Thermo-Catalytic Carbon Dioxide Hydrogenation to Ethanol

The catalytic hydrogenation of carbon dioxide (CO2) represents a transformative approach for reducing greenhouse gas emissions while producing sustainable fuels and chemicals, with ethanol being particularly promising due to its compatibility with existing energy infrastructure. Despite significant progress in converting CO2 to C1 products (e.g., methane, methanol), selective synthesis of C2+ compounds like ethanol remains challenging because of competing reaction pathways and byproduct formation. Recent advances in thermo-catalytic CO2 hydrogenation have explored diverse catalyst systems including noble metals (Rh, Pd, Au, Ir, Pt) and non-noble metals (Co, Cu, Fe), supported on zeolites, metal oxides, perovskites, silica, metal–organic frameworks, and carbon-based materials. These studies reveal that catalytic performance hinges on the synergistic effects of multimetallic sites, tailored support properties and controlled reaction micro-environments to optimize CO2 activation, controlled hydrogenation and C−C coupling. Mechanistic insights highlight the critical balance between CO2 reduction steps and selective C−C bond formation, supported by thermodynamic analysis, advanced characterization techniques and theoretical calculations. However, challenges persist, such as low ethanol yields and undesired byproducts, necessitating innovative catalyst designs and optimized reactor configurations. Future efforts must integrate computational modeling, in situ/operando studies, and renewable hydrogen sources to advance scalable and economically viable processes. This review consolidates key findings, proposes potential reaction mechanisms, and outlines strategies for designing high-efficiency catalysts, ultimately providing reference for industrial application of CO2-to-ethanol technologies.