We studied the tribological properties of amorphous molybdenum sulfide (MoSx) thin-film coatings during sliding friction in an oxidizing environment at a low temperature (−100 °C). To obtain films with different sulfur contents (x ~ 2, 3, and 4), we used reactive pulsed laser deposition, where laser ablation of the Mo target was performed in H2S at various pressures. The lowest coefficient of friction (0.08) was observed during tribo-testing of the MoS3 coating. This coating had good ductility and low wear; the wear of a steel counterbody was minimal. The MoS2 coating had the best wear resistance, due to the tribo-film adhering well to the coating in the wear track. Tribo-modification of the MoS2 coating, however, caused a higher coefficient of friction (0.16) and the most intensive wear of the counterbody. The MoS4 coating had inferior tribological properties. This study explored the mechanisms of possible tribo-chemical changes and structural rearrangements in MoSx coatings upon contact with a counterbody when exposed to oxygen and water. The properties of the tribo-film and the efficiency of its transfer onto the coating and/or the counterbody largely depended on local atomic packing of the nanoclusters that formed the structure of the amorphous MoSx films.

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Systematic and in-depth studies of the structure, composition, and efficiency of hydrogen evolution reactions (HERs) in MoSx films, obtained by means of on- and off-axis pulsed laser deposition (PLD) from a MoS2 target, have been performed. The use of on-axis PLD (a standard configuration of PLD) in a buffer of Ar gas, with an optimal pressure, has allowed for the formation of porous hybrid films that consist of Mo particles which support a thin MoSx~2+δ (δ of ~0.7) film. The HER performance of MoSx~2+δ/Mo films increases with increased loading and reaches the highest value at a loading of ~240 μg/cm2. For off-axis PLD, the substrate was located along the axis of expansion of the laser plume and the film was formed via the deposition of the atomic component of the plume, which was scattered in Ar molecules. This made it possible to obtain homogeneous MoSx~3+δ (δ~0.8–1.1) films. The HER performances of these films reached saturation at a loading value of ~163 μg/cm2. The MoSx~3+δ films possessed higher catalytic activities in terms of the turnover frequency of their HERs. However, to achieve the current density of 10 mA/cm2, the lowest over voltages were −162 mV and −150 mV for the films obtained by off- and on-axis PLD, respectively. Measurements of electrochemical characteristics indicated that the differences in the achievable HER performances of these films could be caused by their unique morphological properties.

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Pulsed laser ablation of MoS2 and WO3 targets at appropriate pressures of background gas (Ar, air) were used for the preparation of new hybrid nanostructured catalytic films for hydrogen production in an acid solution. The films consisted of a nanostructured WO3−y underlayer that was covered with composite MoS3/np-Mo nanocatalyst. The use of dry air with pressures of 40 and 80 Pa allowed the formation of porous WO3−y films with cauliflower- and web-like morphology, respectively. The ablation of the MoS2 target in Ar gas at a pressure of 16 Pa resulted in the formation of amorphous MoS3 films and spherical Mo nanoparticles. The hybrid MoS3/np-Mo//WO3−y films deposited on transparent conducting substrates possessed the enhanced (photo)electrocatalytic performance in comparison with that of any pristine one (MoS3/np-Mo or WO3−y films) with the same loading. Modeling by the kinetic Monte Carlo method indicated that the change in morphology of the deposited WO3−y films could be caused by the transition of ballistic deposition to diffusion limited aggregation of structural units (atoms/clusters) under background gas pressure growth. The factors and mechanisms contributing to the enhancement of the electrocatalytic activity of hybrid nanostructured films and facilitating the effective photo-activation of hydrogen evolution in these films are considered.