The Influence of a Surface Treatment of Metallic Titanium on the Photocatalytic Properties of TiO2 Nanotubes Grown by Anodic Oxidation

Titanium dioxide (TiO2) nanotubes obtained by the anodic oxidation of titanium metal foils can be used for the photocatalytic degradation of organic pollutants. The aim of our study was to determine the influence of the titanium foil’s surface treatment on the final morphology of the TiO2 nanotubes and their photocatalytic activity. In our experiments, we used two different titanium foils that were electropolished or untreated prior to the anodic oxidation. The morphologies of the starting titanium foils and the resulting TiO2 nanotube layers were investigated and the photocatalytic activities measured by the decomposition of caffeine under UV irradiation. Our results showed that electropolishing of the starting foils produced a more uniform and smoother TiO2 nanotubes surface. In contrast, the TiO2 nanotube surfaces from untreated titanium foils mimic the initial surface roughness of the titanium foil. A comparison of the photocatalytic properties of the TiO2 nanotube layers obtained from the untreated and electropolished titanium foils showed that electropolishing does not necessarily improve the photocatalytic properties of the resulting TiO2 nanotube layer. It was found that the determining factors influencing the photocatalytic activity are the chemical impurities (Ti-nitride) on the surface of the titanium foils and the surface roughness of the TiO2 nanotube layer. The highest photocatalytic activity was achieved with the anodized untreated foil with the minimal presence of Ti-nitride and a relatively high roughness of the TiO2 nanotubes

Effect of the Morphology of the High-Surface-Area Support on the Performance of the Oxygen-Evolution Reaction for Iridium Nanoparticles

The development of affordable, low-iridium-loading, scalable, active, and stable catalysts for the oxygen-evolution reaction (OER) is a requirement for the commercialization of proton-exchange membrane water electrolyzers (PEMWEs). However, the synthesis of high-performance OER catalysts with minimal use of the rare and expensive element Ir is very challenging and requires the identification of electrically conductive and stable high-surface-area support materials. We developed a synthesis procedure for the production of large quantities of a nanocomposite powder containing titanium oxynitride (TiONx) and Ir. The catalysts were synthesized with an anodic oxidation process followed by detachment, milling, thermal treatment, and the deposition of Ir nanoparticles. The anodization time was varied to grow three different types of nanotubular structures exhibiting different lengths and wall thicknesses and thus a variety of properties. A comparison of milled samples with different degrees of nanotubular clustering and morphology retention, but with identical chemical compositions and Ir nanoparticle size distributions and dispersions, revealed that the nanotubular support morphology is the determining factor governing the catalyst’s OER activity and stability. Our study is supported by various state-of-the-art materials’ characterization techniques, like X-ray photoelectron spectroscopy, scanning and transmission electron microscopies, Xray powder diffraction and absorption spectroscopy, and electrochemical cyclic voltammetry. Anodic oxidation proved to be a very suitable way to produce high-surface-area powder-type catalysts as the produced material greatly outperformed the IrO2 benchmarks as well as the Ir-supported samples on morphologically different TiONx from previous studies. The highest activity was achieved for the sample prepared with 3 h of anodization, which had the most appropriate morphology for the effective removal of oxygen bubbles

Nanotubular Titanium Oxynitride with an Ultra-Low Iridium Loading as a High-Performance Oxygen-Evolution-Reaction Thin-Film Electrode

The present study targets one of the grand challenges of electrochemical hydrogen production: a durable and cost-effective oxygen-evolution catalyst. We present a thin-film composite electrode with a unique morphology and an ultra-low loading of iridium that has extraordinary electrocatalytic properties. This is accomplished by the electrochemical growth of a defined, high-surface-area titanium oxide nanotubular film followed by the nitridation and effective immobilization of iridium nanoparticles. The applicative relevance of this production process is justified by a remarkable oxygen-evolution reaction (OER) activity and high stability. Due to the confinement inside the pores and the strong metal-support interaction (SMSI) effects, the OER exhibited a higher turnover. The high durability is achieved by self-passivation of the titanium oxynitride (TiON) surface layer with TiO2, which in addition also effectively embeds the Ir nanoparticles, while still keeping them electrically wired. An additional contribution to the enhanced durability comes from the nitrogen atoms, which according to our DFT calculations reduce the tendency of the Ir nanoparticles to grow. We also introduce an advanced electrochemical characterization platform for the in-depth study of thin-film electrodes. Namely, the entire process of the TiON-Ir electrode’s preparation and the electrochemical evaluation can be tracked with scanning electron microscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) at identical locations. In general, the novel experimental approach allows for the unique morphological, structural and compositional insights into the preparation and electrocatalytic performance of thin films, making it useful also outside electrocatalysis applications

