Preparing high-performance oxygen evolution reaction (OER) catalysts with low precious metal loadings for water electrolysis applications (e.g., for green hydrogen production) is challenging and requires electrically conductive, high-surface-area, and stable support materials. Combining the properties of stable TiO₂ with those of active iridium oxide, we synthesized highly active electrodes for OER in acidic media. TiO₂ powders (both commercially available Degussa P-25^® and hydrothermally prepared in the laboratory from TiOSO₄, either as received/prepared or following ammonolysis to be converted to titania black), were decorated with IrO₂ by UV photodeposition from Ir(III) aqueous solutions of varied methanol scavenger concentrations. TEM, EDS, FESEM, XPS, and XRD measurements demonstrate that the optimized version of the photodeposition preparation method (i.e., with no added methanol) leads to direct deposition of well-dispersed IrO₂ nanoparticles. The electroactive surface area and electrocatalytic performance towards OER of these catalysts have been evaluated by cyclic voltammetry (CV), Linear Sweep Voltammetry (LSV), and Electrochemical Impedance Spectroscopy (EIS) in 0.1 M HClO₄ solutions. All TiO₂-based catalysts exhibited better mass-specific (as well as intrinsic) OER activity than commercial unsupported IrO₂, with the best of them (IrO₂ on Degussa P-25^® ΤiO₂ and laboratory-made TiO₂ black) showing 100 mAmg_Ir⁻¹ at an overpotential of η = 243 mV. Chronoamperometry (CA) experiments also proved good medium-term stability of the optimum IrO₂/TiO₂ electrodes during OER.

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.

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 5000C for 2 h), as catalyst supports for the oxygen evolution reaction (OER). Ir has been subsequently 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 mgIr-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.

This study investigates amorphous anodized porous TiO₂ (a-TiO₂) as a substrate for iridium-based oxygen evolution catalysts. The substrates were prepared via anodization of Ti foil in a glycerol-based solution for 15 min @ 60 V. Nickel was subsequently electrodeposited to act both as a conductive and sacrificial layer for the galvanic deposition of iridium from an Ir(IV) chloro-complex solution. Electrochemical anodization resulted in a uniform IrO_x layer on the a-TiO₂ substrate, featuring Ir aggregates ~250 nm in size and an Ir:Ni atomic ratio of ca. 7, as determined by EDS analysis. The quantity of Ni determined by ICP-MS bulk analysis indicated that Ni resided also within the porous matrix. Varying the Ni deposition charge density (q_Ni) revealed that an intermediate loading (1463 mC cm⁻²) provided the best balance between Ir accessibility during the galvanic replacement step and electronic continuity. The optimized IrO_x/Ir-Ni/a-TiO₂ electrode achieved excellent OER performance (η = 344 mV @ 10 mA cm⁻²; 1.68 mA μg_Ir⁻¹ @ η = 300 mV) at an ultra-low Ir loading of 2.15 μg_Ir cm⁻² and demonstrated good short-term stability, with only a 20 mV potential increase over 4 h of continuous operation at 5.5 mA cm⁻². Overall, this strategy offers a scalable pathway for producing efficient OER electrodes with minimal noble metal loading.