Rutile Oxide Research Articles

Oxygen Vacancy-Electron Polarons Featured InSnRuO2 Oxides: Orderly and Concerted In-Ov-Ru-O-Sn Substructures for Acidic Water Oxidation.

Polymetallic oxides with extraordinary electrons/geometry structure ensembles, trimmed electron bands, and way-out coordination environments, built by an isomorphic substitution strategy, may create unique contributing to concertedly catalyze water oxidation, which is of great significance for proton exchange membrane water electrolysis (PEMWE). Herein, well-defined rutile InSnRuO2 oxides with density-controllable oxygen vacancy (Ov)-free electron polarons are firstly fabricated by in situ isomorphic substitution, using trivalent In species as Ov generators and the adjacent metal ions as electron donors to form orderly and concerted In-Ov-Ru-O-Sn substructures in the tetravalent oxides. For acidic water oxidation, the obtained InSnRuO2 displays an ultralow overpotential of 183 mV (versus RHE) and a mass activity (MA) of 103.02 A mgRu -1, respectively. For a long-term stability test of PEMWE, it can run at a low and unchangeable cell potential (1.56 V) for 200 h at 50 mA cm-2, far exceeding current IrO2||Pt/C assembly in 0.5 m H2SO4. Accelerated degradation testing results of PEMWE with pure water as the electrolyte show no significant increase in voltage even when the voltage is gradually increased from 1 to 5 A cm-2. The remarkably improved performance is associated with the concerted In-Ov-Ru-O-Sn substructures stabilized by the dense Ov-electron polarons, which synergistically activates band structure of oxygen species and adjacent Ru sites and then boosting the oxygen evolution kinetics. More importantly, the self-trapped Ov-electron polaron induces a decrease in the entropy and enthalpy, and efficiently hinder Ru atoms leaching by increasing the lattice atom diffusion energy barrier, achieves long-term stability of the oxide. This work may open a door to design next-generation Ru-based catalysts with polarons to create orderly and asymmetric substructures as active sites for efficient electrocatalysis in PEMWE application.

Absence of magnetic order in RuO2: insights from μSR spectroscopy and neutron diffraction

Altermagnets are a novel class of magnetic materials, where magnetic order is staggered both in coordinate and momentum space. The metallic rutile oxide RuO2, long believed to be a textbook Pauli paramagnet, recently emerged as a putative workhorse altermagnet when resonant X-ray and neutron scattering studies reported nonzero magnetic moments and long-range collinear order. While some experiments seem consistent with altermagnetism, magnetic order in RuO2 remains controversial. We show that RuO2 is nonmagnetic, both in bulk and thin film. Muon spectroscopy complemented by density-functional theory finds at most 1.14 × 10−4 μB/Ru in bulk and at most 7.5 × 10−4 μB/Ru in 11 nm epitaxial films, at our spectrometers’ detection limit, and dramatically smaller than previously reported neutron results that were used to rationalize altermagnetic behavior. Our own neutron diffraction measurements on RuO2 single crystals identify multiple scattering as the source for the false signal in earlier studies.

Biochar-Supported Titanium Oxide for the Photocatalytic Treatment of Orange II Sodium Salt

Recent improvements in advanced technology for toxic chemical remediation have involved the application of titanium oxide nanoparticles as a photocatalyst. However, the large energy bandgap associated with titanium oxide nanoparticles (3.0–3.20 eV) is a limitation for their application as a photocatalyst within the solar spectrum. Various structural modification methods have led to significant reductions in the energy bandgap but not without their disadvantages, such as electron recombination. In the current investigation, biochar was made from the leaves of an invasive plant (Acacia saligna) and subsequently applied as a support in the synthesis of titanium oxide nanoparticles. The characterization of biochar-supported titanium oxide nanoparticles was performed using scanning electron microscopy, Fourier transformer infrared, X-ray diffraction, and Brunauer–Emmett–Teller analyses. The results showed that the titanium oxide was successfully immobilized on the biochar’s external surface. The synthesized biochar-supported titanium oxide nanoparticles exhibited the phenomenon of small hysteresis, which represents the typical type IV isotherm attributed to mesoporous materials with low porosity. Meanwhile, X-ray diffraction analysis revealed the presence of a mixture of rutile and anatase crystalline phase titanium oxide. The synthesis of biochar-supported titanium oxide nanoparticles was highly efficient in the degradation of Orange II Sodium dye under solar irradiation. Moreover, 83.5% degradation was achieved when the biochar-supported titanium oxide nanoparticles were used as photocatalysts in comparison with the reference titanium oxide, which only achieved 20% degradation.

