Physicochemical Characterization of Ca- and Cu-Decorated TiO2 Microparticles and Investigation of Their Antimicrobial Properties.

Ca- and Cu-decorated TiO2 microparticles are titanium dioxide nanoparticles that have been decorated with calcium and copper ions. TiO2, CaO, and CuO are low-cost, non-toxic, and non-hazardous materials. The aim of the present study was the physicochemical characterization of Ca- and Cu-decorated TiO2 microparticles and the evaluation of their antimicrobial activity. Thus, Ca2+ and Cu2+ species were incorporated onto TiO2 surfaces by a two-step wet method. The obtained TiO2-CaO-CuO composites were characterized by several experimental techniques. The electronic structure and charge properties of the composites were investigated by density functional theory calculations. Furthermore, the composites were successfully tested for inhibitory effects on Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, and Candida albicans standard strains. The zeta potential data indicate that the physiological condition of investigated microbial strains was strongly affected in presence of a dispersion of 10 µg/L of composites in a saline phosphate buffer also, the recorded SEM images show a damaged microbial cell surface in the presence of composites.

A rapid transition from subduction to Barrovian metamorphism: geochronology of mafic-ultramafic relicts of oceanic crust in the Central Alps, Switzerland.

Relicts of subducted oceanic lithosphere provide key information for the tectonic reconstructions of convergent margins. In the Central Alps, such relicts occur as isolated mafic-ultramafic lenses within the migmatites of the southern Adula nappe and Cima-Lunga unit. Analysis of the major-, minor-, and accessory minerals of these ophiolitic relicts, combined with zircon and rutile U-Pb ages and zircon oxygen isotopes, allows the reconstruction of different stages of their complex evolution. The mafic-ultramafic suite in Valle di Moleno consists of chlorite-harzburgites associated with metarodingites and retrogressed eclogites. Relic omphacite and kyanite in retrogressed eclogites provide evidence for subduction-related metamorphism. Increasing XPrp in the garnet mantle towards the rim documents heating during high-pressure metamorphism up to 800-850 °C. Polyphase inclusions and chemical zoning in garnet suggest fluid-assisted melting during high-pressure metamorphism dated at 31.0 ± 0.9 Ma. In Val Cama, chlorite-harzburgites, metarodingites and calcsilicate-metasediments occur. Detrital zircon ages in the metasediment suggest a Mesozoic deposition. The metarodingite-metaperidotite-metasediment association and the low δ18O signatures of zircon (δ18O 3.0-3.7‰), inherited from seafloor metasomatism of the protoliths, show that the rocks are derived from former altered oceanic crust. Amphibolite facies metamorphism related to the Central Alps Barrovian evolution in Val Cama occurred at 28.8 ± 1.5 Ma. The combined data from Moleno and Cama indicate a rapid transition (~ 2 Ma) from subduction to collisional metamorphism with corresponding exhumation rates of 3-6 cm/year. Fast exhumation tectonics may have been favored by slab break-off or slab extraction. U-Pb dating of rutile from both localities yields ages of ~ 20 Ma, suggesting that these rocks remained at amphibolite-facies conditions for about 10 Ma and underwent a second fast exhumation of 3 cm/year associated with vertical movements along the Insubric line. Supplementary Information: The online version contains supplementary material available at 10.1186/s00015-024-00462-7.

Rutile-Type Co0.5Ti0.5NbO4-Based Cathode with In Situ Exsolved Metal Particles for Direct CO2 Electrolysis.

