Recent Advances in Molybdenum-Based Catalysts for the Reverse Water-Gas Shift Reaction.

The reverse water-gas shift (RWGS) reaction is one of the most promising strategies to bridge large-scale CO2 utilization with transitional syngas conversion processes. As promising materials for the RWGS reaction, Mo-based catalysts feature accessible raw materials and high activity. However, developing catalysts combining high activity, complete selectivity, and long-term stability poses major challenges. In this context, we provide a comprehensive and critical analysis of recent advances in Mo-based catalysts for the RWGS reaction. This review emphasizes the structure-performance relationships in various Mo-based catalysts, including promotional effects, metal-support interactions, and vacancy engineering that enable enhanced CO2 conversion, product selectivity, and long-term durability. We also address the ongoing debate surrounding the nature of active sites and elucidate their dynamic evolution, offering forward-looking perspectives on the rational design of improved Mo-based catalysts. Furthermore, we outline the fundamental reaction mechanisms, with emphasis on the role of advanced in situ/operando characterization techniques. By critically evaluating current challenges and future opportunities, this work aims to inspire innovations in RWGS technology and support the transition toward sustainable CO2 utilization for the production of synthetic chemicals and fuels.