Anodic TiO2 Nanotube Layers Research Articles

Can electrodeposited Ti replace rolled Ti as substrate for the growth of anodic TiO2 nanotube layers?

This study conducted a deep investigation of TiO2 nanotube (TNT) layers of two different thicknesses anodically grown on electrodeposited Ti films. The Ti films were grown from molten salts on Ni foils. The structure of the starting metals was compared by XRD (X-Ray Diffraction) and EBSD (Electron Backscatter Diffraction analyses), which showed a strong orientation towards the titanium (101) for the electrodeposited substrate, compared to the rather polycrystalline structure of the rolled Ti. The photoelectrochemical and electrochemical properties of 1 μm and 5 μm thick TNT layers anodically grown on these substrates were examined and compared with TNT layers of the same thickness. No significant morphological and compositional differences were found using SEM (Scanning Electron Microscopy) and XPS (X-ray Photoelectron Spectroscopy) between the TNT layers grown on the two substrates. However, higher photocurrent densities and ICPE values were observed for TNT layers grown on electrodeposited Ti. An in-depth investigation using Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) analyses showed increased conductivity of the TNT layers produced on electrodeposited Ti compared to their counterparts. The carrier density (ND) for the TNT layers on electrodeposited Ti, calculated from Mott-Schottky measurements, showed a higher doping level than the TNT layers grown on Ti foils. This increase in ND results in more optimal photoelectrochemical performance of the TNT layers grown on electrodeposited Ti. All in all, the results presented herein pave the way for the use of electrodeposited Ti, with all its inherent benefits, and allow the further study of its promising properties in a wide range of applications.

Recent advances in TiO2 nanotube layers – A mini review of the latest developments in nanotube preparation and applications in photocatalysis and microwave sensing

AbstractSelf‐organized anodic TiO2 nanotube (TNT) layers prepared by anodization of Ti substrates have attracted great interest within the last 20 years, due to their unique properties and low‐cost synthesis. This mini review article aims to shortly summarize the most recent developments in the TNT layer synthesis and applications. It presents the synthesis of high aspect ratio (HAR) TNT layers in a short time by accelerating the TNT layer growth rates in lactic acid containing electrolytes. Furthermore, the etching of TNT layers towards TNT bundles of homogeneous size and single tube powders is discussed, as well as the possibility to grow TNT layers on non‐planar Ti substrates, which cannot be directly connected to the potentiostat (e.g., Ti spheres or 3D Ti meshes). As a relatively new application, the employment of TNT layers in microwave resonator sensors is introduced. Last, but not least, approaches of upscaling the TNT layer size from the laboratory scale towards significantly larger scale are outlined and reviewed.

Non-thermal regimes of laser annealing of semiconductor nanostructures: crystallization without melting

As-prepared nanostructured semiconductor materials are usually found in an amorphous form, which needs to be converted into a crystalline one for improving electronic properties and achieving enhanced application functionalities. The most utilized method is thermal annealing in a furnace, which however is time- and energy-consuming and not applicable for low-temperature melting substrates. An alternative is laser annealing, which can be carried out in a relatively short time and, additionally, offers the possibility of annealing localized areas. However, laser-annealed nanostructures are often distorted by melting, while preserving the as-prepared morphology is essential for practical applications. In this work, we analyze conditions of non-thermal ultrafast laser annealing of two kinds of nanostructures: anodic TiO2 nanotube layers and Ge/Si multilayer stacks. For both cases, regimes of crystallization have been found, which yield in preserving the initial nanomaterial morphologies without any melting signs. On these examples, ultrafast non-thermal mechanisms of structural material transformation are discussed, which can provide new opportunities for conversion of amorphous semiconductor nanomaterials into a desired crystalline form that is of high demand for existing and emerging technologies.

