Inverse Opal-like Porous MoSe_x Films for Hydrogen Evolution Catalysis: Overpotential-Pore Size Dependence

Transition metal dichalcogenides (TMDs) are prized as electrocatalysts for hydrogen evolution reaction (HER). Common TMD syntheses entail conditions of high temperatures and reagents that are detrimental to the environment. The electrochemical synthesis of TMDs is advocated as a viable alternative to the conventional synthetic procedures in terms of simplicity, ecological sustainability, and versatility of deposition on various surfaces at room temperature. In this work, we demonstrate the successful fabrication of electrocatalytic inverse opal porous MoSe_x films, where 2 ≤ x ≤ 3, via solid template-assisted electrodeposition from the simultaneous electroreduction of molybdic acid and selenium dioxide as the respective metal and chalcogen precursors in an aqueous electrolyte. The electrosynthesized porous MoSe_x films contain pores with diameters of 0.1, 0.3, 0.6, or 1.0 μm, depending on the size of the polystyrene bead template used. The investigation reveals that porous MoSe_x films with a pore size of 0.1 μm, which prevailed over the other pore sizes, are endowed with the lowest HER overpotential of 0.57 V at -30 mA cm^-2 and a Tafel slope of 118 mV dec^-1, alluding to the adsorption step as rate limiting. Across all pore sizes, the Volmer adsorption step limits the HER mechanism. Nevertheless, the pore size dictates the catalytic activity of the porous MoSe_x films apropos of HER overpotential such that the HER performance of smaller pore sizes of 0.1 and 0.3 μm surpasses those with wider pore sizes of 0.6 and 1.0 μm. The observed trends in their HER behavior may be rationalized by the tunable surface wettability as pore sizes vary. These fundamental findings offer a glimpse into the efficacy of electrodeposited porous TMDs as electrocatalysts and exemplify the feasibility of the electrosynthesis method in altering the morphological structure of the TMDs.