Adatom Doping of Transition Metals in ReSe₂ Nanosheets for Enhanced Electrocatalytic Hydrogen Evolution Reaction

 

Ik Seon Kwon 권익선 (제1저자, 박사과정), In Hye Kwak, Suyeon Ju, Sungwoo Kang, Seungwu Han, Yun Chang Park, Jucheol Park and Jeunghee Park (박정희 교수님),*  

ACS Nano 2020, 14, 12184-12194 (Impact factor: 14.588)

Abstract : Two-dimensional Re dichalcogenide nanostructures are promising electrocatalysts for the hydrogen evolution reaction (HER). Herein, we report the adatom doping of various transition metals (TM = Mn, Fe, Co, Ni, and Cu) in ReSe₂ nanosheets synthesized using a solvothermal reaction. As the atomic number of TM increases from Mn to Cu, the adatoms on Re sites become more favored over the substitution. In the case of Ni, the fraction of adatoms reaches 90%. Ni doping resulted in the most effective enhancement in the HER catalytic performance, which was characterized by overpotentials of 82 and 109 mV at 10 mA cm^–2 in 0.5 M H2SO₄ and 1 M KOH, respectively, and the Tafel slopes of 54 and 81 mV dec^–1. First-principles calculations predicted that the adatom doping structures (TMs on Re sites) have higher catalytic activity compared with the substitution ones. The adsorbed H atoms formed a midgap hybridized state via direct bonding with the orbitals of TM adatom. The present work provides a deeper understanding into how TM doping can provide the catalytically active sites in these ReSe₂ nanosheets.