The Synthesis of Hexaazatrinaphthylene‐Based 2D Conjugated Copper Metal‐Organic Framework for Highly Selective and Stable Electroreduction of CO2 to Methane

Abstract 2D conjugated MOFs have attracted significant interests in recent years owing to their special structural features and promising physical and chemical properties. These intriguing attributes, to a large extent, stem from the nature of incorporated ligands. The available ligands for the construction of 2D conjugated MOFs are still limited, especially those that have heteroatoms included and exposed to the pores. In this work, we designed and synthesized a highly symmetric hexaazatrinaphthylene (HATNA)‐based ligand with two different coordination sites. Through selective coordination, a highly crystalline and porous 2D conjugated copper metal‐organic framework was constructed. Due to the synergic effects of HATNA and copper catecholate node, this HATNA‐based 2D conjugated MOF can mediate the electrocatalytic reduction of CO 2 to methane with high selectivity of 78 % at high current density of 8.2 milliamperes per square centimetre (mA cm −2 ) for long durability over 12 hours.