Search Results (20)

Black titania, a conductive ceramic material class, has garnered significant interest due to its unique optical and electrochemical properties. However, synthesising and properly characterising these structures pose a considerable challenge. This diverse material family comprises various titanium oxide phases, many of them non-stoichiometric. The term “black TiO₂” was first introduced in 2011 by Xiaobo Chen, but Arne Magneli’s groundbreaking discovery and in-depth investigation of black titania in 1957 laid the foundation for our understanding of this material. The non-stoichiometric black titanium oxides were then called the Magneli phases. Since then, the science of black titania has advanced, leading to numerous applications in photocatalysis, electrocatalysis, supercapacitor electrodes, batteries, gas sensors, fuel cells, and microwave absorption. Yet, the literature is rife with conflicting reports, primarily due to the inadequate analysis of black titania materials. This review aims to provide an overview of black titania nanostructures synthesis and the proper characterisation of the most common and applicable black titania phases. Full article

The development of promising biocompatible composites based on hydroxyapatite with a metallic component is of great interest to researchers. This article describes the synthesis of hydroxyapatite powder by the hydrolytic method and presents the results of mechanical grinding of hydroxyapatite powder. Additionally, in order to study the interaction between titanium and hydroxyapatite powders, the results of their thermal treatment in the temperature range of 600–900 °C are presented. As a result of the hydrolytic method, a powder consisting of Ca₅(PO₄)₃(OH) and CaO phases with a fraction of 400–600 μm was obtained. According to the results of mechanical grinding, it was determined that with an increase in grinding time from 30 to 120 min, the intensive main diffraction lines corresponding to hydroxyapatite decrease. During the thermal treatment of titanium and hydroxyapatite powders, titanium oxidizes forming suboxides and titanium dioxide (TiO₂). At higher temperatures, the hydroxyapatite phase disappears from the mixture, and titanium oxide, calcium phosphate compound, and small amounts of calcium titanate and titanium hydrophosphate are present. Full article

Magnéli phase titanium oxides, also called titanium sub-oxides (Ti_nO_2n−1, 4 < n < 9), are a series of electrically conducting ceramic materials. The synthesis and applications of these materials have recently attracted tremendous attention because of their applications in a number of existing and emerging areas. Titanium sub-oxides are generally synthesized through the reduction of titanium dioxide using hydrogen, carbon, metals or metal hydrides as reduction agents. More recently, the synthesis of nanostructured titanium sub-oxides has been making progress through optimizing thermal reduction processes or using new titanium-containing precursors. Titanium sub-oxides have attractive properties such as electrical conductivity, corrosion resistance and optical properties. Titanium sub-oxides have played important roles in a number of areas such as conducting materials, fuel cells and organic degradation. Titanium sub-oxides also show promising applications in batteries, solar energy, coatings and electronic and optoelectronic devices. Titanium sub-oxides are expected to become more important materials in the future. In this review, the recent progress in the synthesis methods and applications of titanium sub-oxides in the existing and emerging areas are reviewed. Full article

Ti15Zr15Mo (TMZ alloy) has been studied in recent years for biomedical applications, mainly due to phase beta formation. From the surface modification, it is possible to associate the volume and surface properties with a better biomedical response. This study aimed to evaluate the possibility of using anodization to obtain TiO₂ nanotubes due to the presence of valve-type metal (Zr) in their composition. X-ray photoelectron spectroscopy (XPS) was performed to determine the surface chemical composition in both after-processing conditions (passive layer) and after-processing plus anodization (TiO₂ nanotube growth). The anodization resulted in nanotubes with diameters and thicknesses of 126 ± 35 and 1294 ± 193 nm, respectively, and predominated anatase phase. Compared to the passive layer of titanium, which is less than ~10 nm, the oxide layer formed was continuous and thicker. High-resolution spectra revealed that the oxide layer of the element alloys contained different oxidation states. The major phase in all depths for the nanotube samples was TiO2. While the stable form of each oxide was found to predominate on the surface, the inner part of the oxide layer consisted of suboxides and metallic forms. This composition included different oxidation states of the substrate elements Ti, Zr, and Mo. Full article

