Citation: Min Zhou, Hai-Feng Wang. Insight into the photoexcitation effect on the catalytic activation of H₂ and C-H bonds on TiO₂(110) surface[J]. Chinese Chemical Letters, ;2022, 33(10): 4705-4709. doi: 10.1016/j.cclet.2021.12.074 shu

Insight into the photoexcitation effect on the catalytic activation of H₂ and C-H bonds on TiO₂(110) surface

Min Zhou ,
Hai-Feng Wang ^*,

Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China

hfwang@ecust.edu.cn

Received Date: 11 November 2021
Revised Date: 24 December 2021
Accepted Date: 27 December 2021
Available Online: 2 January 2022

Figures(4)

Semiconductor photocatalysis holds great promise for breaking the inert chemical bonds under mild condition; however, the photoexcitation-induced modulation mechanism has not been well understood at the atomic level. Herein, by performing the DFT+U calculations, we quantitatively compare H₂ activation on rutile TiO₂(110) under thermo- versus photo-catalytic condition. It is found that H₂ dissociation prefers to occur via the heterolytic cleavage mode in thermocatalysis, but changes to the homolytic cleavage mode and gets evidently promoted in the presence of photoexcited hole (h⁺). The origin can be ascribed to the generation of highly oxidative lattice O-radical (O_br^·-) with a localized unoccupied O-2p state. More importantly, we identify that this photo-induced promotion effect can be practicable to another kind of important chemical bond, i.e., C–H bond in light hydrocarbons including alkane, alkene and aromatics; an exception is the C(sp¹)-H in alkyne (HC≡CH), which encounters inhibition effect from photoexcitation. By quantitative analysis, the origins behind these results are attributed to the interplay between two factors: C-H bond energy (E_bond) and the acidity. Owing to the relatively high E_bond and acidity, it favors the C(sp¹)-H bond to proceed with the heterolytic cleavage mode in both thermo- and photo-catalysis, and the photoexcited O_br^·- is adverse to receiving the transferred proton. By contrast, for the other hydrocarbons with moderate/low E_bond, the O_br^·- would enable to change their activation mode to a more favored homolytic one and evidently decrease the C–H activation barrier. This work may provide a general picture for understanding the photocatalytic R–H (R = H, C) bond activation over the semiconductor catalyst.
- Density functional theory calculation,
- Photocatalysis,
- H₂ activation,
- C-H bond activation,
- TiO₂
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Insight into the photoexcitation effect on the catalytic activation of H2 and C-H bonds on TiO2(110) surface

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通讯作者: 陈斌, bchen63@163.com

Insight into the photoexcitation effect on the catalytic activation of H₂ and C-H bonds on TiO₂(110) surface