Intrinsic Effects of Thickness, Surface Chemistry and Electroactive Area on Nanostructured MoS2 Electrodes with Superior Stability for Hydrogen Evolution

Abstract Developing inexpensive, earth abundant materials for electrocatalytic and photoelectrochemical water splitting is critical to the decarbonisation of our energy system. Aerosol-assisted chemical vapour deposition (AACVD) is a potentially scalable, one-step synthesis technique that can produce large area, homogenous edge-aligned films of transition metal dichalcogenides including MoS2. Herein, we report a hydrogen evolution reaction (HER) study on such electrode films under acidic conditions. Using iR compensated near-steady state DC current-potential measurements and linear sweep voltammetry, the HER onset potential is recorded at −175 mV vs. RHE (current density 0.1 mA cm−2), while a current density of 10 mA cm−2 per nominal area is reached at an overpotential of −430 mV vs. RHE. A Tafel slope of 113 mV dec−1 suggests the existence of increased edge-active sites on the surface of 2H-MoS2. The electrodes offered high stability over 5000 cycles, which continued to improve with cycling, with the current density at −350 mV improved by a factor exceeding 20 between the 1st and 5000th cycle. X-ray photoelectron spectroscopy, contact angle measurements and electrochemical impedance spectroscopy were employed to provide thorough insights on the changes in the intrinsic properties of the material, which led to the observed HER activity enhancement with cycling. It is shown that a reduction in the surface oxide layer and increased electrowetting are the reasons for the improved performance. Electrodes of differing thicknesses were prepared and their performance was compared in association with the surface morphology. The best performing electrode had the lowest mass loading of MoS2, which is attributed to improved faradaic efficiency through the resistive 2H-MoS2 electrode.