One-Pot Ethyl Acetate Production from Ethanol Photooxidation on Rutile TiO2(110): Strong Photon Energy Dependence

Rulin Sun; Xinlu Liu; Xiao Chen; Li Che; Xueming Yang; Qing Guo

doi:10.1021/acs.jpclett.2c00048

One-Pot Ethyl Acetate Production from Ethanol Photooxidation on Rutile TiO₂(110): Strong Photon Energy Dependence

J Phys Chem Lett. 2022 Jan 27;13(3):801-807. doi: 10.1021/acs.jpclett.2c00048. Epub 2022 Jan 19.

Authors

Rulin Sun¹, Xinlu Liu¹, Xiao Chen^{2

3}, Li Che¹, Xueming Yang^{2

4

3}, Qing Guo^{2

3}

Affiliations

¹ College of Environmental Sciences and Engineering, Dalian Maritime University, Dalian, Liaoning 116026, People's Republic of China.
² Shenzhen Key Laboratory of Energy Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong 518055, People's Republic of China.
³ Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong 518055, People's Republic of China.
⁴ State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, People's Republic of China.

PMID: 35044191
DOI: 10.1021/acs.jpclett.2c00048

Abstract

Ethyl acetate (EA) production from sequential ethanol (EtOH) photooxidation on a rutile(R)-TiO₂(110) surface has been investigated by the temperature-programmed desorption (TPD) method at 355 and 266 nm. Significant EA product is detected under 266 nm irradiation, which is most likely to be formed via cross-coupling of primary dissociation products, aldehyde (CH₃CHO) and ethoxy groups. On the contrary, EA formation at 355 nm is negligible. In addition, the initial rate of EA formation from EtOH at 266 nm is nearly 2 orders of magnitude faster than that at 355 nm. Quantitative analysis suggests that EA formation from sequential EtOH photooxidation on R-TiO₂(110) is strongly dependent on photon energy or the energy of hot holes. This experimental result raises doubt about the traditional photocatalysis model on TiO₂ where charge carriers relax to their respective band edges prior to charge transfer to adsorbates during the photocatalytic process, leading to no dependence on photon energy in TiO₂ photocatalysis.