Rutile-type Co0.5Ti0.5NbO4 (CTO)-based materials doped with Fe3+ or Ni2+ were investigated as cathode electrodes to modify their electrical conductivity and electrocatalysis toward CO2 splitting. Higher electric conductivity was found in Co0.4Fe0.2Ti0.4NbO4 (CTO-Fe, 0.78 S cm-1) and Co0.25Ni0.25Ti0.5NbO4 (CTO-Ni, 2.10 S cm-1) compared to CTO (0.49 S cm-1) after the reduction at 800 °C in Ar-5% H2. Co and Co-Ni particles exsolved in situ from the surface of CTO, CTO-Fe, and CTO-Ni after reduction. CTO-Ni and CTO-Fe cathodes did better in the CO2 electrolysis at 800 °C than the CTO one, but the CTO-Ni cell was unstable after 10 h of operation due to the carbon deposition that blocked the electrode. The cell with CTO-Fe demonstrated a good stability for CO2 splitting in 100 h. This work demonstrates that rutile-type CTO-based cathodes are promising to provide an efficient and candidate oxide cathode for the electrolysis of CO2.

Enhanced humidity sensing properties of Ta2O5 and ITO doped rutile-TiO2 porous ceramics.

In this study, we investigated the humidity sensing properties of TiO2-based ceramics doped with tantalum pentoxide (Ta2O5) and indium tin oxide (ITO). Pure TiO2, 1%Ta-doped TiO2 (1%TTO), 1%ITO-doped TiO2 (1%ISTO), and 1%(Ta2O5 + ITO) co-doped TiO2 (1%ISTTO) ceramic samples were obtained by sintering at 1200 °C for 3 h. The rutile phase was observed in all samples. The lattice parameters of the single and co-doped samples were larger than those of pure TiO2, confirming the substitution of dopants. Porosity was observed in all ceramics. The mean grain sizes of all doped samples were significantly reduced compared to undoped TiO2. A homogeneous element dispersion was observed in the 1%TTO and 1%ISTTO ceramics, while segregation particles of related In-rich elements was observed in the 1%ISTO ceramic. Giant dielectric properties were not achieved in any samples due to the porosity. Nevertheless, excluding the undoped TiO2, the dielectric properties of all porous ceramics varied significantly with changes in humidity. The 1%ISTTO ceramic demonstrated superior humidity sensing properties, including a low maximum hysteresis error of 3.6% at 102 Hz. In contrast, the 1% TTO and 1% ISTO ceramics showed higher maximum hysteresis errors of 7.2% and 19.8%, respectively. Notably, the response and recovery times were 7.05 ± 0.18 and 2.48 ± 0.39 min, respectively, with good repeatability. This improvement is likely due to the synergistic effect of oxygen vacancies and Ta Ti · defects on the surface, enhancing the humidity sensing properties of the 1% ISTTO ceramic, coupled with its optimal microstructure due to its lowest porosity and grain size.

Modeling adsorption reactions of ammonium perchlorate on rutile and anatase surfaces.

In this work, the effects of two TiO2 polymorphs on the decomposition of ammonium perchlorate (NH4ClO4) were studied experimentally and theoretically. The interactions between AP and various surfaces of TiO2 were modeled using density functional theory (DFT) calculations. Specifically, the adsorption of AP on three rutile surfaces (1 1 0), (1 0 0), and (0 0 1), as well as two anatase surfaces (1 0 1), and (0 0 1) were modeled using cluster models, along with the decomposition of adsorbed AP into small molecules. The optimized complexes of the AP molecule on TiO2 surfaces were very stable, indicating strong covalent and hydrogen bonding interactions, leading to highly energetic adsorption reactions. The calculated energy of adsorption (ΔEads) ranged from -120.23 to -301.98 kJ/mol, with highly exergonic calculated Gibbs free energy (ΔGads) of reaction, and highly exothermic enthalpy of reaction (ΔHads). The decomposition of adsorbed AP was also found to have very negative ΔEdec values between -199.08 and -380.73 kJ/mol. The values of ΔGdec and ΔHdec reveal exergonic and exothermic reactions. The adsorption of AP on TiO2 surfaces anticipates the heat release of decomposition, in agreement with experimental results. The most common anatase surface, (1 0 1), was predicted to be more reactive for AP decomposition than the most stable rutile surface, (1 1 0), which was confirmed by experiments. DFT calculations show the mechanism for activation of the two TiO2 polymorphs is entropy driven.