Bio-AFM exploits enhanced response of human gingival fibroblasts on TiO2 nanotubular substrates with thin TiO2 coatings

The present work studies anodic TiO2 nanotube (TNT) layers and their surface modifications for enhancing the cell behavior of human gingival fibroblast cells (hGFs) with the contribution of bio-AFM (Atomic Force Microscopy) method. TNT layers, prepared via electrochemical anodization of Ti, with an average tube diameter of 15, 30, and 100 nm, were used as primary substrates for the study. Flat Ti foils were used as reference substrates. Part of the substrates was coated by ultrathin TiO2 coatings (≈ 0.3 nm thin) using Atomic Layer Deposition (ALD). The cell growth and adhesion of hGFs on the TNT layers and Ti foils were compared between ALD coated and uncoated ones. The supplemental coatings altered the surface chemistry of the TNT layers, particularly shading the fluorine and carbon impurities within anodic TiO2, while preserving the original structure and morphology. The presented approach of very mild surface modification remarkably effects the material's biocompatibility and possess great prospect as implant materials. For the first time, the TNT/cell interface was investigated using bio-AFM in terms of Young's modulus, stiffness, cell adhesive force and roughness. Improved biocompatibility was studied in terms of increased cell viability, density, cell cytoskeleton orientation and overall stiffness of the hGFs.

Large-Scale Anodic TiO2 Nanotube Layers: Gas Phase Photocatalysis and Virus Killing

Self-organized TiO2 nanotube layers have attracted considerable scientific and technological interest over the past 15 years motivated for their wide range of applications including (photo-) catalysis, hydrogen generation and biomedical uses [1,2]. The synthesis of the 1D TiO2 nanotube layers is carried out by a conventional electrochemical anodization of valve Ti metal sheets in various electrolytes.By now, the synthesis of TiO2 nanotube layers with different nanotube dimensions (diameter, length) and the application of these nanotube layers is well established on the laboratory scale. However, for real applications outside the laboratory scale, such as photocatalysis [3], TiO2 nanotube layers of much larger size are necessary. To date, just a few efforts were carried out to scale up the size of the nanotube layers to more than a few cm2 [3-7] due to the difficulty of controlling the parameters of the anodization process on a larger scale. The main challenge is the huge current received during the anodization of large substrates. This, in turn, leads to an increase in the electrolyte temperature that may result in dielectric breakdown of the growing nanotube layers.In this presentation, the preparation of TiO2 nanotube layers on larger area titanium substrates (dozens of cm2) will be discussed, taking into account the control of the anodization parameters. The TiO2 nanotube layers with different thicknesses and nanotube diameters were employed for gas phase photocatalysis, following the ISO standards [3,8]. In addition, results from antivirotic tests of these layers will be demonstrated. Experimental details and photocatalytic results will be presented and discussed.

Decrypting the growth of anodic TiO2 nanotube layers in eco-friendly fluoride-free nitrate-based electrolyte for enhanced photocatalytic degradation of organic pollutants

Anodic TiO2 nanotube (TNT) layers were prepared in eco-friendly fluoride-free organic-aqueous-based electrolytes containing cerium ammonium nitrate. Nanotubes with controllable morphology (tube diameter and tube length) and surface features (porosity and surface roughness) were obtained by varying percentual ratios of ethylene glycol (Ex%) and water (Wy%) in the electrolyte (Ex%Wy%). Obtained TNT layers were studied for photocatalytic degradation of methylene blue (MB) under UVA irradiation. The most promising, TNT layers were prepared in E75%W25% electrolyte with a thickness of approx. 1.9 μm with a tube diameter of approx. 33 nm, and exhibited the highest photocatalytic degradation rate (k = 0.0151 min−1).

Pt single atoms dispersed in a hybrid MOFox-in-nanotube structure for efficient and long-term stable photocatalytic H2 generation

Hierarchical structures produced by thermal conversion of MOFs within the anodic TiO2 nanotube layers combine the excellent light harvesting, carrier transport, and Pt SA anchoring to achieve a remarkable photocatalytic H2 evolution performance.

Anodic TiO2 Nanotube Layers for Wastewater and Air Treatments: Assessment of Performance Using Sulfamethoxazole Degradation and N2O Reduction.

