Se-Rich MoSe₂ Nanosheets and Their Superior Electrocatalytic Performance for Hydrogen Evolution Reaction

Two-dimensional MoSe₂ has emerged as a promising electrocatalyst for the hydrogen evolution reaction (HER), although its catalytic activity needs to be further improved. Herein, we report Se-rich MoSe₂ nanosheets synthesized using a hydrothermal reaction, displaying much enhanced HER performance at the Se/Mo ratio of 2.3. The transition from the 2H to the 1T' phase occurred as Se/Mo exceeded 2. Structural analysis revealed the presence of Se adatoms as well as the formation of Se-Se bonding. Based on first-principles calculations, we propose two equally stable Se-rich structures. In the first one, excess Se atoms bridge two MoSe₂ layers <i>via</i> the interlayer Se-Se bonds. In the second one, the Se atoms substitute for the Mo atoms, and extra Se atoms are added closest to the Mo-substituted Se. Calculation of Gibbs free energy along the reaction path indicates that the Se adatoms of the second model are the most active sites for HER.