We propose the use of Optical Coherence Tomography (OCT) as a tool for the quality control of 3-D-printed ceramics. Test samples with premeditated defects, namely single- and two-component samples of zirconia, titania, and titanium suboxides, were printed by stereolithography-based DLP (Digital Light Processing) processes. The OCT tomograms obtained on the green samples showed the capability of the method to visualize variations in the layered structure of the samples as well as the presence of cracks and inclusions at depths up to 130 µm, as validated by SEM images. The structural information was visible in cross-sectional images as well as in plan-view images. The optical signal measured from the printed zirconia oxide and titanium oxide samples showed strong attenuation with depth and could be fit with an exponential decay curve. The variations of the decay parameter correlated very well with the presence of defects and material variation. When used as an imaging quantity, the decay parameter projects the position of the defects into 2-D (X,Y) coordinates. This procedure can be used in real time, it reduces the data volume up to 1000 times, and allows for faster subsequent data analysis and transfer. Tomograms were also obtained on sintered samples. The results showed that the method can detect changes in the optical properties of the green ceramics caused by sintering. Specifically, the zirconium oxide samples became more transparent to the light used, whereas the titanium suboxide samples became entirely opaque. In addition, the optical response of the sintered zirconium oxide showed variations within the imaged volume, indicating material density variations. The results presented in this study show that OCT provides sufficient structural information on 3-D-printed ceramics and can be used as an in-line tool for quality control. Full article

This article’s objective is the synthesis of new composites based on thermoplastic polyurethane (TPU) and TiO₂ nanowires (NWs) as free-standing films, highlighting their structural and optical properties. The free-standing TPU–TiO₂ NW films were prepared by a wet chemical method accompanied by a thermal treatment at 100 °C for 1 h, followed by air-drying for 2 h. X-ray diffraction (XRD) studies indicated that the starting commercial TiO₂ NW sample contains TiO₂ tetragonal anatase (A), cubic Ti_0.91O (C), and orthorhombic Ti₂O₃ (OR), as well as monoclinic H₂Ti₃O₇ (M). In the presence of TPU, an increase in the ratio between the intensities of the diffraction peaks at 43.4° and 48° belonging to the C and A phases of titanium dioxide, respectively, is reported. The increase in the intensity of the peak at 43.4° is explained to be a consequence of the interaction of TiO₂ NWs with PTU, which occurs when the formation of suboxides takes place. The variation in the ratio of the absorbance of the IR bands peaked at 765–771 cm⁻¹ and 3304–3315 cm⁻¹ from 4.68 to 4.21 and 3.83 for TPU and the TPU–TiO₂ NW composites, respectively, with TiO₂ NW concentration equal to 2 wt.% and 17 wt.%, indicated a decrease in the higher-order aggregates of TPU with a simultaneous increase in the hydrogen bonds established between the amide groups of TPU and the oxygen atoms of TiO₂ NWs. The decrease in the ratio of the intensity of the Raman lines peaked at 658 cm⁻¹ and 635 cm⁻¹, which were assigned to the vibrational modes E_g in TiO₂ A and E_g in H₂Ti₃O₇ (I_TiO2-A/I_H2Ti3O7), respectively, from 3.45 in TiO₂ NWs to 0.94–0.96 in the TPU–TiO₂ NW composites, which indicates that the adsorption of TPU onto TiO₂ NWs involves an exchange reaction of TPU in the presence of TiO₂ NWs, followed by the formation of new hydrogen bonds between the -NH- of the amide group and the oxygen atoms of Ti_xO_2x-mn, Ti₂O₃, and Ti_0.91O. Photoluminescence (PL) studies highlighted a gradual decrease in the intensity of the TPU emission band, which is situated in the spectral range 380–650 nm, in the presence of TiO₂ NW. After increasing the TiO₂ NW concentration in the TPU–TiO₂ NW composite mass from 0 wt.% to 2 wt.% and 17 wt.%, respectively, a change in the binding angle of the TPU onto the TiO₂ NW surface from 12.6° to 32° and 45.9°, respectively, took place. Full article

The fabrication of nanostructured composite materials is an active field of materials chemistry. However, the ensembles of nanostructured titanium monoxide and suboxide species decorated with polyaniline (PANI) species have not been deeply investigated up to now. In this study, such composites were formed on both hydrothermally oxidized and anodized Ti substrates via oxidative polymerization of aniline. In this way, highly porous nanotube-shaped titanium dioxide (TiO₂) and nano leaflet-shaped titanium monoxide (TiO_x) species films loaded with electrically conductive PANI in an emeraldine salt form were designed. Apart from compositional and structural characterization with Field Emission Scanning Electron Microscopy (FESEM) and Raman techniques, the electrochemical properties were identified for each layer using cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Based on the experimentally determined EIS parameters, it is envisaged that TiO-based nanomaterials decorated with PANI could find prospective applications in supercapacitors and biosensing. Full article