High-Mobility Carriers in Epitaxial IrO2 Films Grown using Hybrid Molecular Beam Epitaxy.

Binary rutile oxides of 5d metals such as IrO2 stand out in comparison to their 3d and 4d counterparts due to limited experimental studies, despite rich predicted quantum phenomena. Here, we investigate the electrical transport properties of IrO2 by engineering epitaxial thin films grown using hybrid molecular beam epitaxy. Our findings reveal phonon-limited carrier transport and thickness-dependent anisotropic in-plane resistance in IrO2 (110) films, the latter suggesting a complex relationship between strain relaxation and orbital hybridization. Magnetotransport measurements reveal a previously unobserved nonlinear Hall effect. A two-carrier analysis of this effect shows the presence of minority carriers with mobility exceeding 3000 cm2/(V s) at 1.8 K. These results point toward emergent properties in 5d metal oxides that can be controlled using dimensionality and epitaxial strain.

Oxidation Behavior of Lightweight Al0.2CrNbTiV High Entropy Alloy Coating Deposited by High-Speed Laser Cladding

High-temperature oxidation resistance is the major influence on the high-temperature service stability of refractory high entropy alloys. The oxidation behavior of lightweight Al0.2CrNbTiV refractory high entropy alloy coatings with different dilution ratios at 650 °C and 800 °C deposited by high-speed laser cladding was analyzed in this paper. The oxidation kinetic was analyzed, the oxidation resistance mechanism of the Al0.2CrNbTiV coating was clarified with the analysis of the formation and evolution of the oxidation layer, and the effect of the dilution rate on high-temperature performances was revealed. The results showed that the oxide layer was mainly composed of rutile oxides (Ti, Cr, Nb)O2 after isothermal oxidation at 650 °C and 800 °C for 50 h. The Al0.2CrNbTiV coating in low dilution exhibited better oxidation performance at 650 °C, due to the dense oxide layer formed with the synergistic growth of fine AlVO3 particles and (Ti, Cr, Nb)O2, and higher percentage of Cr, Nb in (Ti, Cr, Nb)O2 strengthened the lattice distortion effect to inhibit the penetration of oxygen. The oxide layer formed at 800 °C for the Al0.2CrNbTiV coating was relatively loose, but the oxidation performance of the coating in high dilution improved due to the precipitation of Cr2Nb-type Laves phases along grain boundaries, which inhibits the diffusion of oxygen.

Order-Disorder Transition in Rutile VO2(M) Electrodes during Li Intercalation and Extraction.

Transition metal oxides are widely employed as electrode materials in Li-ion batteries. During battery operation, Li ions are intercalated and extracted from the framework of the electrode structure, causing structural transitions. In some materials, the process can drive order-disorder transitions; however, insights into such processes are generally lacking, although they are essential for our understanding of battery aging and in the design of new sustainable battery chemistries. Herein, we investigate the intercalation-induced order-disorder transition in rutile VO2(M) electrodes by means of galvanostatic charge/discharge cycling, operando powder X-ray diffraction, and total X-ray scattering with pair distribution function analysis. The study reveals that the rutile structure transforms irreversibly into a highly disordered layered Li x VO2 structure, which is capable of reversibly intercalating Li ions. Our findings point out general trends for the intercalation-driven transitions in rutile oxides.

Effect of Co-Sputtered Copper and Titanium Oxide Coatings on Bacterial Resistance and Cytocompatibility of Osteoblast Cells.