Dual-pathway charge transfer mechanism of anatase/rutile TiO2-Ag3PO4 hollow photocatalyst promotes efficient degradation of pesticides.

Exploring high-performance photocatalysts still remains a big challenge due to poor charge separation efficiency. Herein, we prepare a novel anatase/rutile TiO2-Ag3PO4 hollow photocatalyst (A/R-TiO2-Ag3PO4) for addressing this challenge. Microstructural characterization and photoelectric measurements confirm that the synergy of hollow structure and dual-heterojunction can provide abundant active sites and boost efficient charge separation through dual-pathway charge transfer mechanism. The A/R-TiO2-Ag3PO4 photocatalyst exhibits the highest photocurrent density (15.25 µA cm-2), which is 8.4 and 5.2 times than that of A-TiO2-Ag3PO4 (1.82 µA cm-2) and P25-Ag3PO4 (2.93 µA cm-2), respectively. Photo-degradation experiment shows that A/R-TiO2-Ag3PO4 presents a high degradation percentage (98.7 %) of thiamethoxam (THX) within 30 min, which is 1.45 and 1.23 times than that of A-TiO2-Ag3PO4 (68.1 %) and P25-Ag3PO4 (80.7 %), respectively. Furthermore, the degradation percentage of THX by A/R-TiO2-Ag3PO4 is as high as 96.4 % after seven successive cycles, indicating excellent cycling stability. Therefore, this work provides a new insight into exploring other high-performance photocatalysts by combining hollow structure and dual-heterojunction.

Crystallographic Pathways to Tailoring Metal-Insulator Transition through Oxygen Transport in VO2.

The metal-insulator (MI) transition of vanadium dioxide (VO2) is effectively modulated by oxygen vacancies, which decrease the transition temperature and insulating resistance. Oxygen vacancies in thin films can be driven by oxygen transport using electrochemical potential. This study delves into the role of crystallographic channels in VO2 in facilitating oxygen transport and the subsequent tuning of electrical properties. A model system is designed with two types of VO2 thin films: (100)- and (001)-oriented, where channels align parallel and perpendicular to the surface, respectively. Growing an oxygen-deficient TiO2 layer on these VO2 films prompted oxygen transport from VO2 to TiO2. Notably, in (001)-VO2 film, where oxygen ions move along the open channels, the oxygen migration deepens the depleted region beyond that in (100)-VO2, leading to more pronounced changes in metal-insulator transition behaviors. The findings emphasize the importance of understanding the intrinsic crystal structure, such as channel pathways, in controlling ionic defects and customizing electrical properties for applications.

TiO2 Nanoparticles with Adjustable Phase Composition Prepared by an Inverse Microemulsion Method: Physicochemical Characterization and Photocatalytic Properties.

Titania nanoparticles (NPs) find wide application in photocatalysis, photovoltaics, gas sensing, lithium batteries, etc. One of the most important synthetic challenges is maintaining control over the polymorph composition of the prepared nanomaterial. In the present work, TiO2 NPs corresponding to anatase, rutile, or an anatase/rutile/brookite mixture were obtained at 80 °C by an inverse microemulsion method in a ternary system of water/cetyltrimethylammonium bromide/1-hexanol in a weight ratio of 17:28:55. The only synthesis variables were the preparation of the aqueous component and the nature of the Ti precursor (Ti(IV) ethoxide, isopropoxide, butoxide, or chloride). The materials were characterized with X-ray diffraction, scanning/transmission electron microscopy, N2 adsorption-desorption isotherms, FTIR and Raman vibrational spectroscopies, and diffuse reflectance spectroscopy. The synthesis products differed significantly not only in phase composition, but also in crystallinity, textural properties, and adsorption properties towards water. All TiO2 NPs were active in the photocatalytic decomposition of rhodamine B, a model dye pollutant of wastewater streams. The mixed-phase anatase/rutile/brookite nanopowders obtained from alkoxy precursors showed the best photocatalytic performance, comparable to or better than the P25 reference. The exceptionally high photoactivity was attributed to the advantageous electronic effects known to accompany multiphase titania composition, namely high specific surface area and strong surface hydration. Among the single-phase materials, anatase samples showed better photoactivity than rutile ones, and this effect was associated, primarily, with the much higher specific surface area of anatase photocatalysts.

