The formation of unsaturated IrOx in SrIrO3 by cobalt-doping for acidic oxygen evolution reaction.

Electrocatalytic water splitting is a promising route for sustainable hydrogen production. However, the high overpotential of the anodic oxygen evolution reaction poses significant challenge. SrIrO3-based perovskite-type catalysts have shown great potential for acidic oxygen evolution reaction, but the origins of their high activity are still unclear. Herein, we develop a Co-doped SrIrO3 system to enhance oxygen evolution reaction activity and elucidate the origin of catalytic activity. In situ experiments reveal Co activates surface lattice oxygen, rapidly exposing IrOx active sites, while bulk Co doping optimizes the adsorbate binding energy of IrOx. The Co-doped SrIrO3 demonstrates high oxygen evolution reaction electrocatalytic activity, markedly surpassing the commercial IrO2 catalysts in both conventional electrolyzer and proton exchange membrane water electrolyzer.

Construction of a transition-metal sulfide heterojunction photocatalyst driven by a built-in electric field for efficient hydrogen evolution under visible light.

Photocatalytic H2 evolution is of prime importance in the energy crisis and in lessening environmental pollution. Adopting a single semiconductor as a photocatalyst remains a formidable challenge. However, the construction of an S-scheme heterojunction is a promising method for efficient water splitting. In this work, CdS nanoparticles were loaded onto NiS nanosheets to form CdS/NiS nanocomposites using hollow Ni(OH)2 as a precursor. The differences in the Fermi energy levels between the two components of CdS and NiS resulted in the formation of a built-in electric field in the nanocomposite. Density functional theory (DFT) calculations reveal that the S-scheme charge transfer driven by the built-in electric field can accelerate the effective separation of photogenerated carriers, which is conducive to efficient photocatalytic hydrogen evolution. The hydrogen evolution rate of the optimized photocatalyst is 39.68 mmol·g-1 h-1, which is 6.69 times that of CdS under visible light. This work provides a novel strategy to construct effective photocatalysts to relieve the environmental and energy crisis.

Enhanced Tribological Performance of Low-Friction Nanocomposite WSexSy/NP-W Coatings Prepared by Reactive PLD.

A novel laser-based method for producing nanocomposite coatings consisting of a tungsten sulfoselenide (WSexSy) matrix and W nanoparticles (NP-W) was developed. Pulsed laser ablation of WSe2 was carried out in H2S gas under appropriate laser fluence and reactive gas pressure. It was found that moderate sulfur doping (S/Se ~0.2-0.3) leads to significant improvement in the tribological properties of WSexSy/NP-W coatings at room temperature. Changes in the coatings during tribotesting depended on the load on the counter body. The lowest coefficient of friction (~0.02) with a high wear resistance was observed in a N2 environment at an increased load (5 N), resulting from certain structural and chemical changes in the coatings. A tribofilm with a layered atomic packing was observed in the surface layer of the coating. The incorporation of nanoparticles into the coating increased its hardness, which may have influenced the formation of the tribofilm. The initial matrix composition, which had a higher content of chalcogen atoms ((Se + S)/W~2.6-3.5), was altered in the tribofilm to a composition close to the stoichiometric one ((Se + S)/W~1.9). W nanoparticles were ground and retained under the tribofilm, which impacted the effective contact area with the counter body. Changes in the tribotesting conditions-lowering the temperature in a N2 environment-resulted in considerable deterioration of the tribological properties of these coatings. Only coating with a higher S content that was obtained at increased H2S pressure exhibited remarkable wear resistance and a low coefficient of friction, measuring 0.06, even under complicated conditions.

Pulsed Laser Phosphorus Doping and Nanocomposite Catalysts Deposition in Forming a-MoSx/NP-Mo//n+p-Si Photocathodes for Efficient Solar Hydrogen Production.

Pulsed laser deposition of nanostructured molybdenum sulfide films creates specific nonequilibrium growth conditions, which improve the electrocatalytic properties of the films in a hydrogen evolution reaction (HER). The enhanced catalytic performance of the amorphous a-MoSx (2 ≤ x ≤ 3) matrix is due to the synergistic effect of the Mo nanoparticles (Mo-NP) formed during the laser ablation of a MoS2 target. This work looks at the possibility of employing a-MoSx/NP-Mo films (4 and 20 nm thickness) to produce hydrogen by photo-stimulated HER using a p-Si cathode. A simple technique of pulsed laser p-Si doping with phosphorus was used to form an n+p-junction. Investigations of the energy band arrangement at the interface between a-MoSx/NP-Mo and n+-Si showed that the photo-HER on an a-MoSx/NP-Mo//n+p-Si photocathode with a 20 nm thick catalytic film proceeded according to a Z-scheme. The thickness of interfacial SiOy(P) nanolayer varied little in photo-HER without interfering with the effective electric current across the interface. The a-MoSx/NP-Mo//n+p-Si photocathode showed good long-term durability; its onset potential was 390 mV and photocurrent density was at 0 V was 28.7 mA/cm2. The a-MoSx/NP-Mo//n+p-Si photocathodes and their laser-based production technique offer a promising pathway toward sustainable solar hydrogen production.

Tribological Properties of WS2 Thin Films Containing Graphite-like Carbon and Ni Interlayers.

The development and production of thin-film coatings having very low friction is an urgent problem of materials science. One of the most promising solutions is the fabrication of special nanocomposites containing transition-metal dichalcogenides and various carbon-based nanophases. This study aims to explore the influence of graphite-like carbon (g-C) and Ni interface layers on the tribological properties of thin WS2 films. Nanocrystalline WS2 films were created by reactive pulsed laser deposition (PLD) in H2S at 500 °C. Between the two WS2 nanolayers, g-C and Ni nanofilms were fabricated by PLD at 700 and 22 °C, respectively. Tribotesting was carried out in a nitrogen-enriched atmosphere by the reciprocal sliding of a steel counterbody under a relatively low load of 1 N. For single-layer WS2 films, the friction coefficient was ~0.04. The application of g-C films did not noticeably improve the tribological properties of WS2-based films. However, the application of thin films of g-C and Ni reduced the friction coefficient to 0.013, thus, approaching superlubricity. The island morphology of the Ni nanofilm ensured WS2 retention and altered the contact area between the counterbody and the film surface. The catalytic properties of nickel facilitated the introduction of S and H atoms into g-C. The sliding of WS2 nanoplates against an amorphous g-C(S, H) nanolayer caused a lower coefficient of friction than the relative sliding of WS2 nanoplates. The detected behavior of the prepared thin films suggests a new strategy of designing antifriction coatings for practical applications and highlights the ample opportunities of laser techniques in the formation of promising thin-film coatings.

Application of Pulsed Laser Deposition in the Preparation of a Promising MoSx/WSe2/C(В) Photocathode for Photo-Assisted Electrochemical Hydrogen Evolution.

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.

Specific Features of Reactive Pulsed Laser Deposition of Solid Lubricating Nanocomposite Mo-S-C-H Thin-Film Coatings.

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.

Performance and Mechanism of Photoelectrocatalytic Activity of MoSx/WO3 Heterostructures Obtained by Reactive Pulsed Laser Deposition for Water Splitting.

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.

Pulsed Laser Deposition of Nanostructured MoS3/np-Mo//WO3-y Hybrid Catalyst for Enhanced (Photo) Electrochemical Hydrogen Evolution.

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.