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.
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.
Platelet activation plays a key role in the pathogenesis of cardiovascular complications in patients with coronary and cerebrovascular ischemic disease. The most important task in the treatment and prevention such complications is the complete suppression of platelet activity. Inhibition of platelet aggregation is currently a key therapeutic approach in the treatment and prevention of cardiovascular atherosclerotic origin. The development of new and more effective methods for prediction of the response of patients to antiplatelet therapy and its subsequent correction appears to be the most important task of modern physics, biophysics, and medicine. Platelets obtained from patient specimens have been investigated by Surface-enhanced Raman spectroscopy (SERS) with the diode-pumped solid-state laser (λ = 532 nm) on Au/Ti rough surfaces. As a result, a set of optimal experimental parameters for platelets discrimination have been determined. Platelet spectral data for healthy volunteers, healthy volunteers on antiplatelet therapy and individuals with cardiovascular pathology on antiplatelet therapy have been analyzed. We suggest that the obtained results allow the usage of the SERS as a diagnostic tool for determination of both inhibition of platelet aggregation and its structure conformation.
This work studies the factors that affect the efficiency of the photoelectrochemical hydrogen evolution reaction (HER) using MoSx/WO3 nano-heterostructures obtained by reactive pulsed laser deposition (RPLD) on glass substrates covered with fluorinated tin oxide (FTO). Another focus of the research is the potential of MoSx nanofilms as a precursor for MoOz(S) nanofilms, which enhance the efficiency of the photo-activated oxygen evolution reaction (OER) using the MoOz(S)/WO3/FTO heterostructures. The nanocrystalline WO3 film was created by laser ablation of a W target in dry air at a substrate temperature of 420 °C. Amorphous MoSx nanofilms (2 ≤ x ≤ 12) were obtained by laser ablation of an Mo target in H2S gas of varied pressure at room temperature of the substrate. Studies of the energy band structures showed that for all MoSx/WO3/FTO samples, photo-activated HER in an acid solution proceeded through the Z-scheme. The highest photoelectrochemical HER efficiency (a photocurrent density ~1 mA/cm2 at a potential of ~0 V under Xe lamp illumination (~100 mW/cm2)) was found for porous MoS4.5 films containing the highest concentration of catalytically active sites attributed to S ligands. During the anodic posttreatment of porous MoSx nanofilms, MoOz(S) films with a narrow energy band gap were formed. The highest OER efficiency (a photocurrent density ~5.3 mA/cm2 at 1.6 V) was detected for MoOz(S)/WO3/FTO photoanodes that were prepared by posttreatment of the MoSx~3.2 precursor. The MoOz(S) film contributed to the effective photogeneration of electron–hole pairs that was followed by the transport of photoelectrons from MoOz(S) into the WO3 film and the effective participation of holes possessing strong oxidation ability in the OER on the surface of the MoOz(S) film.
We studied the possibility of using pulsed laser deposition (PLD) for the formation of a MoSx/WSe2 heterostructure on a dielectric substrate. The heterostructure can be employed for effective solar water splitting to produce hydrogen. The sapphire substrate with the conducting C(B) film (rear contact) helped increase the formation temperature of the WSe2 film to obtain the film consisting of 2H-WSe2 near-perfect nanocrystals. The WSe2 film was obtained by off-axis PLD in Ar gas. The laser plume from a WSe2 target was directed along the substrate surface. The preferential scattering of selenium on Ar molecules contributed to the effective saturation of the WSe2 film with chalcogen. Nano-structural WSe2 film were coated by reactive PLD with a nanofilm of catalytically active amorphous MoSx~4. It was established that the mutual arrangement of energy bands in the WSe2 and MoSx~4 films facilitated the separation of electrons and holes at the interface and electrons moved to the catalytically active MoSx~4. The current density during light-assisted hydrogen evolution was above ~3 mA/cm2 (at zero potential), whilst the onset potential reached 400 mV under irradiation with an intensity of 100 mW/cm2 in an acidic solution. Factors that may affect the HER performance of MoSx~4/WSe2/C(В) structure are discussed.
This work investigates the structure and chemical states of thin-film coatings obtained by pulsed laser codeposition of Mo and C in a reactive gas (H2S). The coatings were analysed for their prospective use as solid lubricating coatings for friction units operating in extreme conditions. Pulsed laser ablation of molybdenum and graphite targets was accompanied by the effective interaction of the deposited Mo and C layers with the reactive gas and the chemical states of Mo- and C-containing nanophases were interdependent. This had a negative effect on the tribological properties of Mo–S–C–H nanocomposite coatings obtained at H2S pressures of 9 and 18 Pa, which were optimal for obtaining MoS2 and MoS3 coatings, respectively. The best tribological properties were found for the Mo–S–C–H_5.5 coating formed at an H2S pressure of 5.5 Pa. At this pressure, the x = S/Mo ratio in the MoSx nanophase was slightly less than 2, and the a-C(S,H) nanophase contained ~8 at.% S and ~16 at.% H. The a-C(S,H) nanophase with this composition provided a low coefficient of friction (~0.03) at low ambient humidity and 22 °C. The nanophase composition in Mo–S–C–H_5.5 coating demonstrated fairly good antifriction properties and increased wear resistance even at −100 °C. For wet friction conditions, Mo–S–C–H nanocomposite coatings did not have significant advantages in reducing friction compared to the MoS2 and MoS3 coatings formed by reactive pulsed laser deposition.
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