Variations in orientation relationships between rutile inclusions and garnet host relate to magmatic growth zoning.

Rutile inclusions in almandine-spessartine garnet from a peraluminous pegmatoid from the Moldanubian zone (Bohemian Massif, AT) show distinct changes in aspect ratio, shape preferred orientations (SPO) and crystallographic orientation relationships (COR) along the transition between microstructurally different growth zones in the garnet core and rim. For identification of the COR characteristics we pool specific CORs based on their common axial relationship into three COR groups: Group 103R/111G, Group 001R/111G and Group 001R/100G. The rutile inclusions in the garnet core domains are elongated along the four Grt ⟨ 111 ⟩ directions and are dominated by COR Group 103R/111G. The garnet rim zone additionally contains rutile needles elongated along Grt ⟨ 100 ⟩ . Here, Group 001R/111G and 001R/100G are more abundant than in the garnet core. Needle-shaped rutile in the rim shows a systematic correlation between SPOs and CORs as needles elongated parallel to Grt ⟨ 111 ⟩ are dominated by Group 103R/111G and 001R/111G, whereas those needles elongated parallel to Grt ⟨ 100 ⟩ exclusively pertain to CORs of 001R/100G. Furthermore, the frequency of each particular SPO in the garnet rim clearly depends on the local growth direction of the particular Grt{112} sector. Facet-specific variations in rutile SPO frequencies in different sectors and growth zones of garnet were observed even between equivalent directions, indicating that the microstructures and textures of rutile inclusions reflect varying parameters of garnet growth. The characteristic differences in COR groups of different garnet growth zones are referred to compositional changes in the bulk melt or compositional boundary layer, associated with magmatic fractional crystallisation. Supplementary Information: The online version contains supplementary material available at 10.1007/s00410-024-02146-9.

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.

Analysis of Ag-DP25/PET plasmonic nano-composites as a visible-light photocatalyst for wastewater treatment: Experimental/theoretical studies, and the DFT-MB degradation mechanism.

The development of polymeric-composites Agx%DP25-PET (x = 0,1,2,3) may significantly boost the potential application of Agx%DP25 (x = 0,1,2,3) photocatalytic powders. Producing large-scale nano-composites with hybrid-surfaces, that are also flexible materials and easy to employ in a variety of environments. A set of photocatalytic nan-composites embedded with the polymeric binder poly (acrylonitrile-co-butadiene)-dicarboxy terminated (C7H9N) were performed and evaluated for wastewater treatment applications. The results reveal that the flexible polymeric composites (Agx%DP25-PET, x = 0,1,2,3) have photocatalytic activity in aqua media to degrade methylene blue (MB) under visible-light. The addition of C7H9N to immobilize photocatalytic powders on the PET surface reduces photo-generated electron-hole recombination. The materials were characterized by HR-TEM, SEM/EDX, XRD, FT-IR, UV-Vis DRS and PL. The Agx%DP25-PET (x = 0,1,2,3) photocatalytic reactions exhibited productive discoloration/degradation rates, in both aerobic (AE) and anaerobic (AN) environments. The superior photodegradation of Ag2%DP25-PET was attributed to a combination of two effects: LSPR (localized surface plasmon resonance) and Ag-TiO2/environment affinities. The findings of molecular dynamics (MD) simulation and Fukui Function (FF) based on density functional theory (DFT) provide significant insight into the photocatalytic requirements for MB discoloration/degradation. The experimental/theoretical analysis aimed to offer an in-depth understanding of medium/surface interactions on decorated TiO2 materials, as well as how these interactions affect overall degradation behavior.

Study of rutile TiO2(110) single crystal by transient absorption spectroscopy in the presence of Ce4+cations in aqueous environment. Implication on water splitting.

