Morphological Effects and Stabilization of the Metallic 1T Phase in Layered V‐, Nb‐, and Ta‐Doped WSe₂ for Electrocatalysis

Abstract

Layered transition-metal dichalcogenides (TMDs) are valued for their electrocatalytic properties toward the hydrogen-evolution reaction (HER) and oxygen-reduction reaction (ORR). One effective strategy to activate the electrocatalytic properties of TMDs is through doping. The optimistic outlook of doped-MoS as an electrocatalyst witnessed in previous reports spurred us to examine the effect of doping WSe with Group 5 transition-metal species, namely V, Nb, and Ta, in aspects of inherent electroactivities and catalysis. Apart from the mild reduction signal unique to the Group 5 transition-metal dopants, the Group 5 transition-metal-doped WSe materials are found to possess largely identical inherent electrochemistry to the undoped WSe with a characteristic anodic peak. Living up to expectations, the Group 5 transition-metal-doped WSe materials exhibit improved electrocatalytic HER efficiency, as evident by the lower HER overpotentials and Tafel slopes relative to undoped WSe . After doping with V, Nb, or Ta species, an increased number of active sites is observed given the distinct changes in morphology from thick bulky pieces in undoped WSe to thinner fragments in doped WSe . Although undoped WSe exists in the semiconducting 2H phase, the Group 5 transition-metal-doped WSe materials are dominated by the metallic 1T phase. Doping WSe with V, Nb, or Ta stabilizes the catalytic 1T phase and appears to induce the transition from the 2H to 1T phase. In contrast to the enhanced HER performance of WSe upon doping, Group 5 transition-metal dopants proved futile in activating the ORR electrocatalytic behavior of WSe , for which the ORR efficiency is unchanged. Therefore, these findings facilitate the understanding of the role of Group 5 transition-metal dopants in the electrochemical and catalytic properties of WSe relative to their morphological features and provide an evaluation of the efficacy of doping TMDs in electrocatalytic applications.

Chemical Vapor Deposition Mediated Phase Engineering for 2D Transition Metal Dichalcogenides: Strategies and Applications

“…[ 65 ] By doping WSe 2 with transition metals such as V, Nb, Ta, or Cr, the stable 2H phase transforms into the 1T phase. [ 66 ] It was also reported that the doping of semiconducting WS 2 with Ta and Nb produces 1T phase (>50%). [ 67 ]…”

Metallic Transition Metal Dichalcogenides of Group VIB: Preparation, Stabilization, and Energy Applications

“…Specifically, there are two main strategies for metallic group VIB TMDs to improve HER performances: doping (or intercalation) and composite structure design. Some atoms such as group V transition metals (V, Nb, and Ta), [276] Sn, [277] N, and P, [278] are proven to be beneficial for different reasons. The introduction of transition metals and Sn could not only stabilize the metastable phase via electron donations, but also enhance the integral conductivity which is largely contributed to the electron transfer in Volmer and Heyrovsky steps.…”

Vanadium Dopants: A Boon or a Bane for Molybdenum Dichalcogenides‐Based Electrocatalysis Applications

“…For instance, studies have reported that when TMDs are doped with metallic heteroatom, their differential free energy of hydrogen adsorption, Δ G H get altered and proton‐transfer kinetics were accelerated, which are beneficial for hydrogen evolution reaction (HER). [ 30–35 ] Doping of TMDs with vanadium (V) reportedly improves the electrical properties of Group 6 TMDs as it changes the semiconducting behaviors to semimetallic, enhance electrical conductivity, and increase carrier concentrations. [ 24,36–38 ]…”