The preparation of anodic TiO2 nanotube layers has been performed using electrochemical anodization of Ti foil for 4 h at different voltages (from 0 V to 80 V). In addition, a TiO2 thin layer has been also prepared using the sol-gel method. All the photocatalysts have been characterized by XRD, SEM, and DRS to investigate the crystalline phase composition, the surface morphology, and the optical properties, respectively. The performance of the photocatalyst has been assessed in versatile photocatalytic reactions including the reduction of N2O gas and the oxidation of aqueous sulfamethoxazole. Due to their high specific surface area and excellent charge carriers transport, anodic TiO2 nanotube layers have exhibited the highest N2O conversion rate (up to 10% after 22 h) and the highest degradation extent of sulfamethoxazole (about 65% after 4 h) under UVA light. The degradation mechanism of sulfamethoxazole has been investigated by analyzing its transformation products by LC-MS and the predominant role of hydroxyl radicals has been confirmed. Finally, the efficiency of the anodic TiO2 nanotube layer has been tested in real wastewater reaching up to 45% of sulfamethoxazole degradation after 4 h.

Magnetically guidable single TiO2 nanotube photocatalyst: Structure and photocatalytic properties

The influence of annealing temperature, the crystallinity, textural properties of magnetically guidable anodic TiO2 nanotubes in form of single tube powders on the photocatalytic decomposition of model organic dye is investigated for the first time. The powders were prepared from self-organized anodic TiO2 nanotube layers (grown on Ti) by etching in piranha solution, detaching them from the Ti substrate, and annealing in a wide range of temperatures (400–900 °C). The nanotubular shape was preserved up to 800 °C. Powders annealed up to 800 °C did not contain any detectable rutile phase, which is unique among other TiO2 nanomaterials at this temperature. Part of the obtained TiO2 ST-NT powders was decorated with Fe3O4 nanoparticles using an oleic acid-based synthesis. The TiO2 ST-NT and TiO2 ST-NT@Fe3O4NPs powders were characterized in terms of morphology, crystallinity, and specific surface area. Finally, all materials were exploited for the photocatalytic decomposition of a model dye. The best photocatalytic performance of TiO2 ST-NT and TiO2 ST-NT@Fe3O4NPs powders were obtained at annealing temperatures of 600 and 700 °C, respectively. The synergy resulting from annealing, crystallite size, and specific surface area enhances the photocatalytic activity of TiO2 ST-NT and TiO2 ST-NT@Fe3O4NPs powders under UV light. This approach goes beyond the classical Kasuga alkaline hydrothermal approach, enabling the preparation of large quantity of TiO2 nanotubes without any impurities (such as e.g. Na or Ca content resulting from the Kasuga approach).

Bipolar Electrochemistry for the Synthesis of Anodic TiO2 Nanotube Layers

Self-organized TiO2 nanotube (TNT) layers have attracted considerable scientific and technological interest over the past 17 years motivated for their wide range of applications including (photo-) catalysis, hydrogen generation and biomedical uses [1,2]. The synthesis of these TNT layers is carried out by electrochemical anodization of valve Ti metal substrates in various F--containing electrolytes using a conventional 2-electrode set-up with the Ti substrate as anode and a Pt-foil as cathode.Instead of using a conventional set-up, also bipolar electrochemistry can be employed for the anodization of valve metals [3-7]. In this set-up, the Ti substrate is placed in an electrolyte between two so-called feeder electrodes, which are connected to the potentiostat. Due to the electric field between the feeder electrodes, the Ti substrate is polarized. If the applied potential between the feeder electrodes is high enough, redox reactions can be driven on the Ti substrate. This method opens new doors for the preparation of TNT layers with gradients in dimensions (i.e. diameter and length of the nanotubes) [3-5] as well as for the preparation of TNT layers on Ti substrates, which cannot be directly connected to the potentiostat, e.g. Ti spheres [8].In this presentation, the preparation of TNT layers on small Ti spheres [8] as well as on 3D printed Ti substrates [9] using bipolar electrochemistry will be shown and discussed. Furthermore, we will also show the possibility of using closed bipolar electrochemical cells, consisting of two closed half-cells with the Ti substrate as obstacle between the cells [10].

