Tunable Catalytic Platforms: Metal–Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction Toward Value-Added Chemicals

The electrochemical reduction of carbon dioxide (CO2RR) into value-added chemicals using renewable electricity is a pivotal strategy for achieving a sustainable carbon cycle. However, this process is plagued by intrinsic challenges, including poor product selectivity, competing hydrogen evolution, and catalyst instability. Metal–organic frameworks (MOFs), with their highly designable periodic structures, atomically dispersed active sites, and tunable pore microenvironments, have emerged as a uniquely versatile platform to address these issues. This review articulates a multi-scale design philosophy that enables precise steering of the CO2RR pathway. We systematically elaborate on hierarchical tuning strategies, beginning with molecular-scale engineering of active sites (metal nodes and organic ligands) to define intrinsic activity and intermediate binding. This is synergistically integrated with the optimization of electronic structure and charge transport to overcome conductivity bottlenecks, meso-scale modulation of crystal morphology and defects to enhance mass transport and site accessibility, and the construction of heterogeneous interfaces for tandem catalysis and synergistic effects. Through this coherent, cross-scale design framework, MOF-based catalysts demonstrate exceptional capability in the precise control of reaction pathways, leading to remarkably selective synthesis of target high-value products, from C1 compounds (CO, HCOOH, CH4, CH3OH) to C2+ species (C2H4, C2H5OH) and urea. Finally, we outline future directions centered on dynamic mechanistic understanding, electrode engineering for industrial current densities, and stability enhancement, thereby providing a comprehensive material design guideline to advance CO2RR technology. This work positions MOFs as a quintessential tunable catalytic platform for the sustainable conversion of CO2.