To achieve low-carbon and sustainable development it is imperative to explore water treatment technologies in a carbon-neutral model. Because of its advantages of high efficiency, low consumption, and no secondary pollution, electrocatalytic oxidation technology has attracted increasing attention in tackling the challenges of organic wastewater treatment. The performance of an electrocatalytic oxidation system depends mainly on the properties of electrodes materials. Compared with the instability of graphite electrodes, the high expenditure of noble metal electrodes and boron-doped diamond electrodes, and the hidden dangers of titanium-based metal oxide electrodes, a titanium sub-oxide material has been characterized as an ideal choice of anode material due to its unique crystal and electronic structure, including high conductivity, decent catalytic activity, intense physical and chemical stability, corrosion resistance, low cost, and long service life, etc. This paper systematically reviews the electrode preparation technology of Magnéli phase titanium sub-oxide and its research progress in the electrochemical advanced oxidation treatment of organic wastewater in recent years, with technical difficulties highlighted. Future research directions are further proposed in process optimization, material modification, and application expansion. It is worth noting that Magnéli phase titanium sub-oxides have played very important roles in organic degradation. There is no doubt that titanium sub-oxides will become indispensable materials in the future. Full article

The application potential of Pt/Ti₄O₇ has been reported, but the lack of research on the relationship between Pt loading, MSI, and catalytic activity hinders further development. Micron-sized Ti₄O₇ powders synthesized by a thermal reduction method under an H₂ atmosphere were used as a support material for Pt-based catalysts. Using a modified polyol method, Pt/Ti₄O₇-5, Pt/Ti₄O₇-10, and Pt/Ti₄O₇-20 with different mass ratios (Pt to Pt/Ti₄O₇ is 0.05, 0.1, 0.2) were successfully synthesized. Uniformly dispersed platinum nanoparticles exhibit disparate morphologies, rod-like for Pt/Ti₄O₇-5 and approximately spherical for Pt/Ti₄O₇-10 and Pt/Ti₄O₇-20. Small-angle deflections and lattice reconstruction induced by strong metal–support interactions were observed in Pt/Ti₄O₇-5, which indicated the formation of a new phase at the interface. However, lattice distortions and dislocations for higher loading samples imply the existence of weak metal–support interactions. A possible mechanism is proposed to explain the different morphologies and varying metal–support interactions (MSI). With X-ray photoelectron spectroscopy, spectrums of Pt and Ti display apparent shifts in binding energy compared with commercial Pt-C and non-platinized Ti₄O₇, which can properly explain the changes in absorption ability and oxygen reduction reaction activity, as described in the electrochemical results. The synthetic method, Pt loading, and surface coverage of the support play an important role in the adjustment of MSI, which gives significant guidance for better utilizing MSI to prepare the target catalyst. Full article

The Ti/SnO₂ interface has been investigated in situ via the technique of x-ray photoelectron spectroscopy. Thin films (in the range from 0.3 to 1.1 nm) of titanium were deposited on SnO₂ substrates via the e-beam technique. The deposition was carried out at two different substrate temperatures, namely room temperature and 200 °C. The photoelectron spectra of tin and titanium in the samples were found to exhibit significant differences upon comparison with the corresponding elemental and the oxide spectra. These changes result from chemical interaction between SnO₂ and the titanium overlayer at the interface. The SnO₂ was observed to be reduced to elemental tin while the titanium overlayer was observed to become oxidized. Complete reduction of SnO₂ to elemental tin did not occur even for the lowest thickness of the titanium overlayer. The interfaces in both the types of the samples were observed to consist of elemental Sn, SnO₂, elemental titanium, TiO₂, and Ti-suboxide. The relative percentages of the constituents at the interface have been estimated by curve fitting the spectral data with the corresponding elemental and the oxide spectra. In the 200 °C samples, thermal diffusion of the titanium overlayer was observed. This resulted in the complete oxidation of the titanium overlayer to TiO₂ upto a thickness of 0.9 nm of the overlayer. Elemental titanium resulting from the unreacted overlayer was observed to be more in the room temperature samples. The room temperature samples showed variation around 20% for the Ti-suboxide while an increasing trend was observed in the 200 °C samples. Full article

Presently, in the context of the novel coronavirus pneumonia epidemic, several antibiotics are overused in hospitals, causing heavy pressure on the hospital’s wastewater treatment process. Therefore, developing stable, safe, and efficient hospital wastewater treatment equipment is crucial. Herein, a bench-scale electrooxidation equipment for hospital wastewater was used to evaluate the removal effect of the main antibiotic levofloxacin (LVX) in hospital wastewater using response surface methodology (RSM). During the degradation process, the influence of the following five factors on total organic carbon (TOC) removal was discussed and the best reaction condition was obtained: current density, initial pH, flow rate, chloride ion concentration, and reaction time of 39.6 A/m², 6.5, 50 mL/min, 4‰, and 120 min, respectively. The TOC removal could reach 41% after a reaction time of 120 min, which was consistent with the result predicted by the response surface (40.48%). Moreover, the morphology and properties of the electrode were analyzed. The degradation pathway of LVX was analyzed using high-performance liquid chromatography–mass spectrometry (LC–MS). Subsequently, the bench-scale electrooxidation equipment was changed into onboard-scale electrooxidation equipment, and the onboard-scale equipment was promoted to several hospitals in Dalian. Full article

