Electronegativity principle for hydrogen evolution activity using first-principles calculations.

The catalytic activity of a heterogeneous catalyst is routinely described by the Sabatier principle using molecule/proton adsorption energy Δ as the thermodynamic descriptor. This descriptor, however, fails in quantitatively tracking the reaction rate due to the lack of charge transfer information during a reaction. Herein, we use density functional theory (DFT) calculations combining both canonical and grand-canonical ensembles to report a positive correlation between reaction kinetics and interfacial charge transfer for the hydrogen evolution reaction (HER).