Anodic TiO2 nanotube layers decorated by Pd nanoparticles using ALD: An efficient electrocatalyst for methanol oxidation

Herein, we report the performance of Pd nanoparticles (NPs) prepared by Atomic Layer Deposition (ALD) as a catalyst for methanol electro-oxidation. Pd NPs were decorated onto anodic TiO2 nanotube (TNT) layers as supporting material that possess a large available surface area and direct electrical contact via the underlying titanium foil. Different Pd loadings (150 – 300 – 450 – 600 ALD cycles) show different particles sizes ranging between 7 and 12 nm, as revealed by transmission electron microscopy. Coalescence dominated visibly from 450 ALD cycles, which led to a porous Pd layer all along the TNT walls rather than the growth of individual particles. Electrocatalytic performance was investigated by cyclic voltammetry (CV), where the catalytic activity increased proportional with Pd loading up to the highest values for 400 and 450 cycles, whereas a further increase in the number of ALD cycles (NALD) did not show any additional improvement in methanol oxidation current densities. TNT layers decorated with 400, 450 and 600 Pd ALD cycles show featureless curves suggesting complete anti-poisoning ability or possibly a proof of a direct conversion from CH3OH to CO2 (without any intermediate byproducts). The lack of an oxidation peak during the anodic scan and therefore a reduction peak during the cathodic scan, confirms Pd NPs (stabilized by TiO2) efficiently utilize OHads and chemisorbed CH3OH in a way that its CO poisoning was inhibited. As a result, the tuned high surface area TNT layers exhibited excellent performance as a supporting material for Pd NPs against formation of electrochemical poisoning species. Finally, the mechanism of the TNT layers interaction with Pd NPs, which led to the propelling methanol oxidation reaction without loss in performance over cycling is postulated.

Bipolar Electrochemistry for the Synthesis of Anodic TiO2 Nanotube Layers

Self-organized TiO2 nanotube (TNT) layers have attracted considerable scientific and technological interest over the past 17 years motivated for their wide range of applications including (photo-) catalysis, hydrogen generation and biomedical uses [1,2]. The synthesis of these TNT layers is carried out by electrochemical anodization of valve Ti metal substrates in various F--containing electrolytes using a conventional 2-electrode set-up with the Ti substrate as anode and a Pt-foil as cathode.Instead of using a conventional set-up, also bipolar electrochemistry can be employed for the anodization of valve metals [3-7]. In this set-up, the Ti substrate is placed in an electrolyte between two so-called feeder electrodes, which are connected to the potentiostat. Due to the electric field between the feeder electrodes, the Ti substrate is polarized. If the applied potential between the feeder electrodes is high enough, redox reactions can be driven on the Ti substrate. This method opens new doors for the preparation of TNT layers with gradients in dimensions (i.e. diameter and length of the nanotubes) [3-5] as well as for the preparation of TNT layers on Ti substrates, which cannot be directly connected to the potentiostat, e.g. Ti spheres [8].In this presentation, the preparation of TNT layers on small Ti spheres [8] as well as on 3D printed Ti substrates [9] using bipolar electrochemistry will be shown and discussed. Furthermore, we will also show the possibility of using closed bipolar electrochemical cells, consisting of two closed half-cells with the Ti substrate as obstacle between the cells [10].

Scaling up anodic TiO2 nanotube layers – Influence of the nanotube layer thickness on the photocatalytic degradation of hexane and benzene

In this work, the preparation of homogenous TiO2 nanotube (TNT) layers with different thicknesses via anodization on Ti substrates with a large geometrical area of two times 5 cm x 10 cm (i.e. both sides of the Ti substrate) is shown for the first time. TNT layers with four different thicknesses of ∼0.65 µm, ∼1 µm, ∼7 µm, and ∼14 µm were prepared with excellent conformality and homogeneity over the anodized area. These TNT layers were successfully employed as photocatalysts for the degradation of hexane and benzene as model compounds in the gas phase under ISO standards, showing an increase of the conversion for both model compounds with the TNT layer thickness. While a stable hexane conversion was observed for all TNT layers during the measuring time of three hours, in case of benzene degradation an initial conversion decrease was monitored before the conversion stabilized. Despite this trend, SEM and XPS analyses did not reveal any significant amount of reaction products on the TNT layer surface.

