Oxygen vacancy-triggered performance enhancement of toluene oxidation over Cu catalysts: a combined kinetics and mechanistic investigation

• Published in: Journal of materials chemistry. A, Materials for energy and sustainability Materials for energy and sustainability, 2024-08, Vol.12 (33), p.21884-21894
• Main Authors: Zhang, Xiangxue, Fei, Nina, Wang, Qianhong, Khan, Ali Raza, Chen, Wenyao, Qian, Gang, Zhang, Jing, Chen, De, Duan, Xuezhi, Zhou, Xinggui, Yuan, Weikang
• Format: Article
• Language: English
• Subjects: Aluminum oxide; Benzaldehyde; Benzoates; Benzoic acid; Benzyl alcohol; Carbon dioxide; Catalysts; Catalytic activity; Cleavage; Copper; Decomposition reactions; Hydrogen bonds; Kinetics; Metal oxides; Organic compounds; Oxidation; Oxygen; Performance degradation; Phenols; Reaction kinetics; Storage capacity; Toluene; VOCs; Volatile organic compounds; Zinc oxide; Zirconium dioxide
• ISSN: 2050-7488; 2050-7496
• DOI: 10.1039/D4TA02283A

Oxygen vacancy regulation in metal catalysts has emerged as a crucial strategy for efficiently degrading volatile organic compounds (VOCs), while the acquisition of kinetic and mechanistic insights into the oxygen vacancy roles remains highly desirable yet challenging. Herein, we conduct a combined kinetics and mechanistic investigation into the oxygen vacancy effects of Cu catalysts on toluene oxidation. Cu catalysts with varying oxygen vacancy contents are prepared using three representative metal oxide supports, including reducible ZrO 2 with strong oxygen storage capacity, reducible ZnO, and unreducible Al 2 O 3 . Toluene oxidation and CO oxidation are tested for these catalysts, revealing the superior catalytic activity of the Cu/ZrO 2 catalyst. Multiple characterization studies demonstrate that the strong reducibility and abundance of oxygen vacancies within the Cu/ZrO 2 catalyst are the key factors for these reactions. A redox-based kinetics strategy is further applied to decouple the reduction and oxidation steps, thus affording a rate diagram to elucidate the promotional effects of oxygen vacancies on toluene decomposition. Additionally, in situ DRIFTS study unveils the reaction pathway, showing the transformation from toluene into benzyl alcohol, benzaldehyde, benzoate, phenol, anhydride, carbonate, and ultimately CO 2 . As a result, the oxygen vacancy-tuned rate-relevant step is disclosed, shifting from C–H bond cleavage for the Cu/Al 2 O 3 catalyst with limited oxygen vacancies to the CO and CC bond cleavage for the Cu/ZnO and Cu/ZrO 2 catalysts with more oxygen vacancies. The kinetic and mechanistic insights gained here would help guide the design of highly efficient oxidative catalysts by tuning the oxygen vacancies of the support.