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

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.

2D Layered Material Alloys: Synthesis and Application in Electronic and Optoelectronic Devices

“…Each of these techniques manifests its own advantages and disadvantages, and they will be critically introduced in detail below. It is noteworthy that a series of solution‐processed synthesis methods, such as, hydrothermal reaction, [ 99 , 100 , 101 ] thermolysis, [ 102 ] Schlenk line synthesis, [ 103 ] and liquid exfoliation, [ 104 , 105 ] suffer from insurmountable contamination issues (e.g., dispersants, residuals and by‐products), low crystalline quality of products and poor compatibility with the state‐of‐the‐art micro‐fabrication technology, which severely hamper their application in the field of electronic and optoelectronic devices. Therefore, these approaches have not been included in this review.…”

Enhanced electrocatalysis of WSe 2 nanosheets by partial oxidation for hydrogen generation

“…Although TMDCs exhibit a variety of chemical compositions, binary alloys of TMDCs are less attractive due to their highly inert basal planes towards electrocatalysis 4,12 . Most of the research on TMDCs and transition metal phosphides (TMPs) has been focused on improving the intrinsic properties by modifying the morphologies, chemical composition, defect engineering, etc 4,12–19 . Whilst, some of the article has reported the acceleration of catalytic activity by localised surface plasmon resonances (LSPR) in metal decorated electrocatalysts 5,20,21 …”

“…4,12 Most of the research on TMDCs and transition metal phosphides (TMPs) has been focused on improving the intrinsic properties by modifying the morphologies, chemical composition, defect engineering, etc. 4,[12][13][14][15][16][17][18][19] Whilst, some of the article has reported the acceleration of catalytic activity by localised surface plasmon resonances (LSPR) in metal decorated electrocatalysts. 5,20,21 So far, most of the research was focused on the improvement of intrinsic electrocatalytic properties by enhancing the ECSA and has ignored the development of the photosensitive nature.…”

In Situ Growth of NiSe2-MoSe2 Heterostructures on Graphene Nanosheets as High-Performance Electrocatalyst for Hydrogen Evolution Reaction

“…sandwiched between two chalcogen (S or Se) planes [14]. The adjacent layers of 2D TMDs are coupled by van der Waals force to construct bulk crystals [15]. Among them, nonprecious 2D MoSe 2 has received widespread attention as a promising HER catalyst due to its fascinating structures 2 of 13 and low Gibbs free energy [16].…”