytic C-H bond cleavage follow a homolytic manner via the formation of active benzyl radical (C6H5CH2 center dot). Our findings provide an insightful understanding of photocatalytic hydrocarbon functionalization on TiO2 catalysts.

SCI ; EI

English

First ; Corresponding

National Key R&D Program of China[2018YFE0203002] ; National Natural Science Foundation of China["22173041","22103033","22103031","21873096"] ; Strategic Priority Research Program of Chinese Academy of Sciences[XDB17000000] ; Shenzhen Science and Technology Innovation Committee["J C Y J 2 0 1 9 0 8 0 9 1 4 0 2 1 6 6 0","ZDSYS20200421111001787"] ; Guangdong Innovative and Entrepreneurial Research Team Program["2019ZT08L455","2019JC01X091"] ; Chinese Academy of Science[121421KYSB20170012]

Chemistry ; Science & Technology - Other Topics ; Materials Science

Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary

WOS:000831044500001

AMER CHEMICAL SOC

20223412623188

Chemical activation ; Chemical bonds ; Density functional theory ; Oxide minerals ; Temperature programmed desorption ; Titanium dioxide

Minerals:482.2 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Operations:802.3 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Key Lab Energy Chem, Shenzhen 518055, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
3.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China
4.Dalian Maritime Univ, Coll Environm Sci & Engn, Dalian 116026, Liaoning, Peoples R China

Li, Fangliang,Wang, Binli,Chen, Xiao,et al. Photocatalytic C-H Bond Activation of Toluene on Rutile TiO2(110)[J]. Journal of Physical Chemistry C,2022,126(29):11963-11970.

Li, Fangliang.,Wang, Binli.,Chen, Xiao.,Zeng, Weiwang.,Sun, Rulin.,...&Guo, Qing.(2022).Photocatalytic C-H Bond Activation of Toluene on Rutile TiO2(110).Journal of Physical Chemistry C,126(29),11963-11970.

Li, Fangliang,et al."Photocatalytic C-H Bond Activation of Toluene on Rutile TiO2(110)".Journal of Physical Chemistry C 126.29(2022):11963-11970.