Recent progress in propane oxidative dehydrogenation: broad catalytic strategies and the role of vanadium

Abstract

Oxidative dehydrogenation of propane (ODHP) is emerging as an energy-efficient and environmentally favorable alternative to conventional steam cracking for propylene production. This review presents a comprehensive analysis of vanadium-based catalysts, emphasizing how their catalytic performance arises from the balance between active site structure, the physicochemical nature of the support, and the chosen synthesis method, which together control the dispersion and redox behavior of VO_x species. Thermodynamic and environmental aspects of ODHP are first outlined, followed by an in-depth discussion of active site chemistry, including the role of vanadium dispersion, oxidation state distribution, and coordination geometry in controlling C–H activation and product selectivity. Comparative evaluation of recent experimental data reveals that silica-based catalysts with isolated VO₄ species achieve high selectivity and stability, basicity-modified alumina systems suppress deep oxidation to attain selectivities above 94%, mixed-oxide supports balance redox activity with CO_x suppression, and carbon nanostructures or MOF-based supports enhance dispersion, thermal stability, and confinement effects. Recent advances demonstrate that promoter addition, tailored mesoporous supports, and controlled vanadium loading can shift the balance between isolated and polymeric VO_x species. This balance is critical in achieving high propylene selectivity while maintaining sufficient activity, optimizing the trade-off between activity and selectivity. Chemical looping ODHP is highlighted as a promising approach to further improve conversion efficiency and operational stability through controlled lattice oxygen delivery and facile catalyst regeneration. By integrating structural–functional relationships with process design considerations, this review provides a unified framework for developing next-generation vanadium-based ODHP catalysts, offering clear strategies for maximizing propylene yield, selectivity, and catalyst lifetime.