Ce4+cations are commonly used as electron acceptors during the water oxidation to O2reaction over Ir- and Ru-based catalysts. They can also be reduced to Ce3+cations by excited electrons from the conduction band of an oxide semiconductor with a suitable energy level. In this work, we have studied their interaction with a rutile TiO2(110) single crystal upon band gap excitation by femtosecond transient absorption spectroscopy (TAS) in solution in the 350-900 nm range and up to 3.5 ns. Unlike excitation in the presence of water alone the addition of Ce4+resulted in a clear ground-state bleaching (GSB) signal at the band gap energy of TiO2(ca. 400 nm) with a time constantt= 4-5 ps. This indicated that the Ce4+cations presence has quenched the e-h recombination rate when compared to water alone. In addition to GSB, two positive signals are observed and are attributed to trapped holes (in the visible region, 450-550 nm) and trapped electrons in the IR region (>700 nm). Contrary to expectation, the lifetime of the positive signal between 450 and 550 nm decreased with increasing concentrations of Ce4+. We attribute the decrease in the lifetime of this signal to electrostatic repulsion between Ce4+at the surface of TiO2(110) and positively charged trapped holes. It was also found that at the very short time scale (<2-3 ps) the fast decaying TAS signal of excited electrons in the conduction band is suppressed because of the presence of Ce4+cations. Results point out that the presence of Ce4+cations increases the residence time (mobility) of excited electrons and holes at the conduction band and valence band energy levels (instead of being trapped). This might provide further explanations for the enhanced reaction rate of water oxidation to O2in the presence of Ce4+cations.

Direct Photocatalytic Methane Oxidation to Formaldehyde by N Doping Co-Decorated Mixed Crystal TiO2.

In this paper, N-doped TiO2 mixed crystals are prepared via direct calcination of TiN for highly selective oxidation of CH4 to HCHO at room temperature. The structures of the prepared TiO2 samples are characterized to be N-doped TiO2 of anatase and rutile mixed crystals. The crystal structures of TiO2 samples are determined by XRD spectra and Raman spectra, while N doping is demonstrated by TEM mapping, ONH inorganic element analysis, and high-resolution XPS results. Significantly, the production rate of HCHO is as high as 23.5 mmol·g-1·h-1 with a selectivity over 90%. Mechanism studies reveal that H2O is the main oxygen source and acts through the formation of ·OH. DFT calculations indicate that the construction of a mixed crystal structure and N-doping modification mainly act by increasing the adsorption capacity of H2O. An efficient photocatalyst was prepared by us to convert CH4 to HCHO with high yield and selectivity, greatly promoting the development of the photocatalytic CH4 conversion study.

A systematic DFT study of structure and electronic properties of titanium dioxide.

DFT functionals are of paramount importance for an accurate electronic and structural description of transition metal systems. In this work, a systematic analysis using some well-known and commonly used DFT functionals is performed. A comparison of the structural and energetic parameters calculated with the available experimental data is made in order to find the adequate functional for an accurate description of the TiO2 bulk and surface of both anatase and rutile structures. In the absence of experimental data on the surface energy, the theoretical predictions obtained using the high-accuracy HSE06 functional were used as a reference to compare against the surface energy values calculated with the other DFT functionals. A clear improvement in the electronic description of both anatase and rutile was observed by introducing the Hubbard U correction term to PBE, PW91, and OptPBE functionals. The OptPBE-U4 functional was found to offer a good compromise between accurately describing the structural and electronic properties of titania.

Grain Boundary Defect Engineering in Rutile Iridium Oxide Boosts Efficient and Stable Acidic Water Oxidation.

