Effect of Rhenium Doping on Basal Plane Activation of 1H-WX₂ (X = S, Se, Te) Electrocatalysts for Improved Hydrogen Evolution Reaction: A First-Principles Study
DOI:
https://doi.org/10.33003/fjs-2026-1012-5629Keywords:
Rhenium, Doping, Density functional theory, Tungsten dichalcogenides, Hydrogen evolution reaction, Volcano plot, ElectrocatalystsAbstract
The development of earth-abundant and low-cost electrocatalysts for hydrogen evolution reaction (HER) is essential for sustainable hydrogen production through water electrolysis. In this work, density functional theory (DFT) calculations were employed to systematically investigate how substitutional rhenium (Re) doping activates the basal plane of pure 1H-WX₂ (X = S, Se, Te) monolayers. Two doping concentrations, namely 25% and 50%, were considered to elucidate the concentration-dependent catalytic behavior. Our results revealed that the hexagonal crystal symmetry of the host lattice is preserved after Re substitution, and negative dopant formation energies across all 25% doping systems establish their thermodynamic stability while the 50% Re doping systems were thermodynamically unstable due to positive formation energies. Hydrogen adsorption analysis demonstrated that pristine WX₂ monolayers possess weak catalytic activity due to unfavorable hydrogen adsorption free energy (ΔGH*). However, Re doping significantly improved HER performance. Among all investigated systems, the 25% Re-doped WS₂ monolayer (W0.75Re0.25S₂) exhibited the most favorable HER activity with a ΔGH* value of -0.16 eV. Volcano plot analysis further established that moderate Re doping (25%) provides the optimal catalytic performance, whereas excessive doping (50%) leads to hydrogen over-binding. Density of states analysis showed that Re incorporation induces semiconductor-to-metal transitions in all WX₂ systems through the introduction of impurity states near the Fermi level, which may facilitates charge-transfer kinetics during catalysis. This study demonstrates that Re doping is an effective strategy for tuning the catalytic activity of tungsten dichalcogenides and highlights Re-doped WX₂ monolayers, particularly W0.75Re0.25S₂, as promising non-precious electrocatalyst for efficient hydrogen production.
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Copyright (c) 2026 Muhammad Ibrahim Bagudo, Shamsuddeen Sani Alhassan, Mahmud Abdulsalam, Abdullahi Tanimu
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