One of the primary risk factors for implant failure is thought to be implant-related infections during the early healing phase. Developing coatings with cell stimulatory behaviour and bacterial adhesion control is still difficult for bone implants. This study proposes an approach for one-step deposition of biocompatible and antimicrobial Cu-doped TiO2 coatings via glow-discharge sputtering of a mosaic target. During the deposition, the bias of the Ti6Al4V substrates was changed. Structure examination, phase analysis, and surface morphology were carried out using X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The hardness values and hydrophilic and corrosion performance were also evaluated together with cytocompatible and antibacterial examinations against E. coli and S. aureus. The results show great chemical and phase control of the bias identifying rutile, anatase, CuO, or ternary oxide phases. It was found that by increasing the substrate bias from 0 to -50 V the Cu content increased from 15.3 up to 20.7 at% while at a high bias of -100 V, the copper content reduced to 3 at%. Simultaneously, apart from the Cu2+ state, Cu1+ is also found in the biased samples. Compared with the bare alloy, the hardness, the water contact angle and corrosion resistance of the biased coatings increased. According to an assessment of in vitro cytocompatibility, all coatings were found to be nontoxic to MG-63 osteoblast cells over the time studied. Copper release and cell-surface interactions generated an antibacterial effect against E. coli and S. aureus strains. The -50 V biased coating combined the most successful results in inhibiting bacterial growth and eliciting the proper responses from osteoblastic cells because of its phase composition, electrochemical stability, hydrophilicity, improved substrate adhesion, and surface roughness. Using this novel surface modification approach, we achieved multifunctionality through controlled copper content and oxide phase composition in the sputtered films.

Silver-Doped Titanium Oxide Layers for Improved Photocatalytic Activity and Antibacterial Properties of Titanium Implants.

Titanium has a long history of clinical use, but the naturally forming oxide is not ideal for bacterial resistance. Anodization processes can modify the crystallinity, surface topography, and surface chemistry of titanium oxides. Anatase, rutile, and mixed phase oxides are known to exhibit photocatalytic activity (PCA)-driven bacterial resistance under UVA irradiation. Silver additions are reported to enhance PCA and reduce bacterial attachment. This study investigated the effects of silver-doping additions to three established anodization processes. Silver doping showed no significant influence on oxide crystallinity, surface topography, or surface wettability. Oxides from a sulfuric acid anodization process exhibited significantly enhanced PCA after silver doping, but silver-doped oxides produced from phosphoric-acid-containing electrolytes did not. Staphylococcus aureus attachment was also assessed under dark and UVA-irradiated conditions on each oxide. Each oxide exhibited a photocatalytic antimicrobial effect as indicated by significantly decreased bacterial attachment under UVA irradiation compared to dark conditions. However, only the phosphorus-doped mixed anatase and rutile phase oxide exhibited an additional significant reduction in bacteria attachment under UVA irradiation as a result of silver doping. The antimicrobial success of this oxide was attributed to the combination of the mixed phase oxide and higher silver-doping uptake levels.

Antisymmetric planar Hall effect in rutile oxide films induced by the Lorentz force

The conventional Hall effect is linearly proportional to the field component or magnetization component perpendicular to a film. Despite the increasing theoretical proposals on the Hall effect to the in-plane field or magnetization in various special systems induced by the Berry curvature, such an unconventional Hall effect has only been experimentally reported in Weyl semimetals and in a heterodimensional superlattice. Here, we report an unambiguous experimental observation of the antisymmetric planar Hall effect (APHE) with respect to the in-plane magnetic field in centrosymmetric rutile RuO2 and IrO2 single-crystal films. The measured Hall resistivity is found to be linearly proportional to the component of the applied in-plane magnetic field along a particular crystal axis and to be independent of the current direction or temperature. Both the experimental observations and theoretical calculations confirm that the APHE in rutile oxide films is induced by the Lorentz force. Our findings can be generalized to ferromagnetic materials for the discovery of anomalous Hall effects and quantum anomalous Hall effects induced by in-plane magnetization. In addition to significantly expanding knowledge of the Hall effect, this work opens the door to explore new members in the Hall effect family.

An Unexpected Decrease in Vibrational Entropy of Multicomponent Rutile Oxides.

