A Supramolecular Porous Organic Cage Platform Promotes Electrochemical Hydrogen Evolution from Water Catalyzed by Cobalt Porphyrins

Abstract We report a supramolecular porous organic cage platform composed of cobalt porphyrins for catalyzing the electrochemical hydrogen evolution reaction (HER) from water at neutral pH. Owing to its permanent porosity, the supramolecular structure yields a catalyst film with a fivefold increase in the number of electrochemically active cobalt atoms and an improvement in Tafel slope from 170 mV/decade to 119 mV/decade compared to a planar cobalt porphyrin analog, reaching activities over 19,000 turnovers for HER over a 24‐hour period with 100 % Faradaic efficiency.