IrO₂/Ir(Ni) film electrodes of variable Ni content have been prepared via a galvanic replacement method, whereby surface layers of pre-deposited Ni are replaced by Ir, followed by electrochemical anodization. Electrodeposition of Ni on a glassy carbon electrode support has been carried out at constant potential and the charge of electrodeposited Ni controlled so as to investigate the effect of precursor Ni layer thickness on the electrocatalytic activity of the corresponding IrO₂/Ir(Ni)/GC electrodes for the oxygen evolution reaction (OER). After their preparation, these electrodes were characterized by microscopic (SEM) and spectroscopic (EDS, XPS) techniques, revealing the formation of Ir deposits on the Ni support and a thin IrO₂ layer on their surfaces. To determine the electroactive surface area of the IrO₂ coatings, cyclic voltammograms were recorded in the potential range between hydrogen and oxygen evolution and the charge under the anodic part of the curves, corresponding to Ir surface oxide formation, served as an indicator of the quantity of active IrO₂ in the film. The electrocatalytic activity of the coatings for OER was investigated by current–potential curves under steady state conditions, revealing that the catalysts prepared from thinner Ni films exhibited enhanced electrocatalytic performance.

The oxidation of methanol is studied at TiO₂-supported Pt electrodes of varied high surface area carbon content (in the 30-5% w/w range) and C÷Ti atom ratio (in the 3.0-0.4 ratio). The Pt-TiO₂ catalyst is prepared by a photo-deposition process and C nanoparticles (Vulcan XC72R) are added by simple ultrasonic mixing. The optimum C÷Ti atom ratio of the prepared catalyst for methanol electro-oxidation is found to be 1.5, resulting from the interplay of C properties (increased electronic conductivity and methanol adsorption), those of TiO₂ (synergistic effect on Pt and photo-activity), as well as the catalyst film thickness. The intrinsic catalytic activity of the best Pt-TiO₂/C catalyst is better than that of a commercial Pt/C catalyst and could be further improved by nearly 25% upon UV illumination, whose periodic application can also limit current deterioration.

Optimized Pt-based methanol oxidation reaction (MOR) anodes are essential for commercial direct methanol fuel cells (DMFCs) and methanol electrolyzers for hydrogen production. High surface area Ti supports are known to increase Pt catalytic activity and utilization. Pt has been deposited on black titania nanotubes (bTNTs), Ti felts and, for comparison, Ti foils by a galvanic deposition process, whereby Pt(IV) from a chloroplatinate solution is spontaneously reduced to metallic Pt (at 65 °C) onto chemically reduced (by CaH₂) TNTs (resulting in bTNTs), chemically etched (HCl + NaF) Ti felts and grinded Ti foils. All Pt/Ti-based electrodes prepared by this method showed enhanced intrinsic catalytic activity towards MOR when compared to Pt and other Pt/Ti-based catalysts. The very high/high mass specific activity of Pt/bTNTs (ca 700 mA mg_Pt⁻¹ at the voltammetric peak of 5 mV s⁻¹ in 0.5 M MeOH) and of Pt/Ti-felt (ca 60 mA mg_Pt⁻¹, accordingly) make these electrodes good candidates for MOR anodes and/or reactive Gas Diffusion Layer Electrodes (GDLEs) in DMFCs and/or methanol electrolysis cells.

A combination of thermal (500–750 °C in air) and hydrometallurgical (acidic) treatments have been applied to dried tannery sludge, resulting in the initial conversion of Cr(III) to Cr(VI) and its subsequent leaching as wastewater with high Cr(VI) concentration content (3000–6000 mg/L), presenting an extraction efficiency over 90%. The optimal electrochemical conditions for the subsequent Cr(VI) reduction with respect to acid concentration and acid kind were established by applying appropriate rotating disc electrode (RDE) experiments, using a glassy carbon (GC) electrode, and found to be equal or higher than 0.5 M H₂SO₄ (for the respective Cr(III) concentration range studied). The result from leaching Cr(VI) wastewater was further treated in small electrochemical bench-scale reactor for its conversion back to Cr(III) form, potentially reusable in the tanning industry. Ti-based anodes and a reticulated vitreous carbon (RVC) cathode were used to treat small (350–800 mL) samples in batch, as well as in batch-recirculation prototype electrochemical reactors, under the application of constant current or appropriately applied potential to achieve Cr(VI) conversion/reduction efficiency over 95%.

In this work, we have used both plain titania nanotubes, TNTs, and their reduced black analogues, bTNTs, that bear metallic conductivity (prepared by solid state reaction of TNTs with CaH₂ at 500 °C for 2 h), as catalyst supports for the oxygen evolution reaction (OER). Ir was subsequently been deposited on them by the galvanic replacement of electrodeposited Ni by Ir(IV) chloro-complexes; this was followed by Ir electrochemical anodization to IrO₂. By carrying out the preparation of the TNTs in either two or one anodization steps, we were able to produce close-packed or open-structure nanotubes, respectively. In the former case, larger than 100 nm Ir aggregates were finally formed on the top face of the nanotubes (leading to partial or full surface coverage); in the latter case, Ir nanoparticles smaller than 100 nm were obtained, with some of them located inside the pores of the nanotubes, which retained a porous surface structure. The electrocatalytic activity of IrO₂ supported on open-structure bTNTs towards OER is superior to that supported on close-packed bTNTs and TNTs, and its performance is comparable or better than that of similar electrodes reported in the literature (overpotential of η = 240 mV at 10 mA cm⁻²; current density of 70 mA cm⁻² and mass specific current density of 258 mA mg_Ir⁻¹ at η = 300 mV). Furthermore, these electrodes demonstrated good medium-term stability, maintaining stable performance for 72 h at 10 mA cm⁻² in acid.