“Nano Lab” advanced characterization platform for studying electrocatalytic iridium nanoparticles dispersed on TiOx_xNy_y supports prepared on Ti transmission electron microscopy grids

Aiming at speeding up the discovery and understanding of promising electrocatalysts, a novel experimental platform, i.e., the Nano Lab, is introduced. It is based on state-of-the-art physicochemical characterization and atomic-scale tracking of individual synthesis steps as well as subsequent electrochemical treatments targeting nanostructured composites. This is provided by having the entire experimental setup on a transmission electron microscopy (TEM) grid. Herein, the oxygen evolution reaction nanocomposite electrocatalyst, i.e., iridium nanoparticles dispersed on a high-surface-area TiO$_x$N$_y$ support prepared on the Ti TEM grid, is investigated. By combining electrochemical concepts such as anodic oxidation of TEM grids, floating electrode-based electrochemical characterization, and identical location TEM analysis, relevant information from the entire composite’s cycle, i.e., from the initial synthesis step to electrochemical operation, can be studied. We reveal that Ir nanoparticles as well as the TiO$_x$N$_y$ support undergo dynamic changes during all steps. The most interesting findings made possible by the Nano Lab concept are the formation of Ir single atoms and only a small decrease in the N/O ratio of the TiO$_x$N$_y$−Ir catalyst during the electrochemical treatment. In this way, we show that the precise influence of the nanoscale structure, composition, morphology, and electrocatalyst’s locally resolved surface sites can be deciphered on the atomic level. Furthermore, the Nano Lab’s experimental setup is compatible with ex situ characterization and other analytical methods, such as Raman spectroscopy, X-ray photoelectron spectroscopy, and identical location scanning electron microscopy, hence providing a comprehensive understanding of structural changes and their effects. Overall, an experimental toolbox for the systematic development of supported electrocatalysts is now at hand

Unveiling the potential of (CoFeNiMnCr)3_3O4_4 high-entropy oxide synthesized from CoFeNiMnCr high-entropy alloy for efficient oxygen-evolution reaction

Electrochemical water-splitting is a promising green technology for the production of hydrogen. One of the bottlenecks, however, is the oxygen evolution half-reaction (OER), which could be overcome with the development of a suitable electrocatalyst. Recently, non-noble metal, high-entropy oxides (HEO) have been investigated as potential OER electrocatalysts, but complex synthesis approaches that usually produce the material in powder form limit their wider utilization. Here, an innovative synthesis strategy of formulating a nanostructured (CoFeNiMnCr)$_3$O$_4$ HEO thin film on a CoFeNiMnCr high entropy alloy (HEA) using facile electrochemical and thermal treatment methods is presented. The CoFeNiMnCr HEA serves as exceptional support to be electrochemically treated in an ethylene glycol electrolyte with ammonium fluoride to form a rough and microporous structure with nanopits. The electrochemically treated CoFeNiMnCr HEA surface is more prone to oxidation during a low-temperature thermal treatment, leading to the growth of a spinel (CoFeNiMnCr)$_3$O$_4$ HEO thin film. The (CoFeNiMnCr)$_3$O$_4$ HEO exhibits a superior overpotential of 341 mV at 10 mA cm$^{−2}$ and a Tafel slope of 50 mV dec$^{−1}$ along with remarkable long-term stability in alkaline media. The excellent catalytic activity and stability for the OER can serve as a promising platform for the practical utilization of (CoFeNiMnCr)$_3$O$_4$ HEO

Iridium stabilizes ceramic titanium oxynitride support for oxygen evolution reaction

Decreasing iridium loading in the electrocatalyst presents a crucial challenge in the implementation of proton exchange membrane (PEM) electrolyzers. In this respect, fine dispersion of Ir on electrically conductive ceramic supports is a promising strategy. However, the supporting material needs to meet the demanding requirements such as structural stability and electrical conductivity under harsh oxygen evolution reaction (OER) conditions. Herein, nanotubular titanium oxynitride (TiON) is studied as a support for iridium nanoparticles. Atomically resolved structural and compositional transformations of TiON during OER were followed using a task-specific advanced characterization platform. This combined the electrochemical treatment under floating electrode configuration and identical location transmission electron microscopy (IL-TEM) analysis of an in-house-prepared Ir-TiON TEM grid. Exhaustive characterization, supported by density functional theory (DFT) calculations, demonstrates and confirms that both the Ir nanoparticles and single atoms induce a stabilizing effect on the ceramic support via marked suppression of the oxidation tendency of TiON under OER conditions