Structure-performance relationships in MOF-derived electrocatalysts for CO2 reduction

Metal-organic frameworks (MOFs) hold great potential as electrocatalysts for the reduction of carbon dioxide (CO₂), due to their highly tunable and porous structures. However, unlocking their full potential necessitates a comprehensive understanding of structure-performance relationships to guide rational design. This review provides a meticulous analysis of MOF electrocatalysts for electrocatalytic CO₂ reduction (ECR), emphasizing correlations between composition, morphology, and catalytic performance. Key structure-function aspects are explored across various MOF-derived materials, encompassing the impact of metal identity, organic linker chemistry, porosity, defect concentration, and particle morphology. Physicochemical properties related to substrate adsorption and active site availability are linked to catalytic activities, product selectivities, energy efficiencies, and overpotentials. The review identifies several performance-limiting factors, including suboptimally tuned active sites and weak structure-selectivity linkages. However, the modular nature of MOFs presents opportunities to address these challenges through synthetic tuning. Future prospects, involving advanced characterization techniques, are also discussed. Finally, a separate section is devoted to the potential (industrial) valorization of the process. This critical review aims to distill guiding principles for design and optimization from existing trends, facilitating the development of MOF electrocatalysts capable of driving sustainable CO₂ reduction at industrial scales. The realization of this promising technology holds the potential to provide renewable fuels and mitigate climate change through carbon capture and conversion utilizing intermittent renewable energy sources.