Identifying Photocatalytic Active Sites of C2H6 C-H Bond Activation on TiO2 via Combining First-Principles Ground-State and Excited- State Electronic Structure Calculations

Wang, Xiaoning2,3; Wan, Lingyun2,3; Wang, Zijian2,3; Liu, Xiaofeng4; Gao, Yunzhi2,3; Wang, Lei2,3; Liu, Jie2,3; Guo, Qing1; Hu, Wei2,3; Yang, Jinlong2,3

2022-07-21

10.1021/acs.jpclett.2c01100

Journal of Physical Chemistry Letters   Impact Factor & Quartile

1948-7185

The activation of C-H bonds at low temperatures has attracted widespread interest in heterogeneous catalysis, which involves complex thermocatalytic and photocatalytic reaction processes. Herein, we systematically investigate the photothermal catalytic process of C-H bond activation in C2H6 dehydrogenation on rutile TiO2(110). We demonstrate that the photochemical activity of theC(2)H(6) molecule adsorbed on TiO2(110) is site-sensitive and that C2H6 is more easily adsorbed at the Ti5c site with a lower dehydrogenation energy barrier. The first C-H bond activation of the C(2)H(6 )adsorbed at the Ti5c site tends to occur in the ground state, whereas Obr-adsorbed C2H6 is more photoactive during the initial adsorption. During the dehydrogenation of C2H6, the photogenerated electrons are always located at the Ti4+ sites of the TiO2 substrate while the photogenerated holes can be captured by C(2)H(6 )to activate the C-H bond.

SCI ; EI

English

NI Journal Papers

Corresponding

National Natural Science Foundation of China["22173093","22003061"] ; Hefei National Laboratory for Physical Sciences at the Microscale["KF2020003","SK2340002001"] ; Chinese Academy of Sciences Pioneer Hundred Talents Program[KJ2340007002] ; Anhui Initiative in Quantum Information Technologies[AHY090400] ; Center of Chinese Academy Project for Young Scientists in Basic Research[YSBR-005] ; Fundamental Research Funds for the Central Universities from the University of Science and Technology of China["WK2340000091","WK2060000018"]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Atomic, Molecular & Chemical

WOS:000829607500001

AMER CHEMICAL SOC

20223312579947

Calculations ; Catalysis ; Chemical activation ; Electronic structure ; Excited states ; Ground state ; Oxide minerals ; Titanium dioxide

Minerals:482.2 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2 ; Mathematics:921 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
2.Univ Sci & Technol China, Dept Chem Phys, Hefei 230026, Anhui, Peoples R China
3.Univ Sci & Technol China, Hefei Natl Res Ctr Phys Sci Microscale, Hefei 230026, Anhui, Peoples R China
4.Hefei Univ Technol, Sch Phys, Hefei 230009, Anhui, Peoples R China

Wang, Xiaoning,Wan, Lingyun,Wang, Zijian,et al. Identifying Photocatalytic Active Sites of C2H6 C-H Bond Activation on TiO2 via Combining First-Principles Ground-State and Excited- State Electronic Structure Calculations[J]. Journal of Physical Chemistry Letters,2022,13(28):6532-6540.

Wang, Xiaoning.,Wan, Lingyun.,Wang, Zijian.,Liu, Xiaofeng.,Gao, Yunzhi.,...&Yang, Jinlong.(2022).Identifying Photocatalytic Active Sites of C2H6 C-H Bond Activation on TiO2 via Combining First-Principles Ground-State and Excited- State Electronic Structure Calculations.Journal of Physical Chemistry Letters,13(28),6532-6540.

Wang, Xiaoning,et al."Identifying Photocatalytic Active Sites of C2H6 C-H Bond Activation on TiO2 via Combining First-Principles Ground-State and Excited- State Electronic Structure Calculations".Journal of Physical Chemistry Letters 13.28(2022):6532-6540.