Se-Rich MoSe<sub>2</sub> Nanosheets and Their Superior Electrocatalytic Performance for Hydrogen Evolution Reaction.

Kwon, Ik Seon; Kwak, In Hye; Debela, Tekalign Terfa; Abbas, Hafiz Ghulam; Park, Yun Chang; Ahn, Jae-Pyoung; Park, Jeunghee; Kang, Hong Seok · ACS Nano · 2020

basic_science · Level V

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Abstract

Two-dimensional MoSe<sub>2</sub> 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 MoSe<sub>2</sub> 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 MoSe<sub>2</sub> 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.