High-entropy oxides (HEOs), featuring infinite chemical composition and exceptional physicochemical properties, are attracting much attention. The configurational entropy caused by a component disorder of HEOs is popularly believed to be the main driving force for thermal stability, while the role of vibrational entropy in the thermodynamic landscape has been neglected. In this study, we systematically investigated the vibrational entropy of multicomponent rutile oxides (including Fe0.5Ta0.5O2, Fe0.333Ti0.333Ta0.333O2, Fe0.25Ti0.25Ta0.25Sn0.25O2, and Fe0.21Ti0.21Ta0.21Sn0.21Ge0.16O2) by precise heat capacity measurements. It is found that vibrational entropy gradually decreases with increasing component disorder, beyond what one could expect from an equilibrium thermodynamics perspective. Moreover, all multicomponent rutile oxides exhibit a positive excess vibrational entropy at 298.15 K. Upon examinations of configuration disorder, size mismatch, phase transition, and polyhedral distortions, we demonstrate that the excess vibrational entropy plays a pivotal role in lowering the crystallization temperature of multicomponent rutile oxides. These findings represent the first experimental confirmation of the role of lattice vibrations in the thermodynamic landscape of rutile HEOs. In particular, vibrational entropy could serve as a novel descriptor to guide the predictive design of multicomponent oxide materials.

Anatase and rutile titanium oxide nanoparticles induce acute kidney injury by coadministration with paraquat, cisplatin or 5-aminosalicylic acid.

Nanoparticles are used in a variety of fields; for example, titanium oxide nanoparticles are used in paints, food additives, cosmetics, and sunscreen materials. Although the use of titanium oxide nanoparticles is regulated, their safety has not been established. Furthermore, the interaction between titanium oxide nanoparticles and various chemical substances and pharmaceuticals is unknown. We co-administered rutile-type titanium oxide nanoparticles (nTR) or anatase-type titanium oxide nanoparticles (nTA) to mice together with paraquat (PQ), cisplatin (CDDP), or anti-5-aminosalicylic acid (5-ASA), and investigated the extent, if any, of liver and kidney injury. As a result, when nTA and nTR were administered alone, no increases were observed in aspartate aminotransferase (AST) and alanine aminotransferase (ALT), which are indicators of liver damage, or urea nitrogen (BUN), which is an indicator of kidney damage. Next, nTA and nTR were co-administered with PQ, CDDP or 5-ASA. Although no increase in ALT or AST was observed, BUN levels increased significantly and acute kidney injury was induced. The findings suggested that titanium oxide nanoparticles induce acute kidney injury through their interaction with chemicals and drugs.

Uncovering the active sites of single atom-doped rutile oxides during methane activation by data-driven approach

Uncovering the active sites of single atom-doped rutile oxides during methane activation by data-driven approach

The Thermophysical Properties of TcO2

Technetium-99 is a highly radioactive isotope with a long half-life that is common in nuclear waste. It volatizes at a low temperature, which poses a significant challenge to the clean-up and containment processes. Due to difficulties in purifying technetium compounds, their thermophysical properties have not been measured or calculated. Here, first principle methods are used along with the quasi quasi-harmonic harmonic approximation to compute the Debye temperature, volumetric thermal expansion coefficient, bulk modulus, and heat capacity of rutile TcO2 for temperatures ranging from 0 to 1500 K and applied pressures ranging from 0 to 255 GPa. The computed atomic structures agree well with the results from diffraction measurements. The computed thermophysical properties are in the neighborhood of other rutile metal oxides and, in particular, are within approximately 10–13% of rutile ReO2, which is frequently used as a substitute for TcO2 in experimental studies.

Fabrication and properties of lateral Josephson junctions with a RuO2 weak link

Ruthenium dioxide (RuO2) is a metallic rutile oxide with a number of interesting properties. For a long time, it was considered to be a highly conductive normal metal and a Pauli paramagnet. Recently, it was found that the material is antiferromagnetic, with small magnetic moments of the order of 0.05 Bohr magneton and an ordering temperature above 300 K. The presence of magnetic moments should have clear consequences when trying to induce superconductivity in RuO2. We used a selective area chemical vapor deposition method to grow nanostrips of RuO2 on TiO2 substrates. On these nanostrips, superconducting contacts were made of MoGe, and a weak link was fabricated with a Focused Ion Beam. We find that the device behaves as a Josephson junction, including a Fraunhofer-like response to a magnetic field, for distances between the contacts below 70 nm. We estimate the induced singlet coherence length ξ to be about 12 nm, which seems a reasonable number when small magnetic moments are present.

