Role and regulation of surface oxygen vacancies in vanadium-based oxides for chemical looping oxidative dehydrogenation of propane.

Redox catalysts play a critical role in chemical looping oxidative dehydrogenation of propane (CL-ODH). However, challenges persist in modulating lattice oxygen in metal oxides and maintaining surface oxygen coverage to prolong the oxidative dehydrogenation stage. This paper describes the role of oxygen vacancies by evaluating numerous vacancy distribution patterns, including surface and bulk distributions, to identify VO surfaces across a wide range of reduction degrees, guided by calculated oxygen vacancy formation energy. The surface reactions are classified into three distinct stages based on surface oxygen vacancy coverage (Ovc), with transitions between stages attributed to the excessive reactivity of lattice oxygen, variations in vanadium valence states, and the localized limitations of vacancy effects. Additionally, four high-valent metal dopants (W, Mo, Nb, and Os) identified through charge transfer energy (CTE)-based descriptors effectively reduce oxygen reactivity while optimizing the utilization of bulk lattice oxygen to maintain favorable surface Ovc. These findings provide essential theoretical insights and a strategic framework for the rational design of redox catalysts in CL-ODH applications.