Hydrogen bonding mediated spillover enabling superior alkaline industrial-level current density hydrogen evolution

Abstract

Efficient and stable electrocatalysts for the hydrogen evolution reaction (HER) in alkaline media at high current densities are necessary for industrial H₂ production. Herein, the results of theoretical and experimental studies of a spillover-based low-fluorine-doped platinum nanocrystal catalyst are described. Density functional theory calculations reveal that the formation of hydrogen bonds between doped fluorine atoms and water molecules weakens the H–OH bonds, promoting water dissociation. Experimentation reveals that cooperative active sites in low-fluorine-doped platinum nanocrystals initiate the spillover of adsorbed hydrogen, proven by in situ electrochemical surface enhanced Raman spectroscopy. The developed catalyst exhibits excellent alkaline HER activity, with a low overpotential of 274 mV at 500 mA cm⁻² and high stability over more than 24 h at high current density. Fluorine doping can also be exploited for the post-modification of commercial Pt/C. In summary, a facile design for efficient, stable electrocatalysts is reported, paving the way toward industrial alkaline hydrogen production.