CH3 radical-mediated direct methane to methanol conversion over CuO supported on rutile oxides

Direct conversion of methane into methanol is an attractive strategy for the production of manifold value-added chemicals. Herein, we investigated the conversion of methane to methanol over CuO supported on the rutile metal oxides (TiO2, SnO2 and RuO2) based on results of density functional theory (DFT) calculations. The results show that the oxygen site of the supported CuO exhibits the characteristics of a radical anion. This radical anionic oxygen site enables homolytic C-H cleavage by abstracting the hydrogen atom, resulting in a CH3 radical. The CH3 radical captured by the Cu site next to the radical anionic oxygen enables the coupling of CH3 and OH to form a C-O bond, resulting in methanol. The free energy of activation for C-H activation and C-O formation were found to correlate linearly with the p band center of the radical anionic oxygen, but the slope has the opposite signs, i.e., a lower free energy of activation for C-H scission corresponds to a higher free energy formation for C-O formation. Among rutile oxides studied, SnO2 offers a balanced reactivity for C-H activation and C-O formation. These findings demonstrate the presence of the radical anionic oxygen on rutile oxide-supported CuO catalyst and their crucial role in regulating the reactivity for direct methane to methanol conversion. The mechanistic insights from this study will benefit the development of supported copper oxide catalysts for effective methane conversion.

Provenance of the Oligocene Barail Sandstones Exposed In and Around Longsa Village, Wokha District, Nagaland: Reflections from Petrography and Heavy Minerals

Petrographic and heavy mineral compositions of the Oligocene Barail sandstones exposed in and around Longsa village of Wokha District, Nagaland, have been utilized for provenance interpretation. Grey and yellow coloured sandstones of the study area are comprised of angular to sub-rounded monocrystalline, non-undulatory quartz and the various lithic fragments. The overall composition of sandstones (Q-90.10%, F-1.70 %, RF-8.18%) matches with those of sublith-arenites category. The heavy mineral assemblage of the studied Barail sandstones is represented by euhedral/rounded to sub-rounded grains of zircon, tourmaline, rutile, kyanite, sillimanite, andalusite, titanite, staurolite and iron oxide. The studied sandstone composition suggests that the Barail sediments were derived from mixed provenance. Heavy mineral analysis also corroborates the above. Keywords: Petrography, Heavy Minerals, Provenance, Barail Group, Nagaland

Phase Reduction and Thermodynamic Analysis of Ilmenite Ore by Carbothermal-Iodination using Different Carbon Reductants

The present study is on the combination of carbothermal reduction and iodination reaction (carboiodination) process for the phase reduction of ilmenite ore (FeTiO3). The aim is to understand the phase reduction and thermodynamic reaction analysis of ilmenite ore by a combined method of carbothermal-iodination using different carbon reductants (graphite and palm char). Graphite was used as a standard carbon reductant while palm char as a renewable carbon reductant was prepared via the pyrolysis technique. Ilmenite was mixed with carbon reductants and then first reduced by using a carbothermal reduction process at 1550℃. Then, the reduced samples were further investigated with iodination reaction in different temperature ranges of 900-1000 °C using a vertical tube furnace with mixed argon and iodine gas (0.2 L/min). The proximate and ultimate analyses of carbon reductants were analysed by CHON analyser and their microstructure by using SEM, while XRF and XRD were used for analyzing the chemical compositions and the phase reductions of raw ilmenite ore and reduced samples, respectively. The thermodynamics of possible reactions during carbothermal-iodination reactions were calculated by HSC Chemistry 6.0 software. By comparing graphite and palm char, palm char had an amorphous structure, with porous and high carbon content showing high potential for usage as a reductant in titanium extraction from ilmenite ore. The phases of ilmenite ore were ilmenite, rutile, and anatase transformed into rutile, pseudobrookite, and titanium oxide detected by XRD. Further reduction was performed by palm char where more rutile (TiO2) and titanium oxide (Ti3O5) developed from the iodination reaction at the highest temperature compared to graphite due to better properties and amorphous structure. The rutile and titanium oxide were found as stable phases from the thermodynamic analysis and confirmed with XRD. From the findings, the combination of carbothermal-iodination of ilmenite ore was possible and promising for rutile (TiO2) production in mineral extractions.