Proton exchange membrane water electrolysis (PEMWE) is considered a promising technology for coupling with renewable energy sources to achieve clean hydrogen production. However, constrained by the sluggish kinetics of the anodic oxygen evolution reaction (OER) and the acidic abominable environment render the grand challenges in developing the active and stable OER electrocatalyst, leading to low efficiency of PEMWE. Herein, we develop the rutile-type IrO2 nanoparticles with abundant grain boundaries and the continuous nanostructure through the joule heating and sacrificial template method. The optimal candidate (350-IrO2) demonstrates remarkable electrocatalytic activity and stability during the OER, presenting a promising advancement for efficient PEMWE. DFT calculations verified that grain boundaries can modulate the electronic structure of Ir sites and optimize the adsorption of oxygen intermediates, resulting in the accelerated kinetics. 350-IrO2 affords a rapid OER process with 20 times higher mass activity (0.61 A mgIr -1) than the commercial IrO2 at 1.50 V vs. RHE. Benefiting from the reduced overpotential and the preservation of the stable rutile structure, 350-IrO2 exhibits the stability of 200 h test at 10 mA cm-2 with only trace decay of 11.8 mV. Moreover, the assembled PEMWE with anode 350-IrO2 catalyst outputs the current density up to 2 A cm-2 with only 1.84 V applied voltage, long-term operation for 100 h without obvious performance degradation at 1 A cm-2.

Designing a highly near infrared-reflective black nanoparticles for autonomous driving based on the refractive index and principle.

HYPOTHESIS: The development of highly NIR reflective black single-shell hollow nanoparticles (BSS-HNPs) can overcome the Light Detection and Ranging (LiDAR) sensor limitations of dark-tone materials. The crystalline phase of TiO2 and the refractive index can be controlled by calcination temperature. The formation of hollow structure and the refractive index is expected to simultaneously increase the light reflection and LiDAR detectability. EXPERIMENTS: The BSS-HNPs are synthesized using the sol-gel method, calcination, NaBH4 reduction, and etching to form a hollow structure with true blackness. The computational bandgap calculation is conducted to determine the bandgap energy (Eg) of the white and black TiO2 with different crystalline structures. The blackness of the as-synthesized materials is determined by the Commission on Illumination (CIE) L*a*b* color system. FINDINGS: The hydrophilic nature of BSS-HNPs enables the formulation of hydrophilic paints, allowing the mono-layer coating. With the synergistic effects of hollow structure and the refractive index, BSS-HNPs manifested superb NIR reflectance at LiDAR detection wavelengths. The high detectability, blackness, and hollow structure of BSS-HNPs can expand the variety of LiDAR-detectable dark-tone materials.

Functionalization of the NiTi Shape Memory Alloy Surface through Innovative Hydroxyapatite/Ag-TiO2 Hybrid Coatings.

The objective of this research was to develop a surface modification for the NiTi shape memory alloy, thereby enabling its long-term application in implant medicine. This was achieved through the creation of innovative multifunctional hybrid layers comprising a nanometric molecular system of silver-rutile (Ag-TiO2), known for its antibacterial properties, in conjunction with bioactive submicro- and nanosized hydroxyapatite (HAp). The multifunctional, continuous, crack-free coatings were produced using the electrophoretic deposition method (EPD) at 20 V/1 min. Structural and morphological analyses through Raman spectrometry and scanning electron microscopy (SEM) provided comprehensive insights into the obtained coating. The silver within the layer existed in the form of nanometric silver carbonates (Ag2CO3) and metallic nanosilver. Based on DTA/TG results, dilatometric measurements, and high-temperature microscopy, the heat treatment temperature for the deposited layers was set at 800 °C for 2 h. The procedures applied resulted in the creation of a new generation of materials with a distinct structure compared with the initial nanopowders. The resulting composite layer, measuring 2 µm in thickness, comprised hydroxyapatite (HAp), apatite carbonate (CHAp), metallic silver, silver oxides, Ag@C, and rutile exhibiting a defective structure. This structural characteristic contributes significantly to its heightened activity, influencing both bioactivity and biocompatibility properties.

Facet-Dependent Interfacial Charge Transfer between T-Phase VS2 Nanoflakes and Rutile TiO2 Single Crystals.

