Advances in thermal catalytic hydrogenation of CO₂ to higher alcohols

The hydrogenation of carbon dioxide (CO2) to higher alcohols (C2+OH, carbon number ≥2) represents an effective pathway for CO2 resource utilization. This approach offers dual benefits of mitigating carbon emissions while synthesizing high-value-added chemicals that can serve as sustainable fuels. However, the inherent inertness of CO2 molecules and the complex reaction pathways involved in higher alcohols formation—encompassing multiple steps such as CO2/CO activation, C–C coupling, and selective chain termination—pose significant challenges for developing efficient catalysts. This review systematically summarizes recent advances in thermos-catalytic CO2 hydrogenation for higher alcohols synthesis, focusing on representative catalytic systems including noble metal-based, modified Co-based, modified Cu-based, modified Fe-based, modified Cu-Fe-based as well as tandem or relay multifunctional catalysts. By analyzing the synergistic mechanisms of strategies, such as alkali metal promotion, transition metal doping, support modulation, and precursor optimization in enhancing catalytic performance, we identify the core research challenges: the precise construction of active sites, dynamic control and balancing of reactive intermediate concentrations, and efficient regulation of C–C coupling processes. Finally, we prospectively discuss emerging directions, including artificial intelligence-assisted catalyst design and advanced in situ characterization techniques, providing critical insights to bridge fundamental research and industrial application of this technology.