文献类型：期刊文献

英文题名：Kinetics evidence for oxidized-site ensemble effects in surfactant-modified vanadium phosphorus oxide catalysts for n-butane oxidation

作者：Khan, Ali Raza[1];Chen, Bingxu[2];Zhang, Zhongyao[1];Shi, Yao[1];Chen, Wenyao[1];Gu, Longqin[2];Zhou, Xinggui[1];Duan, Xuezhi[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn & Low Carbon Technol, Shanghai, Peoples R China;[2]Sinopec Shanghai Res Inst Petrochem Technol Co Ltd, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai, Peoples R China

年份：2026

外文期刊名：AICHE JOURNAL

收录：;EI(收录号：20262520957688);WOS:【SCI-EXPANDED(收录号:WOS:001796975600001)】；

基金：This work was financially supported by the National Natural Science Foundation of China (Grants 22408098), Guangxi Science and Technology Innovation Platform Program ("Leitai" Action Plan-Guangxi Laboratory Capacity Building) (LT2504240023), Fundamental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (JYB2025XDXM404), the Shanghai Pilot Program for Basic Research (22TQ1400100-15).

语种：英文

外文关键词：ensemble effects; kinetics modeling; n-butane oxidation; selective oxidation; VPO catalyst

摘要：Selective oxidation of n-butane to maleic anhydride (MA) is fundamentally limited by the activity-selectivity trade-off, and the origin of selectivity control remains debated. Here we show that surfactant-mediated modification of vanadium phosphorus oxide catalysts can shift the reaction network toward MA by suppressing competing carbon oxides (COx) formation. We establish a kinetic framework that explains this selectivity shift through coupled redox-site balance and product-branching kinetics. Kinetic analysis identifies the COx to MA branching parameter (gamma) as a key descriptor of intrinsic selectivity and reveals that MA formation requires an ensemble instead of an isolated site. These results provide direct kinetic evidence that MA selectivity is governed not only by the electronic properties of the redox sites, but also by ensemble-dependent transition-state formation on the site domains. This work offers both a mechanistic interpretation and a practical model for the ensemble effect that influences MA yield in n-butane oxidation.