The hybridizations of two-dimensional (2D) metallic materials with semiconducting transition metal oxides (TMOs) register attractive heterojunctions, which can find various applications in photostimulated circumstances. In this work, we developed an ambient-pressure chemical vapor deposition method to directly grow T-VS2 on atomically smooth rutile TiO2 single crystals with different terminations and thus successfully constructed a heterojunction model of VS2/TiO2 with a well-defined clean interface. Detailed measurements with Kelvin probe force microscopy revealed the facet-dependent charge transfer occurring at the VS2/TiO2 interfaces, seeing variations not only in the amount and direction of the transferred electrons but also in the photoinduced surface potential changes and the dynamics of photogenerated charge carriers under ultraviolet irradiation. Interestingly, ultrathin T-VS2 was found with considerable magnetism at room temperature, disregarding the charge exchange with the TiO2 substrates. These results may bring deep insights into the photoinspired functionalities of the hybridized system combining metallic transition metal dichalcogenides and TMO materials.

Prediction of Feasibility of Polaronic OER on (110) Surface of Rutile TiO2.

The polaronic effects at the atomic level hold paramount significance for advancing the efficacy of transition metal oxides in applications pertinent to renewable energy. The lattice-distortion mediated localization of photoexcited carriers in the form of polarons plays a pivotal role in the photocatalysis. This investigation focuses on rutile TiO2, an important material extensively explored for solar energy conversion in artificial photosynthesis, specifically targeting the generation of green H2 through photoelectrochemical (PEC) H2O splitting. By employing Hubbard-U corrected and hybrid density functional theory (DFT) methods, we systematically probe the polaronic effects in the catalysis of oxygen evolution reaction (OER) on the (110) surface of rutile TiO2. Theoretical understanding of polarons within the surface, coupled with simulations of OER at distinct titanium (Ti) and oxygen (O) active sites, reveals diverse polaron formation energies within the lattice sites with strong preference for bulk and surface bridge (Ob) oxygen sites. Moreover, we provide the evidence for the facilitative role of polarons in OER. We find that hole polarons situated at the equatorial oxygen sites near the Ti-active site, along with bridge site hole polarons distal from the Ob active site yield a small reduction in OER overpotential by ~0.06 eV and ~0.12 eV, respectively. However, subsurface, equatorial, and bridge site hole polarons significantly reduce the Ti-active site OER overpotential by ~0.4 eV through the peroxo-type oxygen pathway. We also observe that the presence of hole polarons stabilizes the *OH, *O, and *OOH intermediate species compared to the scenario without hole polarons. Overall, this study provides a detailed mechanistic insight into polaron-mediated OER, offering a promising avenue for improving the catalytic activity of transition metal oxide-based photocatalysts catering to renewable energy requisites.

ASCOT: A web tool for the digital construction of energy minimized Ag, CuO, TiO2 spherical nanoparticles and calculation of their atomistic descriptors.

ASCOT (an acronym derived from Ag-Silver, Copper Oxide, Titanium Oxide) is a user-friendly web tool for digital construction of electrically neutral, energy-minimized spherical nanoparticles (NPs) of Ag, CuO, and TiO2 (both Anatase and Rutile forms) in vacuum, integrated into the Enalos Cloud Platform (https://www.enaloscloud.novamechanics.com/sabydoma/ascot/). ASCOT calculates critical atomistic descriptors such as average potential energy per atom, average coordination number, common neighbour parameter (used for structural classification in simulations of crystalline phases), and hexatic order parameter (which measures how closely the local environment around a particle resembles perfect hexatic symmetry) for both core (over 4 Å from the surface) and shell (within 4 Å of the surface) regions of the NPs. These atomistic descriptors assist in predicting the most stable NP size based on lowest per atom energy and serve as inputs for developing machine learning models to predict the toxicity of these nanomaterials. ASCOT's automated backend requires minimal user input in order to construct the digital NPs: inputs needed are the material type (Ag, CuO, TiO2-Anatase, TiO2-Rutile), target diameter, a Force-Field from a pre-validated list, and the energy minimization parameters, with the tool providing a set of default values for novice users.