Probing Active Sites on Pristine and Defective MnPX(3) (X: S and Se) Monolayers for Electrocatalytic Water Splitting

[Image: see text] The state-of-the-art density functional theory approach was used to study the structural and electronic properties of pristine and defective MnPX(3) monolayers as well as their activity toward water and hydrogen evolution reaction (HER) catalytic performance. The adsorption behavior of H(2)O on a pristine MnPX(3) structure is of physisorption nature, whereas the adsorption energy is significantly increased for the defective structures. At the same time, the water dissociation process is more energetically favorable, and the reactivity of MnPX(3) is determined by the vacancy configuration. Following Nørskov’s approach, the HER catalytic performance is evaluated by calculating the hydrogen adsorption free energy on the respective MnPX(3) surface. Our calculation results demonstrate that defective 2D MnPX(3) with low coordinated P shows significantly higher HER performance compared to the pristine counterpart.