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Photoelectrochemically active WO3 films were fabricated by electrodeposition from an acidic (pH 2), hydrogen-peroxide-containing electrolyte at −0.5 V vs. SCE. WO3-TiO2 composites were then synthesized under the same conditions, but with 0.2 g/L of anatase TiO2 nanoparticles (⌀ 36 nm), mechanically suspended in the solution by stirring. After synthesis, the films were annealed at 400 °C. Structural characterization by XRD showed that the WO3 films exhibit the crystalline structure of a non-stoichiometric hydrate, whereas, in WO3-TiO2, the WO3 phase was monoclinic. The oxidation of tungsten, as revealed by XPS, was W6+ for both materials. Ti was found to exist mainly as Ti4+ in the composite, with a weak Ti3+ signal. The efficiency of the WO3 films and composites as an oxygen evolution reaction (OER) photo-electrocatalyst was examined. The composite would generate approximately three times larger steady-state photocurrents at 1.2 V vs. SCE in a neutral 0.5 M Na2SO4 electrolyte compared to WO3 alone. The surface recombination of photogenerated electron–hole pairs was characterized by intensity-modulated photocurrent spectroscopy (IMPS). Photogenerated charge transfer efficiencies were calculated from the spectra, and at 1.2 V vs. SCE, were 86.6% for WO3 and 62% for WO3-TiO2. Therefore, the composite films suffered from relatively more surface recombination but generated larger photocurrents, which resulted in overall improved photoactivity.

The electrospark deposition (ESD) technique is a low-heat-input process that has great potential for coating applications and the restoration of damaged high-value parts. Carbon steels are commonly used as a substrate material for ESD coatings. However, we demonstrated that carbon steels could be used successfully as the electrode tool for the ESD process. Furthermore, ESD coatings commonly have a high as–deposited roughness. In view of this, in order to reduce the roughness of the ESD coatings, electrodeposition as a tool to alter surface morphology was investigated. Hence, the micro-leveling power of several electrolytes for Ni, Fe-W, Fe, and Cr electrodeposition were evaluated. The maximum leveling effect was detected for Ni electroplated from the Watts electrolyte. Thus, the novel hybrid coatings based on an ESD layer and a subsequent layer of electrodeposited Ni were obtained. ESD layers were obtained by using the following electrode tools as anodes: several types of carbon steels (St20, St30, and St45), alloys T15K6 (WC + TiC + Co), CuNiZn; and NiCr. The morphology and structure of the obtained hybrid coatings with an electrodeposited Ni top-layer was analyzed and compared to ESD coatings from the point of view of their wear and corrosion behavior. The wear rate of the novel ESD coatings based on carbon steels was comparable with coatings obtained using the NiCr electrode tool. Moreover, for all the studied cases, the corrosion resistance of the hybrid coatings was higher than for their ESD counterparts and close to electrolytic chromium.

One of the methods to improve the performance of a heterogeneous electrocatalyst is the dispersion of a catalytic material on a suitable substrate. In this study, femtosecond laser ablation was used to prepare very rough but also ordered copper surfaces consisting of vertical, parallel ridges. Then, a molybdenum sulfide coating was electrochemically deposited onto these surfaces. It was observed by profilometry that the average roughness of the surface after coating with MoS2 had decreased, but the developed surface area still remained significantly larger than the projected surface area. The electrodes were then used as an electrocatalyst for the hydrogen evolution reaction in acidic media. These were highly efficient, reaching 10 mA cm−2 of HER current at a −181 mV overpotential and a Tafel slope of ~39 mV dec−1. Additionally, scanning electrochemical microscopy was used to observe whether hydrogen evolution would preferentially occur in certain spots, for example, on the peaks, but the obtained results suggest that the entire surface is active. Finally, the electrochemical impedance spectroscopy data showed the difference in the double-layer capacitance between the ablated and non-ablated surfaces (up to five times larger) as well as the parameters that describe the improved catalytic activity of fs-Cu/MoS2 electrodes.

Molybdenum sulphide is an emerging precious-metal-free catalyst for cathodic water splitting. As its active sites catalyse the Volmer hydrogen adsorption step, it is particularly active in acidic media. This study focused on the electrochemical deposition of MoS2 on copper foam electrodes and the characterisation of their electrocatalytic properties. In addition, the electrodeposition was modified by adding a reducing agent—sodium hypophosphite—to the electrolyte. To reveal the role of hypophosphite, X-ray photoelectron spectroscopy (XPS) analysis was carried out in addition to scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). MoS2 films, electrodeposited at various charges passed through the cell (catalyst loadings), were tested for their catalytic activity towards hydrogen evolution in 0.5 M H2SO4. Polarisation curves and Tafel slope analysis revealed that the electrodeposited MoS2 films are highly active. Namely, Tafel slopes fell within the 40–50 mV dec−1 range. The behaviour of as-deposited films was also evaluated by electrochemical impedance spectroscopy over a wide overpotential range (0 to −0.3 V), and two clear time constants were distinguished. Through equivalent electrical circuit analysis, the experimental data were fitted to the appropriate model, and the obtained values of the circuit components were examined as a function of overpotential. It was found that the addition of NaH2PO2 into the electrodeposition solution affects the intrinsic activity of the material. Finally, a method is proposed to approximate the number of active sites from impedance data.