TaS, TaSe, and Their Heterogeneous Films as Catalysts for the Hydrogen Evolution Reaction.

Metallic two-dimensional transition-metal dichalcogenides (TMDs) of the group 5 metals are emerging as catalysts for an efficient hydrogen evolution reaction (HER). The HER activity of the group 5 TMDs originates from the unsaturated chalcogen edges and the highly active surface basal planes, whereas the HER activity of the widely studied group 6 TMDs originates solely from the chalcogen- or metal-unsaturated edges. However, the batch production of such nanomaterials and their scalable processing into high-performance electrocatalysts is still challenging. Herein, we report the liquid-phase exfoliation of the 2H-TaS crystals by using 2-propanol to produce single/few-layer (1H/2H) flakes, which are afterward deposited as catalytic films. A thermal treatment-aided texturization of the catalytic films is used to increase their porosity, promoting the ion access to the basal planes of the flakes, as well as the number of catalytic edges of the flakes. The hybridization of the H-TaS flakes and H-TaSe flakes tunes the Gibbs free energy of the adsorbed atomic hydrogen onto the H-TaS basal planes to the optimal thermo-neutral value. In 0.5 M HSO, the heterogeneous catalysts exhibit a low overpotential (versus RHE, reversible hydrogen electrode) at the cathodic current of 10 mA cm (η) of 120 mV and high mass activity of 314 A g at an overpotential of 200 mV. In 1 M KOH, they show a η of 230 mV and a mass activity of 220 A g at an overpotential of 300 mV. Our results provide new insight into the usage of the metallic group 5 TMDs for the HER through scalable material preparation and electrode processing.