A recently developed multi-ceramic additive manufacturing process (multi-CAMP) and an appropriate device offer a multi-material approach by vat photopolymerization (VPP) of multi-functionalized ceramic components. However, this process is limited to ceramic powders with a certain translucency for visible light. Electrically conductive ceramic powders are therefore ruled out because of their light-absorbing behavior and dark color. The goal of the collaborative work described in the article was to develop a material combination for this multi-material approach of the additive vat photopolymerization method which allows for combining electrical conductivity and electrical insulation plus high mechanical strength in co-sintered ceramic components. As conductive component titanium suboxides are chosen, whereas zirconia forms the mechanically stable and insulation part. Since titanium suboxides cannot be used for vat photopolymerization due to their light-absorbing behavior, titania is used instead. After additive manufacturing, the two-component parts are co-sintered in a reducing atmosphere to transform the titania into its suboxides and, thus, attaining the desired property combination. The article describes the challenges of the co-processing of both materials due to the complex optical properties of titania. Furthermore, the article shows successfully co-sintered testing parts of the material combination of zirconia/titanium suboxide which are made by assembling single-material VPP components in the green state and subsequent common thermal treatment. The results of microstructural and interface investigations such as electrical measurements are discussed. Full article

It is expected that utilization of molybdenum disulfide (MoS₂)-based nanostructured electrocatalysts might replace the Pt-group electrodes most effectively applied for hydrogen evolution reaction from water. Therefore, in the past two decades, various approaches have been reported for fabrication of nanostructured MoS₂-based catalysts, but their applications in practice are still missing due to lower activity and stability. We envisaged that the knowledge about the peculiarities of MoS₂ nanoplatelets attachment to various conductive substrates by hydrothermal processing could be helpful for fabrication of more active and stable working electrodes. Therefore, in this study, the hydrothermal syntheses at the Mo, Ti, Al, anodized Ti, and hydrothermally designed titanium suboxide substrates were performed; the electrodes obtained were characterized; and hydrogen evolution reaction (HER) activity was tested. In this way, MoS₂-based HER catalyst possessing a surprising stability and a low Tafel slope was designed via attachment of nanoplatelet-shaped MoS₂ species to the nanotube-shaped anatase-TiO₂ surface. Full article

We report a non-hydrolytic sol-gel (NHSG) route to engineer original mesoporous Ti_nO_2n−1@TiO₂/C nanocomposites. The synthetic approach is straightforward, solvent-free, additive-free, and meets the challenge of atom economy, as it merely involves TiCl₄ and THF in stoichiometric amounts. We found that these nanocomposites present enhanced electrocatalytic properties towards the oxygen reduction reaction (ORR) in 0.1 M KOH. We believe that these preliminary results will open a window of opportunity for the design of metal suboxides/carbon nanocomposites through NHSG routes. Full article

Electrocatalysts play an important role in oxygen reduction reaction (ORR) in promoting the reaction process. Although commercial Pt/C exhibits excellent performance in ORR, the low duration, high cost, and poor methanol tolerance seriously restrict its sustainable development and application. Ti_nO_2n−1 (3 ≤ n ≤ 10) is a series of titanium sub-oxide materials with excellent electrical conductivity, electrochemical activity, and stability, which have been widely applied in the field of energy storage and catalysis. Herein, we design and synthesize Ti₄O₇/Ti₃O₅ (T4/T3) dual-phase nanofibers with excellent ORR catalytic performance through hydrothermal growth, which is followed by a precisely controlled calcination process. The H₂Ti₃O₇ precursor with uniform size can be first obtained by optimizing the hydrothermal growth parameters. By precisely controlling the amount of reducing agent, calcination temperature, and holding time, the T4/T3 dual-phase nanofibers with uniform morphology and coherent interfaces can be obtained. The orientation relationships between T4 and T3 are confirmed to be ${\left[001\right]}_{\mathrm{T}3}//{\left[031\right]}_{\mathrm{T}4}$ , ${\left(100\right)}_{\mathrm{T}3}//{\left(92\overline{6}\right)}_{\mathrm{T}4}$ , and ${\left(010\right)}_{\mathrm{T}3}//{\left(1\overline{2}6\right)}_{\mathrm{T}4}$ , respectively, based on comprehensive transmission electron microscopy (TEM) investigations. Furthermore, such dual-phase nanofibers exhibit the onset potential and half-wave potential of 0.90 V and 0.75 V as the ORR electrocatalysts in alkaline media, respectively, which illustrates the excellent ORR catalytic performance. The rotating ring-disk electrode (RRDE) experiment confirmed the electron transfer number of 3.0 for such catalysts, which indicates a mixture of two electron and four electron transfer reaction pathways. Moreover, the methanol tolerance and cycling stability of the catalysts are also investigated accordingly. Full article