Revealing the Superior Electrocatalytic Performance of 2D Monolayer WSe$_2$ Transition Metal Dichalcogenide for Efficient H$_2$ Evolution Reaction

Abstract: H$2$ evolution reaction (HER) requires an electrocatalyst to reduce the reaction barriers for the efficient production of H$_2$. Platinum-group metal (PGM) elements such as Pt, Pd, etc. and their derivatives show excellent electrocatalytic activity for HER. The high cost and lack of availability of PGM elements bring constraints over their wide commercial applications, so discovering noble metal-free electrocatalysts with lower possible reaction barriers is paramount important. Two-Dimensional Transition Metal Dichalcogenides (2D TMDs) have emerged as a pinnacle group of materials for many potential applications, including HER. In this work, we have computationally designed a pristine 2D monolayer tungsten diselenide (WSe$_2$) TMD using the first principle-based hybrid Density Functional Theory (DFT) to investigate its structural, electronic properties and the electrocatalytic performance for HER. The possible Volmer-Heyrovsky and Volmer-Tafel reaction mechanisms for HER at the W-edge of the active site of WSe$_2$ were studied by using a non-periodic finite molecular cluster model W${10}$Se$_{21}$. Our study shows that the pristine 2D monolayer WSe$_2$ follows either the Volmer-Heyrovsky or the Volmer-Tafel reaction mechanisms with a single-digit low reaction barrier about 6.11, 8.41 and 6.61 kcal/mol during the solvent phase calculations of H-migration, Heyrovsky and Tafel transition (TS) states, respectively. The lower reaction barriers, high turnover frequency (TOF) ~ 4.24 x $10^6$ sec$^{-1}$ and 8.86 x $10^7$ sec$^{-1}$ during the Heyrovsky and Tafel reaction steps and the low Tafel slope 29.58 mV.dec$^{-1}$ confirm that the pristine 2D monolayer WSe$_2$ might be a promising alternative to PGM based electrocatalyst.