A Coherent Picture of the Hydrogen Oxidation and Evolution Reactions in Aqueous Solutions

Recent studies show the limitations of catalytic activity descriptor-based approaches to rationalize the kinetics of the hydrogen oxidation and evolution reactions (HOR/HER). Herein, we deposited several transition metals (TMs) onto Pt surfaces to disturb and probe the interface in alkaline solutions. The redox transition of these TMs in association with adsorption and desorption of reaction intermediates during the HOR/HER was monitored via in situ X-ray absorption spectroscopy. We propose that the TM facilitates the HOR by anchoring H2O with the H-up configuration (↑H2Oad) that removes Had on Pt via the bifunctional mechanism, based on the first in situ experimental evidence for the presence of ↑H2Oad on surface Ru. Meanwhile, the TM promotes the HER of Pt by anchoring OHad to trigger the hard–soft acid–base (HSAB) mechanism for OHad removal. The revised 2B theory depicts a coherent picture of the HOR/HER kinetics in aqueous solutions.