文献类型：期刊文献

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

作者：Zhang, Xiangxue[1];Fei, Nina[1];Wang, Qianhong[1];Khan, Ali Raza[1];Chen, Wenyao[1];Qian, Gang[1];Zhang, Jing[1];Chen, De[2];Duan, Xuezhi[1];Zhou, Xinggui[1];Yuan, Weikang[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]Norwegian Univ Sci & Technol, Dept Chem Engn, NO-7491 Trondheim, Norway

年份：2024

卷号：12

期号：33

起止页码：21884

外文期刊名：JOURNAL OF MATERIALS CHEMISTRY A

收录：;EI(收录号：20243216811940);WOS:【SCI-EXPANDED(收录号:WOS:001279901200001)】；

基金：This work was financially supported by the Natural Science Foundation of China (22038003, 22178100, 22178101, U22B20141 and 22008066), the Shanghai Pilot Program for Basic Research (22TQ1400100-15), the Innovation Program of Shanghai Municipal Education Commission, the Program of Shanghai Academic/Technology Research Leader (21XD1421000), and the Shanghai Science and Technology Innovation Action Plan (22JC1403800). We thank the BL14W1 XAFS beamline of the Shanghai Synchrotron Radiation Facility (SSRF) for the beam time and assistance in the experiments.

语种：英文

外文关键词：Alumina - Aluminum oxide - Catalyst activity - Catalytic oxidation - Copper - Copper oxides - II-VI semiconductors - Kinetics - Redox reactions - Toluene - Volatile organic compounds - Zinc oxide - Zirconia

摘要：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 ZrO2 with strong oxygen storage capacity, reducible ZnO, and unreducible Al2O3. Toluene oxidation and CO oxidation are tested for these catalysts, revealing the superior catalytic activity of the Cu/ZrO2 catalyst. Multiple characterization studies demonstrate that the strong reducibility and abundance of oxygen vacancies within the Cu/ZrO2 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 CO2. As a result, the oxygen vacancy-tuned rate-relevant step is disclosed, shifting from C-H bond cleavage for the Cu/Al2O3 catalyst with limited oxygen vacancies to the C 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O and CC bond cleavage for the Cu/ZnO and Cu/ZrO2 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. The oxygen vacancy-tuned rate-relevant step for toluene oxidation is revealed by a combined kinetics and mechanistic investigation over Cu catalysts.