Enhancing efficiency of the ternary tri- chalcogenide MnPSe3 towards hydrogen evolution reaction by activating its basal plane

Feasibility of activating the basal planes of a ternary tri-chalcogenide material MnPSe3 towards hydrogen evolution reaction (HER) by internal regulation of substitutional doping is studied using first-principles electronic structure calculations. A fraction of the Mn atoms is replaced by a first-or second-row transition metal atom. While the basal plane of the pristine material is inactive to HER with the change in H adsorption free energy oDGH* thorn of 1.41 eV, some dopants significantly improve the activity of the planes as deduced from the calculated DGH* value. Whether such substitutional doping is energetically favored is checked by calculating the formation energy of each of the materials. Activity enhancement at different concentrations of the dopants is also tested. We find that three elements, Sc, Y, and Mo, out of a total of 19, activate the basal planes with DGH* values of 0.24, 0.18, and 0.23 eV, respectively, raising the possibility of increasing the efficiency of MnPSe3 as an HER catalyst. We also find an interesting correlation between the electronic densities of states of material and the calculated DGH* values. & COPY; 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Automated summary

The feasibility of activating the basal planes of MnPSe3 for hydrogen evolution reaction (HER) by internal regulation of substitutional doping is studied. The activity of the planes is significantly improved by certain dopants, as indicated by the calculated change in H adsorption free energy ΔGH* values. The formation energy of each material is calculated to check the energetic favorability of such substitutional doping, and the activity enhancement at different dopant concentrations is also tested. Three elements, Sc, Y, and Mo, out of a total of 19, are found to activate the basal planes with ΔGH* values of 0.24, 0.18, and 0.23 eV, respectively, suggesting the potential for increasing the efficiency of MnPSe3 as an HER catalyst. An interesting correlation between the electronic densities of states and the calculated ΔGH* values is also observed.