Due to its unique electronic band characteristics (presence of d-orbital in both Mo and Se atoms), MoSe2 has potential to exhibit high electrical conductivity and superior hydrogen evolution reaction (HER) kinetics when compared to other transition-metal dichalcogenides. Though various strategies were employed earlier to obtain MoSe2 structure with different shapes and morphologies, precise control on achieving both Mo- and Se-edge sites and understanding their interaction with reactants in HER remains to be challenging. Here, we successfully demonstrate the vapor diffusion method to grow highly crystalline MoSe2 nanoflowers on carbon cloth in a vertical orientation. Uniformly dispersed nanoflowers with Mo- and Se-edge sites exhibited remarkable electrocatalytic activity on hydrogen reduction in terms of low Tafel slope and high exchange current density. The existence of a strong interaction between MoSe2 and carbon cloth assists in long-term hydrogen production and confirms the exceptional durability of the catalyst. A comprehensive evidence for hydrogen adsorption on dual active sites, viz., Mo- and Se-edges of MoSe2, is provided using X-ray photoelectron spectroscopy and in situ Raman spectroscopy containing a specially designed liquid immersion objective lens.
Keywords: MoSe2; XPS; chemical vapor deposition; electrocatalysis; hydrogen evolution reaction; in situ Raman; nanoflowers.