A Supramolecular Aminocatalyst to Promote Hydrogen Evolution Electrocatalysis with Palladium

Inspired by Nature's proton motive mechanism as well as transporter proteins, we reported herein a supramolecular catalytic strategy based on cyclodextrins for HER electrocatalysis. Supramolecular aminocatalyst with amino β-cyclodextrin (NH₂-β-CD), in concert with palladium, was found to facilitate electrochemical hydrogen evolution (HER) with a low overpotential of 25 mV and a Faradaic efficiency over 95%. Furthermore, we demonstrated that the cavity of cyclodextrin plays a crucial role in formulating transport channels for proton and the evolved hydrogen gas, leading to effective biomimic HER catalysis. The current work opens up an avenue in the design of interfacial molecular catalysts.