Photochemistry of Ethanol on Rutile TiO2(110): Breaking Two Bonds with One Hole

Lai, Yuemiao1,2; Zeng, Yi1,2; Chen, Xiao1,2; Wang, Tao1,2; Yang, Xueming1,2,3,4; Guo, Qing1,2

2023

10.1021/acs.jpcc.2c08684

Journal of Physical Chemistry C   影响因子和分区

1932-7447

1932-7455

Understanding the mechanism of ethanol (EtOH) photochemistry is of significance for photocatalytic H2 production. Here, we reported a systematical study of EtOH photochemistry on rutile (R)-TiO2(110), aiming to illustrate how photogenerated holes and electrons are involved in bond breaking. We found that the yields of aldehyde from the ethoxy group and EtOH photooxidation on R- TiO2(110) are proportional to the square root of the photon flux, demonstrating that one hole can induce molecular EtOH decomposition to aldehyde. The initial O-H bond cleavage occurs mainly via a proton-coupled hole transfer process, and the C-H bond cleavage is a hole-mediated process, leaving two electrons on the surface, in agreement with the "current doubling effect". In addition, the rate of aldehyde formation from the ethoxy group is about 3 orders of magnitude faster than that from EtOH, suggesting that the O-H bond cleavage determines the rate of EtOH photochemistry. The results may considerably broaden our understanding of TiO2 photocatalysis.

SCI ; EI

英语

第一 ; 通讯

National Key R&D Program of China[2018YFE0203002] ; National Natural Science Foundation of China (NSFC Center for Chemical Dynamics)[22173041] ; Strategic Priority Research Program of Chinese Academy of Sciences[XDB17000000] ; Shenzhen Science and Technology Innovation Committee["JCYJ2019080914021660","ZDSYS20200421111001787"] ; Guangdong Innovative & Entrepreneurial Research Team Program["2019ZT08L455","2019JC01X091"] ; International Partnership Program of Chinese Academy of Science[121421KYSB20170012] ; Innovation Program for Quantum Science and Technology[2021ZD0303304]

Chemistry ; Science & Technology - Other Topics ; Materials Science

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

WOS:000922886700001

AMER CHEMICAL SOC

20230413451335

Acetaldehyde ; Ethanol ; Hydrogen production ; Oxide minerals ; Photooxidation

Minerals:482.2 ; Gas Fuels:522 ; Light/Optics:741.1 ; Chemical Reactions:802.2 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Key Lab Energy Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
3.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China
4.Hefei Natl Lab, Hefei 230088, Peoples R China

Lai, Yuemiao,Zeng, Yi,Chen, Xiao,et al. Photochemistry of Ethanol on Rutile TiO2(110): Breaking Two Bonds with One Hole[J]. Journal of Physical Chemistry C,2023,127(4):1863-1869.

Lai, Yuemiao,Zeng, Yi,Chen, Xiao,Wang, Tao,Yang, Xueming,&Guo, Qing.(2023).Photochemistry of Ethanol on Rutile TiO2(110): Breaking Two Bonds with One Hole.Journal of Physical Chemistry C,127(4),1863-1869.

Lai, Yuemiao,et al."Photochemistry of Ethanol on Rutile TiO2(110): Breaking Two Bonds with One Hole".Journal of Physical Chemistry C 127.4(2023):1863-1869.