Heterogeneous Catalytic Systems for Carbon Dioxide Hydrogenation to Value‐Added Chemicals

Utilizing renewable energy to hydrogenate carbon dioxide into fuels eliminates massive CO2 emissions from the atmosphere and diminishes our need for using fossil fuels. This review presents the most recent developments for designing heterogeneous catalysts for the hydrogenation of CO2 to formate, methanol, and C2+ hydrocarbons. Thermodynamic challenges and mechanistic insights are discussed, providing a strong foundation to propose a suitable catalyst. The main body of this review focuses on nanostructured catalysts for constructing efficient heterogeneous systems. The most important factors affecting catalytic performance are highlighted, including active metals, supports and promoters that can potentially be used. The summary of the results and the outlook are presented in the final section. During the past few decades, heterogeneous CO2 hydrogenation has gained much attention and made tremendous progress. Thus, many highly efficient catalysts have been studied to discover their active sites and provide mechanistic insights. This paper summarizes recent advances in CO2 hydrogenation and its conversion into various hydrocarbons such as formate, methanol, and C2+ products. As for formate production, Au and Ru nanocatalysts show superior activity. However, considering the catalyst cost, Cu‐based catalysts have an excellent prospect for methanol production, among other catalysts. Ultra‐small nanoparticles and nanoclusters appear promising to provide highly active cost‐effective catalysts. A growing number of researchers are investigating the possibility of directly synthesizing C2+ products through CO2 hydrogenation. The major challenge in producing heavy hydrocarbons is breaking the ASF limitations, which have been achieved over bifunctional catalysts using zeolites. Using suitable support and promoter can lead to a superior activity, ascribed to structural, electronic, and chemical promotional effects. Catalytic CO2 hydrogenation to formate/formic acid, methanol, and C2+ hydrocarbons enable CO2 utilization to produce renewable low‐carbon fuels and high‐value products. The success of the technology strongly relies on appropriate catalyst formulation, including the choice of active metals, supports and promoters, and the underlying reaction mechanisms that affect the catalytic performance.