Fluoride-free synthesis of anodic TiO2 nanotube layers: a promising environmentally friendly method for efficient photocatalysts.

TiO2 nanotube (TNT) layers are generally prepared in fluoride-based electrolytes via electrochemical anodization that relies on the field-assisted dissolution of Ti metal forming nanoporous/nanotubular structures. However, the usage of fluoride ions is considered hazardous to the environment. Therefore, we present an environmentally friendly synthesis and application of TNT layers prepared in fluoride-free nitrate-based electrolytes. A well-defined nanotubular structure with thickness up to 1.5 μm and an inner tube diameter of ∼55 nm was obtained within 5 min using aqueous X(NO3)Y electrolytes (X = Na+, K+, Sr2+, Ag+). For the first time, we show the photocatalytic performance (using a model organic pollutant), HO˙ radical production, and thorough characterization of TNT layers prepared in such electrolytes. The highest degradation efficiency (k = 0.0113 min-1) and HO˙ radical production rate were obtained using TNT layers prepared in AgNO3 (Ag-NT). The intrinsic properties of Ag-NT such as the valence band maximum of ∼2.9 eV, surface roughness of ∼6 nm, and suitable morphological features and crystal structure were obtained. These results have the potential to pave the way for a more environmentally friendly synthesis of anodic TNT layers in the future using the next generation of fluoride-free nitrate-based electrolytes.

New Protocols for the Synthesis of Anodic TiO2 Nanotube Layers

Self-organized TiO2 nanotube (TNT) layers have attracted considerable scientific and technological interest over the past 17 years motivated for their wide range of applications including (photo-) catalysis, hydrogen generation and biomedical uses [1,2]. The synthesis of these TNT layers is carried out by electrochemical anodization of valve Ti metal substrates in various F--containing electrolytes using a conventional 2-electrode set-up with the Ti substrate as anode and a Pt-foil as cathode.Instead of using a conventional set-up, also bipolar electrochemistry can be employed for the anodization of valve metals [3-7]. In this set-up, the Ti substrate is placed in an electrolyte between two so-called feeder electrodes, which are connected to the potentiostat. Due to the electric field between the feeder electrodes, the Ti substrate is polarized. If the applied potential between the feeder electrodes is high enough, redox reactions can be driven on the Ti substrate. By using electrolytes conventionally employed for the anodic TNT layer synthesis, TNT layers can also be produced using bipolar electrochemistry. This method opens new doors for the preparation of TNT layers with gradients in dimensions (i.e. diameter and length of the nanotubes) [3-5] as well as for the preparation of TNT layers on Ti substrates, which cannot be directly connected to the potentiostat, e.g. Ti spheres [8].In this presentation, the preparation of TNT layers on small Ti spheres using bipolar electrochemistry will be shown and discussed [8]. Furthermore, we will also show the possibility of using closed bipolar electrochemical cells, consisting of two closed half-cells with the Ti substrate as obstacle between the cells.

