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The electrochemical synthesis of α ${\alpha }$ -amino acids at room temperature and pressure is a sustainable alternative to conventional methods like microbial fermentation and Strecker synthesis. A custom-built zero-gap flow electrolyzer was used to study the electrosynthesis of alanine via the electrocatalytic reductive amination (ERA) of the corresponding biomass-derivable α ${\alpha }$ -keto acid precursor - pyruvic acid (PA), and hydroxylamine (NH 2 OH) at very low pH. Non-toxic, abundant, and easy to prepare TiO 2 /Ti electrocatalysts were utilized as the cathode. Three TiO 2 /Ti felt electrodes with different oxide thicknesses were prepared and their characterization results were correlated with their respective electrochemical performance in terms of Faradaic efficiency η ${\eta }$ , and partial current density j ‾ ${\left|\overline{j}\right|}$ . Cyclic voltammetry indicated a different electrocatalytic reduction process on hydrothermally treated electrodes, compared to thermally oxidized ones. Hydrothermally treated electrodes were also found to have the thickest porous anatase layer and achieved 50-75 % alanine conversion efficiencies. Optimization showed that the cell potential, reactant flow rate and the PA: NH 2 OH ratio were crucial parameters in determining the conversion efficiency. η ${\eta }$ and j ‾ ${\left|\overline{j}\right|}$ were found to significantly decrease when an excess of is used and, an optimal alanine η ${\eta }$ of 75 % was achieved at 2.0 V applied cell potential and 10 mL/h reactant flow rate., (© 2024 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

Pt nanoparticles are typically decorated as co-catalyst on semiconductors to enhance the photocatalytic performance. Due to the low abundance and high cost of Pt, reaching a high activity with minimized co-catalyst loadings is a key challenge in the field. We explore a dewetting-dealloying strategy to fabricate on TiO 2 nanotubes nanoporous Pt nanoparticles, aiming at improving the co-catalyst mass activity for H 2 generation. For this, we sputter first Pt-Ni bi-layers of controllable thickness (nm range) on highly ordered TiO 2 nanotube arrays, and then induce dewetting-alloying of the Pt-Ni bi-layers by a suitable annealing step in a reducing atmosphere: the thermal treatment causes the Pt and Ni films to agglomerate and at the same time mix with each other, forming on the TiO 2 nanotube surface metal islands of a mixed PtNi composition. In a subsequent step we perform chemical dealloying of Ni that is selectively etched out from the bimetallic dewetted islands, leaving behind nanoporous Pt decorations. Under optimized conditions, the nanoporous Pt-decorated TiO 2 structures show a>6 times higher photocatalytic H 2 generation activity compared to structures modified with a comparable loading of dewetted, non-porous Pt. We ascribe this beneficial effect to the nanoporous nature of the dealloyed Pt co-catalyst, which provides an increased surface-to-volume ratio and thus a more efficient electron transfer and a higher density of active sites at the co-catalyst surface for H 2 evolution., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Self-standing TiO 2 nanotube layers in the form of membranes are fabricated by self-organizing anodization of Ti metal and a potential shock technique. The membranes are then decorated by sputtering different Pt amounts i) only at the top, ii) only at the bottom or iii) at both top and bottom of the tube layers. The Pt-decorated membranes are transferred either in tube top-up or in tube top-down configuration onto FTO slides and are investigated, after crystallization, as photocatalysts for H 2 generation using either front or back-side light irradiation. Double-side Pt-decoration of the tube membranes leads to higher H 2 generation rates (independently of tube and light-irradiation configuration) compared to membranes decorated at only one side with similar overall Pt amounts. The results suggest that this effect cannot be only ascribed to the overall amount of Pt co-catalyst as such but also to its distribution at both tube extremities. This leads to optimized light absorption and electron diffusion/transfer dynamics: the central part of the membranes acts as light-harvesting zone and electrons therein generated can diffuse towards the Pt/TiO 2 active zones (tube extremities) where they can react with the environment and generate H 2 ., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In the present work we investigate various optical properties (such as light absorption and reflectance) of anodic TiO2 nanotube layers directly transferred as self-standing membranes onto quartz substrates. This allows investigation in a transmission geometry which provides significantly more reliable data than measurements on the metallic Ti substrate. Light transmission and reflectance measurements were carried out for layers of thickness varying from 1.8 to 50 μm, and the layers were investigated in their amorphous and crystalline forms. A series of wavelength-dependent light attenuation coefficients are extrapolated and found to match the photocurrent versus irradiation wavelength behavior. A feature specific to anodic nanotubes is that their intrinsic carbon contamination content causes a proportional sub-bandgap response. Overall, the extracted data provide a valuable basis and understanding for the design of photo-electrochemical devices based on TiO2 nanotubes., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Anodic self-organized TiO2 nanostumps are formed and exploited for self-ordering dewetting of Au-Ag sputtered films. This forms ordered particle configurations at the tube top (crown position) or bottom (ground position). By dealloying from a minimal amount of noble metal, porous Au nanoparticles are then formed, which, when in the crown position, allow for a drastically improved photocatalytic H2 production compared with nanoparticles produced by conventional dewetting processes., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Electrochemical anodization of low-concentration (0.02-0.2 at% Au) TiAu alloys in a fluoride electrolyte leads to self-organized TiO2 nanotubes that show a controllable, regular in situ decoration with elemental Au nanoclusters of ≈5 nm in diameter. The degree of self-decoration can be adjusted by the Au concentration in the alloy and the anodization time. Such Au particle decorated tubes show a high activity for photocatalytic H2 production from ethanol solutions., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Peas in a pod: A highly aligned Au(np)@TiO2 photocatalyst was formed by self-organizing anodization of a Ti substrate followed by dewetting of a gold thin film. This leads to exactly one Au nanoparticle (np) per TiO2 nanocavity. Such arrays are highly efficient photocatalysts for hydrogen generation from ethanol., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A little dopey: Ta-doped titania (TiO2) nanotube (NT) arrays can be grown by electrochemical anodization onto low-Ta-concentration (0.03-0.4 at % Ta) Ti-Ta alloys. Under optimized conditions (0.1 at % Ta, annealing at 650 °C and 7 μm thickness), Ta-doped TiO2 NT arrays show a significantly enhanced activity in photoelectrochemical water splitting under simulated sunlight conditions (see figure)., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)