Recent advances in metal-organic frameworks for catalytic CO₂ hydrogenation to diverse products

Selective hydrogenation of CO₂ to high value-added chemicals, not only gives an effective way to reduce the concentration of CO₂, but also provides the precursors to advance the industrial manufacturing of chemicals and fuels. With the well-defined reticular frameworks and flexible modifiability, metal-organic frameworks (MOFs) can be the ideal platform to construct the enabled catalysts for CO₂ hydrogenation, because they have shown the great potential for the enhancement of catalytic activity, the precise control of selectivity, and the excellent stability. In this review, we systematically summarize the recent advances in MOFs based catalysts for CO₂ hydrogenation towards diverse products. Firstly, synthesis strategies for different kinds of MOFs based catalysts are described. Secondly, selective hydrogenation of CO₂ towards CO and methane is discussed over various metal nanoparticles/MOFs composites. Thirdly, heterogenization and isolation of molecular catalysts by MOFs are elaborated for producing formic acid. Fourthly, selective hydrogenation of CO₂ toward methanol is discussed in terms of interface structures of Cu, Zn, and metal nodes of MOFs, the synergy between auxiliary sites and noble metal, and tandem catalytic systems of molecular catalysts and Lewis acid sites. Subsequently, the integration of multiple metal sites, promoters, and cocatalysts into MOFs is described for the selective hydrogenation of CO₂ to C₂₊ products. After those, the key issue about the stability of MOFs based catalysts for CO₂ hydrogenation reaction is discussed. Finally, the summary and perspective about MOFs based catalysts for selective CO₂ hydrogenation and mechanism research are proposed.