Electrocatalytic Activity of Post Nb‐Doped 2D MoSe2 TMD Toward Highly Effective H2 Evolution Reaction

Abstract Designing highly efficient electrocatalysts for various chemical reactions is an important research area in advanced science and technology. The electrocatalyst is essential for the H 2 evolution reaction (HER) in order to efficiently lower the reaction energy barriers and produce hydrogen. To date, platinum (Pt)‐based catalysts have shown the best performance toward HER due to the optimum hydrogen adsorption energy. However, the expensive, low abundance, and scarcity of Pt‐based catalysts limit their commercialization. Therefore, it is necessary to find out precious Pt‐free electrocatalysts with low potential reaction barriers. 2D transition metal dichalcogenides (TMDs) have proven to be suitable electrocatalysts for HER. In the present study, we deployed the hybrid DFT method to compute the electrocatalytic performance and evaluate the electronic properties of the 2D monolayer Nb‐MoSe 2 material for H 2 evolution. To investigate the electrocatalysis of the subject material, we have computationally designed a nonperiodic molecular cluster model system Nb 1 Mo 9 Se 21 which illustrates both the Mo‐/Nb‐edges (100) and Se‐edges (010) of the 2D monolayer Nb‐MoSe 2 . The reaction barriers for H*‐migration, Heyrovsky, and Tafel transition states (TSs) are 20.63 kcal mol −1 , 6.64 kcal mol −1 , and 8.91 kcal mol −1 , respectively, computed by using the polarizable continuum (PCM) solvation method. The present research demonstrates that the 2D monolayer Nb‐MoSe 2 follows the Volmer–Heyrovsky reaction mechanism during the HER. The low reaction barrier, high turnover frequency (TOF), and low Tafel slope during the hydrogen formation confirm that the 2D monolayer Nb‐MoSe 2 proves to be a good electrocatalyst for the HER.