ABSTRACT
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.
ABSTRACT
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(Ð) structure are discussed.
ABSTRACT
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.
ABSTRACT
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.
