Importance of Hydrophilic Pretreatment in the Hydrothermal Growth of Amorphous Molybdenum Sulfide for Hydrogen Evolution Catalysis

Amorphous Molybdenum Sulfide (MoSx) has been identified as an excellent catalyst for the hydrogen evolution reaction (HER). It is still a challenge to prepare amorphous MoSx as a more active and stable catalyst for the HER Here the amorphous MoSx catalysts are prepared on carbon fiber paper (CFP) substrates at 200 degrees C by a simple hydrothermal method using molybdic acid and thioacetamide. Because the CFP is intrinsically hydrophobic due to its graphene-like carbon structure, two kinds of hydrophilic pretreatment methods, [plasma pretreatment (PP) and electrochemical pretreatment (EP)] are investigated to convert the hydrophobic surface of the CFP to be hydrophilic prior to the hydrothermal growth of MoSx. In the HER catalysis, the MoSx, catalysts grown on the pretreated CFPs reach a cathodic current density of 10 mA/cm(2) at a much lower overpotential of 231 mV on the MoSx/EP-CFP and 205 mV on the MoSx/PP-CFP, compared to a high overpotential of 290 mV on the MoSx of the nonpretreated CFP. Turnover frequency per site is also significantly improved when the MoSx are grown on the pretreated CFPs. However, the Tafel slopes of all amorphous MoSx catalysts are in the range of 46-50 mV/dec., suggesting the Volmer-Heyrovsky mechanism as a major pathway for the HER. In addition, regardless of the presence or absence of the pretreatment, the hydrothermally grown MoSx catalyst on CFP exhibits such excellent stability that the degradation of the cathodic current density is negligible after 1000 cycles in a stability test, possibly due to the relatively high growth temperature.