Multidentate Macrocyclic Salphen‐Based 2D Conjugated Metal–Organic Framework

Abstract

Abstract Two‐dimensional conjugated metal–organic frameworks (2D c ‐MOFs) represent an emerging class of crystalline porous materials with promising electrochemical applications. The design of novel organic ligands for constructing 2D c ‐MOFs remains a crucial research frontier. While the incorporation of macrocycle blocks into 2D c ‐MOFs can introduce intrinsic cavities with advantageous properties, most existing reports are limited to coordinating with only one equivalent metal ion per macrocyclic cavity. In this work, we developed a triangular‐shaped Salphen macrocycle‐based 2D c ‐MOF (SM‐MOF‐Cu) featuring multidentate internal coordination sites. SM‐MOF‐Cu exhibits high crystallinity, permanent porosity, and abundant accessible metal sites. Remarkably, this material demonstrates exceptional performance in the electrocatalytic hydrogenation of acetylene to ethylene (E‐HAE), achieving a Faradaic efficiency of 96.6% for ethylene production at −0.85 V versus the reversible hydrogen electrode (RHE) under continuous pure acetylene feed. This study not only broadens the family of macrocycle‐based 2D c ‐MOFs but also provides new insights into their potential for advanced electrocatalysis.