RESUMO
Atomistic modeling of electrified interfaces remains a major issue for detailed insights in electrocatalysis, corrosion, electrodeposition, batteries, and related devices such as pseudocapacitors. In these domains, the use of grand-canonical density functional theory (GC-DFT) in combination with implicit solvation models has become popular. GC-DFT can be conveniently applied not only to metallic surfaces but also to semiconducting oxides and sulfides and is, furthermore, sufficiently robust to achieve a consistent description of reaction pathways. However, the accuracy of implicit solvation models for solvation effects at interfaces is in general unknown. One promising way to overcome the limitations of implicit solvents is going toward hybrid quantum mechanical (QM)/molecular mechanics (MM) models. For capturing the electrochemical potential dependence, the key quantity is the capacitance, i.e., the relation between the surface charge and the electrochemical potential. In order to retrieve the electrochemical potential from a QM/MM hybrid scheme, an electrostatic embedding is required. Furthermore, the charge of the surface and of the solvent regions has to be strictly opposite in order to consistently simulate charge-neutral unit cells in MM and in QM. To achieve such a QM/MM scheme, we present the implementation of electrostatic embedding in the VASP code. This scheme is broadly applicable to any neutral or charged solid/liquid interface. Here, we demonstrate its use in the context of GC-DFT for the hydrogen evolution reaction (HER) over a noble-metal-free electrocatalyst, MoS2. We investigate the effect of electrostatic embedding compared to the implicit solvent model for three contrasting active sites on MoS2: (i) the sulfur vacancy defect, which is rather apolar; (ii) a Mo antisite defect, where the active site is a surface bound highly polar OH group; and (iii) a reconstructed edge site, which is generally believed to be responsible for most of the catalytic activity. According to our results, the electrostatic embedding leads to almost indistinguishable results compared to the implicit solvent for the apolar system but has a significant effect on polar sites. This demonstrates the reliability of the hybrid QM/MM, electrostatically embedded solvation model for electrified interfaces.
RESUMO
MoS2 is a promising low-cost catalyst for the hydrogen evolution reaction (HER). However, the nature of the active sites remains a subject of debate. By taking the electrochemcal potential explicitly into account using grand-canonical density functional theory (DFT) in combination with the linearized Poisson-Boltzmann equation, we herein revisit the active sites of 2H-MoS2. In addition to the well-known catalytically active edge sites, also specific point defects on the otherwise inert basal plane provide highly active sites for HER. Given that HER takes place in water, we also assess the reactivity of these active sites with respect to H2O. The thermodynamics of proton reduction as a function of the electrochemical potential reveals that four edge sites and three basal plane defects feature thermodynamic overpotentials below 0.2 V. In contrast to current proposals, many of these active sites involve adsorbed OH. The results demonstrate that even though H2O and OH block "active" sites, HER can also occur on these "blocked" sites, reducing protons on surface OH/H2O entities. As a consequence, our results revise the active sites, highlighting the so far overlooked need to take the liquid component (H2O) of the functional interface into account when considering the stability and activity of the various active sites.
