Porosity as a Design Element for Developing Catalytic Molecular Materials for Electrochemical and Photochemical Carbon Dioxide Reduction.

The catalytic reduction of carbon dioxide (CO ) using sustainable energy inputs is a promising strategy for upcycling of atmospheric carbon into value-added chemical products. This goal has inspired the development of catalysts for selective and efficient CO conversion using electrochemical and photochemical methods. Among the diverse array of catalyst systems designed for this purpose, 2D and 3D platforms that feature porosity offer the potential to combine carbon capture and conversion. Included are covalent organic frameworks (COFs), metal-organic frameworks (MOFs), porous molecular cages, and other hybrid molecular materials developed to increase active site exposure, stability, and water compatibility while maintaining precise molecular tunability. This mini-review showcases catalysts for the CO reduction reaction (CO RR) that incorporate well-defined molecular elements integrated into porous materials structures. Selected examples provide insights into how different approaches to this overall design strategy can augment their electrocatalytic and/or photocatalytic CO reduction activity.