Hydrogen Evolution Reaction Activity of Heterogeneous Materials: A Theoretical Model

In this study, we present a new comprehensive methodology to quantify the catalytic activity of heterogeneous materials for the hydrogen evolution reaction (HER) using ab initio simulations. The model is composed of two parts. First, the equilibrium hydrogen coverage is obtained by an iterative evaluation of the hydrogen adsorption free energies (ΔGH) using density functional theory calculations. Afterward, the ΔGH are used in a microkinetic model to provide detailed characterizations of the entire HER considering all three elementary steps, i.e., the discharge, atom + ion, and combination reactions, without any prior assumptions of rate-determining steps. The microkinetic model takes the equilibrium and potential-dependent characteristics into account, and thus both exchange current densities and Tafel slopes are evaluated. The model is tested on several systems, from polycrystalline metals to heterogeneous molybdenum disulfide (MoS2), and by comparing to experimental data, we verify that our model accurately predicts their experimental exchange current densities and Tafel slopes. Finally, we present an extended volcano plot that correlates the electrical current densities of each elementary reaction step to the coverage-dependent ΔGH.

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