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

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.