Heterogeneous catalysts for the direct and oxidative dehydrogenation of n-butane to butadiene: A comprehensive review covering thermodynamics, catalyst development, kinetics and catalyst informatics

Butadiene is an essential chemical feedstock for a variety of industrial products. Rising butadiene demand, decreased supply from ethane crackers, and low natural gas prices stimulate interest in on-purpose butadiene production. Recently, oxidative dehydrogenation (ODH) of n-butane has emerged as a promising approach for producing butadiene instead of the direct dehydrogenation process (DDH). Although many research attempts have been made to enhance the catalytic performance of n-butane ODH, there is still lack of a comprehensive cutting-edge review that critically analyzes and summarizes the reported findings with extracting the hidden knowledge. Accordingly, this review provides insights into recent advances in catalytic systems developed in the light of catalytic properties such as oxygen species, metal-support interaction, particle size, metal dispersion, acidity/basicity, reducibility, porosity, and surface area, all of which are critical to improving catalytic performance for butadiene production. Additionally, discussions regarding reaction mechanisms, reaction kinetics, thermodynamics, applications of machine learning and density functional theory in catalyst development, current challenges, and future perspectives have been presented. Researchers and professionals in the field of heterogeneous catalysis, especially those focusing on the upgrading of hydrocarbons to valuable products, will find this review very helpful and insightful.