A rational design of functional porous frameworks for electrocatalytic CO₂ reduction reaction

The electrocatalytic CO₂ reduction reaction (ECO₂RR) is considered one of the approaches with the most potential to achieve lower carbon emissions in the future, but a huge gap still exists between the current ECO₂RR technology and industrial applications. Therefore, the design and preparation of catalysts with satisfactory activity, selectivity and stability for the ECO₂RR have attracted extensive attention. As a classic type of functional porous framework, crystalline porous materials (e.g., metal organic frameworks (MOFs) and covalent organic frameworks (COFs)) and derived porous materials (e.g., MOF/COF composites and pyrolysates) have been regarded as superior catalysts for the ECO₂RR due to their advantages such as designable porosity, modifiable skeleton, flexible active site structure, regulable charge transfer pathway and controllable morphology. Meanwhile, with the rapid development of nano-characterization and theoretical calculation technologies, the structure-activity relationships of functional porous frameworks have been comprehensively considered, i.e., metallic element type, local coordination environment, and microstructure, corresponding to selectivity, activity and mass transfer efficiency for the ECO₂RR, respectively. In this review, the rational design strategy for functional porous frameworks is briefly but precisely generalized based on three key factors including metallic element type, local coordination environment, and microstructure. Then, details about the structure-activity relationships for functional porous frameworks are illustrated in the order of MOFs, COFs, composites and pyrolysates to analyze the effect of the above-mentioned three factors on their ECO₂RR performance. Finally, the challenges and perspectives of functional porous frameworks for the further development of the ECO₂RR are reasonably proposed, aiming to offer insights for future studies in this intriguing and significant research field.