Secondary Material Modified Anodic TiO2 Nanotube Layers As Efficient Gas Sensors

Gas sensors are extensively used in medical, automotive, agriculture, biogas, and mining industry for safety and environmental monitoring, including the detection of toxic compounds to prevent hazardous emission and explosion as well as air quality monitoring. 1D nanomaterials have shown great potential for sensor preparation due to their high surface-to-volume ratios resulting in countless absorption sites, and fast diffusion of gas molecules. The 1D geometry also facilitates the charge transport process [1,2].Among 1D nanomaterials, self-organized TiO2 nanotube layers have attracted considerable scientific and technological interest due to their wide possible range of applications including (photo-) catalysis, solar cells, hydrogen generation, biomedical uses or sensors [3,4]. The synthesis of the 1D TiO2 nanotube layers is usually carried out by electrochemical anodization of valve Ti metal sheets in various electrolytes. Compared to TiO2 nanotubes prepared by other methods (e.g. hydrothermal), anodic TiO2 nanotube layers have the advantage of being self-ordered with the nanotube openings on the top of the nanotube layer and being well-adhered to the Ti metal substrate, which can further be used as back contact for applications. Furthermore, anodic TiO2 nanotube layers can be produced with tunable tube dimensions [4]. Atomic Layer Deposition (ALD) can be used to produce conformal and homogenous coatings of thin layers of secondary materials an TiO2 nanotube layers, with precise control of the coating thickness, according to the deposition cycles [5]. Therefore, very thin films matching the thickness of the Debye length of a material can be deposited by ALD on the high surface area TiO2 nanotube layers giving the possibility for high sensitivity semiconductor gas sensors.The presentation will focus on the coating of anodic TiO2 nanotube layers with secondary materials using ALD and the possible use for low concentration gas sensing. Such secondary materials are, for instance, SnO2 [6] and ZnO [7]. The produced heterostructures show excellent sensing behavior for NO2 [6], in case of SnO2 coated TiO2 nanotube layers, and for ethanol [7], in case of ZnO coated TiO2 nanotube layers.

(Invited) Anodic TiO2 Nanotube Layers: Efficient Photocatalyst

The self-organized TiO2 nanotube layers have attracted considerable scientific and technological interest over the past 15 years motivated by their possible range of applications including photocatalysis, solar cells, hydrogen generation and biomedical uses [1,2]. The synthesis of these 1D TiO2 nanotube layers is carried out by a conventional electrochemical anodization of valve Ti metal sheet.Among other TiO2 nanomaterials, these nanotube layers stand out due to their directionality, tunability of dimensions, ability to absorb significant amount of incident light and the possibility to utilize nanotube interiors and exteriors for decoration-coating of secondary materials.One of the most significant applications of TiO2 nanomaterials is photocatalysis, which is very effective to decompose various pollutants (e.g. dyes) and kill bacteria [3,4].The presentation will focus on the utilization of the nanotube layer for photocatalytic removal of various species in the liquid phase [5, 6] as well as gas phase [7]. We will demonstrate the photocatalytic performance of recently developed single-wall TiO2 nanotubes and single-tube TiO2 powders [8]. We will also show that various modifications of nanotube ssecondary materials have a positive influence on photo-electrochemical properties of nanotube layers [9,10]. Experimental details and some recent photocatalytic results will be presented and discussed.

Anodic TiO2 Nanotube Layers As Scaffolds for Deposition of Functional Materials

The self-organized 1D TiO2 nanotubular layers have attracted considerable scientific and technological interest over the past two decades, all motivated by a great performance in the range of applications including photo-catalysis, solar cells, hydrogen generation and biomedical uses [1,2]. The synthesis of these nanotubular layers has been carried out by a conventional electrochemical anodization of Ti sheet. Except the 1D character, these nanotubes possess unique features such as tunable dimensionality, structural flexibility, unidirectional electron transport through nanotube walls, chemical and mechanical stability and biocompatibility.One of the major application targets of TiO2 nanotubes has been their utilization as scaffolds or templates for deposition of secondary materials towards new applications [3]. In particular, for the photoelectrochemical applications (e.g. photovoltaics) ordered nanostructures, such as self-organized TiO2 nanotubes, offer the advantage of directed charge transport and controlled phase separation between the donor and acceptor materials, unlike within randomly ordered mesoporous TiO2 supports.Numerous techniques were utilized for this purpose, such as for example hydrothermal routes, electrodeposition or Atomic Layer Deposition (ALD) techniques. Electrodeposition is very powerful technique to deposit metals [4], oxides [5] or other rather complex materials (such as CuInSe2 [6]) within the nanotubes various by means of complete filling or decoration with. On the other hand, ALD can deposit the widest range of secondary materials within TiO2 nanotubes by means of homogenous coatings [7-10].The presentation will be focused in detail on TiO2 nanotube layers of various aspect ratios filled, decorated or coated by various materials using electrodeposition. Experimental details and some very recent photo-electrochemical and structural characterizations of a new type of heterostructured photo-chemical cell will be presented and discussed.References J.M. Macak et al., Curr. Opin. Solid State Mater. Sci., 2007 , 1-2, 3-17.J.Lee, A. Mazare, P. Schmuki, Chem. Rev., 2014, 114, 9385-9454J.M. Macak, Chapter 3 in: D. Losic and A. Santos, Electrochemically Engineered Nanoporous Structures, Springer International Publishing, Switzerland, 2015.J.M. Macak, B.G. Gong, M. Hueppe, P. Schmuki, Adv. Mater., 2007, 19, 3027.L.Wu & G. Zangari, J. Phys. Chem. C, 2010, 114, 11551S.Das & J. M. Macak et al., ChemElectroChem, 2017, 4, 495R. Zazpe et al, Langmuir, 2016, 32, 10551S. Ng et al., Adv. Eng. Mater., DOI: 10.1002/adem.201700589R. Zazpe et al., Nanoscale, 2018, 10, 16601-16612.F.Dvorak et al., Appl. Mater. Today, 2019 , 14, 1-20.

