Metal-organic frameworks and their derivatives for CO₂ electrocatalysis: From methods and designs to products

Curtailing atmospheric CO₂ from industrial processes and automobiles remains a pressing issue to be addressed in alleviating the existential threats of climate change. To this end, the electrochemical CO₂ reduction reaction (eCO₂RR) route, which utilizes metal-based catalysts to convert CO₂ into valuable products, has emerged as a viable alternative to traditional carbon capture and conversion technologies. Metal-organic frameworks (MOFs) and their derivatives among metal-based materials stand out due to their large surface areas, tunable pore structures, and ability to accommodate various metal nodes and organic linkers. Despite extensive studies, a deep understanding of how MOF design strategies influence interfacial properties, reaction mechanisms, and ultimately product selectivity remains challenging. This review thus provides a unique perspective on eCO₂RR using MOFs and MOF derivatives by examining the interplay between synthetic methods, design strategies, and product selectivity, with an emphasis on often-overlooked aspects, such as the specific roles of metal nodes, organic linkers, and wettability. Moreover, our work provides an eCO₂RR-exclusive understanding by systematically examining how particular design strategies (e.g., morphology control, defect engineering, hybrid modulation, local microenvironment regulation, and interfacial properties optimization) are exploited to tune the interfacial properties of MOFs and MOF derivatives and their impacts on the selectivity toward specific product(s) through a "design-synthesis-product-mechanism" framework. Finally, our perspectives on the development of MOFs and MOF derivatives, including current limitations and ideas for future directions in designing high-performance materials for efficient eCO₂RR to value-added products, are provided concisely.