Investigation on Phase Evaluation of Ilmenite Ore by Carbothermal Reduction and Carboiodination Reaction

This article presented the thermochemical calculation and experimental investigation on the phase evaluation of ilmenite ore (FeTiO3) via carbothermal reduction and carboiodination reaction for titanium production using graphite as a reducing agent. The carbothermal reduction and carboiodination reactions were performed in two different furnaces. The carbothermal reduction was evaluated at a temperature of 1550°C with inert argon gas utilizing a horizontal tube furnace. The carboiodination reactions were evaluated in temperatures ranging from 900°C, 950°C, and 1000°C using a vertical tube furnace with mixed iodine gas with argon gas. XRF and XRD were used for analyzing the chemical compositions and the phase evolutions of raw ilmenite ore and the reduced samples, respectively. The findings showed that the Perak ilmenite ore predominantly has a greater concentration of TiO2 (71.27wt%), Fe2O3 (18.85wt%), and some other oxides like aluminum oxide and quartz. In addition, XRD revealed that the ilmenite phase was converted into rutile (TiO2) titanium oxide (Ti3O5, Ti2O3), titanium carbide (TiC), and iron (Fe) phases, after the carbothermal reduction process. However, after the carboiodination reaction, the ilmenite and rutile phases remained at temperatures 900°C, 950°C, and 1000°C. The HSC Chemistry software was used in the determination of the thermochemical calculation and the possible reactions during the reaction which play an important role in shortening the reduction process. The results revealed the carboiodination process is a promising process that can reduce energy consumption and shorten the titanium production processes, and it needs more studies.

A p-type dopable ultrawide-bandgap oxide

A major shortcoming of ultrawide-bandgap (UWBG) semiconductors is unipolar doping, in which either n-type or p-type conductivity is typically possible, but not both within the same material. For UWBG oxides, the issue is usually the p-type conductivity, which is inhibited by a strong tendency to form self-trapped holes (small polarons) in the material. Recently, rutile germanium oxide (r-GeO2), with a band gap near 4.7 eV, was identified as a material that might break this paradigm. However, the predicted acceptor ionization energies are still relatively high (∼0.4 eV), limiting p-type conductivity. To assess whether r-GeO2 is an outlier due to its crystal structure, the properties of a set of rutile oxides are calculated and compared. Hybrid density functional calculations indicate that rutile TiO2 and SnO2 strongly trap holes at acceptor impurities, consistent with previous work. Self-trapped holes are found to be unstable in r-SiO2, a metastable polymorph that has a band gap near 8.5 eV. Group-III acceptor ionization energies are also found to be lowest among the rutile oxides and approach those of GaN. Acceptor impurities have sufficiently low formation energies to not be compensated by donors such as oxygen vacancies, at least under O-rich limit conditions. Based on the results, it appears that r-SiO2 has the potential to exhibit the most efficient p-type conductivity when compared to other UWBG oxides.

In situ preparation of nano cone-like structures of rutile titanium oxides on titanium implants by one-step femtosecond laser irradiation for enhanced mechanical properties and biocompatibility

Titanium oxides (TiO2) nanostructures coating is helpful in improving the utilization of titanium in many areas due to its multifunctional properties. This study introduces a novel approach for the in-situ fabrication of nano cones-like structures of rutile titanium oxides (NCS–TiO2) on the surface of titanium utilizing femtosecond laser technology. Rutile titanium oxides were synthesized with a height of around 80 nm and a diameter of 100 nm, forming NCS that imparts higher hardness, wear resistance, and biocompatibility. Molecular dynamic simulation provides valuable insights into the three-stage formation process of NCS-TiO2. Molecular dynamic simulation revealed that the growth of rutile titanium oxides and the formation of nano cones-like structures are attributed to the interplay between femtosecond laser ablation and the accumulation of thermal energy. The proposed method offers a versatile and straightforward approach for creating functional surfaces on metal substrates, enabling broad applicability and ease of implementation, specifically in titanium and its alloys. This advancement holds great potential for expanding the scope of titanium-based materials and their applications, paving the way for improved mechanical properties and biocompatibility in diverse fields.