High Aspect Ratio TiO2 Nanotube Layers Obtained in a Short Time

In the last two decades, anodic TiO2 nanotube (TNT) layers have gained considerable attention for both their unique physical and chemical properties practical applications [1-3].One of the key parameters that characterize TNT layers is the aspect ratio, which is the ratio between the TNT layer thickness and the nanotube diameter. In particular, TNT layers with a high aspect ratio (HAR) due to their 1D ordered structure, an exceptional morphology and a high surface area, have a great potential in different applications, such as filtration and micro-photo reactors [4,5]. In the last decade, ethylene glycol (EG)-based electrolytes containing small amounts of NH4F and H2O [6] were the most widely used electrolytes to produce high-aspect ratio TNT layers. However, using these electrolytes very long anodization times i.e., several hours or up to several days [7], are needed. Apparently, the synthesis of long and extremely robust HAR TNT layers in a relatively short time remains very challenging until now. Recently, it has been shown that the addition of lactic acid (LA) to EG-based electrolytes can shift the dielectric breakdown potential to significantly higher potentials due to the strong adsorption of lactic acid on TiO2 during the anodization [8]. Thus, considerably higher anodization potentials and increased electrolyte temperatures can be employed and HAR TNT layers can be obtained within less than one hour of anodization.In this presentation we will demonstrate that HAR TNT layers can be obtained within short anodization times using an optimized anodization protocol. The key feature is the use of NH4F/H2O/EG electrolytes containing LA with optimized electrolyte [9].Experimental details and some recent anodization results will be presented and discussed.

Intrinsically Ru-Doped Suboxide TiO2 Nanotubes for Enhanced Photoelectrocatalytic H2 Generation

In the present research, we investigate the synergistic effects of Ru-doping and Ar/H2 reduction treatment on the photoelectrochemical water splitting performance and hydrogen evolution rate of TiO2 nanotube array photoelectrodes. The Ti–Ru alloy with 0.2 at. % Ru was used to grow anodic self-organized Ru-doped TiO2 nanotube layers. An ideal synergy between Ar/H2 reduction treatment and Ru-doping results in the extended absorption toward the visible light region and improved photoelectrocatalytic activity. The black Ru-doped TiO2–x photoanode’s water splitting rate improves remarkably (∼ninefold) compared to the black TiO2–x sample (∼twofold). Moreover, the black Ru-doped TiO2–x photoanode shows a considerable increase in the H2 production rate (1.91 μmol h–1 cm–2) compared with the pristine TiO2 nanotube layer (0.044 μmol h–1 cm–2). We have also developed an ab initio model of pristine, Ru-doped, and Ru-doped hydrogenated TiO2 nanotubes to rationalize our experimental findings from the theoretical perspective.