Molybdenum disulfide (MoS₂) is a semiconducting transition metal dichalcogenide that is known to be a catalyst for both the hydrogen evolution reaction (HER) as well as for hydro-desulfurization (HDS) of sulfur-rich hydrocarbon fuels. Specifically, the edges of MoS₂ nanostructures are known to be far more catalytically active as compared to unmodified basal planes. However, in the absence of the precise details of the geometric and electronic structure of the active catalytic sites, a rational means of modulating edge reactivity remain to be developed. Here we demonstrate using first-principles calculations, X-ray absorption spectroscopy, as well as scanning transmission X-ray microscopy (STXM) imaging that edge corrugations yield distinctive spectroscopic signatures corresponding to increased localization of hybrid Mo 4d states. Independent spectroscopic signatures of such edge states are identified at both the S L_2,3 and S K-edges with distinctive spatial localization of such states observed in S L_2,3-edge STXM imaging. The presence of such low-energy hybrid states at the edge of the conduction band is seen to correlate with substantially enhanced electrocatalytic activity in terms of a lower Tafel slope and higher exchange current density. These results elucidate the nature of the edge electronic structure and provide a clear framework for its rational manipulation to enhance catalytic activity.

Herein, we report high electrocatalytic activity of monoclinic VO₂ (M1 phase) for the oxygen evolution reaction (OER) for the first time. The single-phase VO₂ (M1) nanoparticles are prepared in the form of uniformly covering the surface of individual carbon fibers constituting a carbon fiber paper (CFP). The VO₂ nanoparticles reveal the metal-insulator phase transition at ca. 65 °C (heating) and 62 °C (cooling) with low thermal hysteresis, indicating a high concentration of structural defect which is considered a grain boundary among VO₂ nanoparticles with some particle coalescence. Consequently, the VO₂/CFP shows a high electrocatalytic OER activity with the lowest η₁₀ (350 mV) and Tafel slope (46 mV/dec) values in a 1 M aqueous solution of KOH as compared to those of the vacuum annealed V₂O₅ and the hydrothermally grown VO₂ (M1), α-V₂O₅, and γ′-V₂O₅. The catalytically active site is considered V⁴⁺ components and V^4+/5+ redox couples in VO₂. The oxidation state of V⁴⁺ is revealed to be more favorable to the OER catalysis compared to that of V⁵⁺ in vanadium oxide through comparative studies. Furthermore, the amount of V⁵⁺ component is found to be increased on the surface of VO₂ catalyst during the OER, giving rise to the performance degradation. This work suggests V⁴⁺ and its redox couple as a novel active component for the OER in metal-oxide electrocatalysts.