Large-area Free-standing Metalloporphyrin-based Covalent Organic Framework Films by Liquid-air Interfacial Polymerization for Oxygen Electrocatalysis

Synthesizing large-area free-standing covalent organic framework (COF) films is of vital importance for their applications but is still a big challenge. Herein, we reported the synthesis of large metalloporphyrin-based COF films and their applications for oxygen electrocatalysis. The reaction of meso-benzohydrazide-substituted metal porphyrins with tris-aldehyde linkers afforded free-standing COF films at the liquid-air interface. These films can be scaled up to 3000 cm² area and display great mechanical stability and structural integrity. Importantly, the Co-porphyrin-based films are efficient for electrocatalytic O₂ reduction and evolution reactions. A flexible, all-solid-state Zn-air battery was assembled using the films and showed high performance with a charge-discharge voltage gap of 0.88 V at 1 mA cm^-2 and high stability under bent conditions (0° to 180°). This work thus presents a strategy to synthesize functionalized COF films with high quality for uses in flexible electronics.