Influence of atomic coordination on the activity of lattice oxygen and catalytic oxidation of toluene over regular Cu2O crystalline

Linlin Deng; Mingtai Li; Xin Gao; Xiaokun Yi; Yang Zhao; Yulong Yang; Zitong Zhao; Jiarui Chen; Baojuan Dou; Feng Bin

doi:10.1016/j.jhazmat.2024.136796

Influence of atomic coordination on the activity of lattice oxygen and catalytic oxidation of toluene over regular Cu₂O crystalline

J Hazard Mater. 2024 Dec 4:484:136796. doi: 10.1016/j.jhazmat.2024.136796. Online ahead of print.

Authors

Linlin Deng¹, Mingtai Li², Xin Gao², Xiaokun Yi¹, Yang Zhao², Yulong Yang², Zitong Zhao², Jiarui Chen², Baojuan Dou³, Feng Bin⁴

Affiliations

¹ College of Marine and Environmental Sciences, Tianjin University of Science & Technology, Tianjin 300457, PR China; State Key Laboratory of High-Temperature Gas Dynamics, Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190, PR China.
² College of Marine and Environmental Sciences, Tianjin University of Science & Technology, Tianjin 300457, PR China.
³ College of Marine and Environmental Sciences, Tianjin University of Science & Technology, Tianjin 300457, PR China. Electronic address: bjdou@tust.edu.cn.
⁴ State Key Laboratory of High-Temperature Gas Dynamics, Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190, PR China; School of Engineering Science, University of Chinese Academy of Sciences, Beijing 100049, PR China. Electronic address: binfeng@imech.ac.cn.

PMID: 39647336
DOI: 10.1016/j.jhazmat.2024.136796

Abstract

VOCs oxidation over transition metal catalyst is commonly understood via the Mars-van Krevelen mechanism involving the crucial role of lattice oxygen (O_L) activity, however, how it is influenced by atomic coordination is still unclear. Herein, we use model catalysts of Cu₂O-cub, Cu₂O-oct and Cu₂O-dod with crystal planes of (100), (111) and (110), respectively, to investigate the O_L activity and catalytic oxidation of toluene. The activity of Cu₂O-oct is found to be the highest, followed by Cu₂O-cub and Cu₂O-dod. Experiments results combined with density functional theory show that, although low di-coordinated O atoms leads to the lowest surface oxygen vacancy formation energy (2.47 eV) and the highest surface O_L activity of Cu₂O-cub, it cannot determine the activity. The lowest bulk oxygen vacancy formation energy (3.16 eV) in Cu₂O-oct terminated with tri-coordinated O atoms and open surface can accelerate the migration and replenishment of O_L, thereby promoting the catalytic activity.

Keywords: Atomic coordination; Cu(2)O catalyst; Lattice oxygen; Oxygen vacancy formation energy; Toluene oxidation.