非均相低碳烃氧气氧化催化剂设计与反应机理研究进展OA

Catalytic oxidation represents a pivotal technology for the valorization of light hydrocarbons,where oxidative dehydrogenation(ODH)and epoxidation reactions using molecular oxygen have garnered substantial interest owing to their high atom economy and environmental friendliness.This review systematically summarizes recent advances in the oxidative dehydrogenation of light alkanes(ethane,propane)and the aerobic epoxidation of light olefins(ethylene,propylene).In terms of rational catalyst design,this review elaborates on performance regulation strategies for metal oxide catalysts such as MoVNbTeOx mixed oxides,NiO-based,and V-based systems,as well as carbon/boron-based non-metal catalysts in alkane oxidative dehydrogenation,along with silver-based and copper-based catalysts in alkene epoxidation.These strategies include regulating the oxidation state of active sites,strong metal-support interactions,particle size and crystal facet engineering,and promoter modification.At the mechanistic level,combining density functional theory calculations with in situ characterization techniques,this review delves into the C-H bond activation and alkene desorption pathways in oxidative dehydrogenation,along with the oxygen insertion routes and competing side reactions in epoxidation.Special attention is given to the dynamic evolution of electrophilic and nucleophilic oxygen species and their decisive role in reaction selectivity.Finally,the review outlines persistent challenges in the field,including suppressing over-oxidation and overcoming the trade-off between conversion and selectivity and proposes future research directions such as the precise design of active centers,development of inherently safer processes,and in-depth analysis of complex reaction networks,aiming to support the green transition of the chemical industry.