Applications of Metal–Organic Frameworks and Their Derivatives in Electrochemical CO ₂ Reduction

Highlights

• The electrochemical techniques utilizing metal-organic frameworks (MOFs)-based catalysts for converting CO ₂ into chemical species are discussed.

• The structure–activity relationship of MOF-based catalysts in electrocatalytic CO ₂ reduction reactions is thoroughly reviewed

• The challenges and opportunities of large-scale applications of MOF-based materials in electrochemical CO ₂ reduction reactions are discussed, and possible directions for the future development of MOFs and their derivatives are outlined.

Abstract

Electrochemically reducing CO ₂ to more reduced chemical species is a promising way that not only enables the conversion of intermittent energy resources to stable fuels, but also helps to build a closed-loop anthropogenic carbon cycle. Among various electrocatalysts for electrochemical CO ₂ reduction, multifunctional metal–organic frameworks (MOFs) have been employed as highly efficient and selective heterogeneous electrocatalysts due to their ultrahigh porosity and topologically diverse structures. Up to now, great progress has been achieved in the design and synthesis of highly active and selective MOF-related catalysts for electrochemical CO ₂ reduction reaction (CO ₂RR), and their corresponding reaction mechanisms have been thoroughly studied. In this review, we summarize the recent progress of applying MOFs and their derivatives in CO ₂RR, with a focus on the design strategies for electrocatalysts and electrolyzers. We first discussed the reaction mechanisms for different CO ₂RR products and introduced the commonly applied electrolyzer configurations in the current CO ₂RR system. Then, an overview of several categories of products (CO, HCOOH, CH ₄, CH ₃OH, and multi-carbon chemicals) generated from MOFs or their derivatives via CO ₂RR was discussed. Finally, we offer some insights and perspectives for the future development of MOFs and their derivatives in electrochemical CO ₂ reduction. We aim to provide new insights into this field and further guide future research for large-scale applications.