Electrochemical Stimuli-Driven Facile Metal-Free Hydrogen Evolution from Pyrene-Porphyrin-Based Crystalline Covalent Organic Framework

A [2 + 2] Schiff base type condensation between 5,10,15,20-tetrakis­(4-aminophenyl)­porphyrin (TAP) and 1,3,6,8-tetrakis (4-formylphenyl) pyrene (TFFPy) under solvothermal condition yields a crystalline, quasi-two-dimensional covalent organic framework (SB-PORPy-COF). The porphyrin and pyrene units are alternatively occupied in the vertex of 3D triclinic crystal having permanent microporosity with moderately high surface area (∼869 m2 g–1) and promising chemical stability. The AA stacking of the monolayers give a pyrene bridged conducting channel. SB-PORPy-COF has been exploited for metal free hydrogen production to understand the electrochemical behavior using the imine based docking site in acidic media. SB-PORPy-COF has shown the onset potential of 50 mV and the Tafel slope of 116 mV dec–1. We expect that the addendum of the imine based COF would not only enrich the structural variety but also help to understand the electrochemical behavior of these class of materials.