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At least 163 records · Page 9

Titanium-in-Quartz Geothermometry of Impactites and Peak-Ring Lithologies from the Chicxulub Impact Crater

Since its development by Wark and Watson (2006), the Ti-in-quartz geothermometer (TitaniQ) has been continuously refined and applied to a variety of lithologies from different crustal settings. Assuming quartz crystallized and incorporated Ti under equilibrium conditions and providing TiO2 activity (alpha (sub TiO2)) is reasonably constrained, crystallization temperatures at typical crustal pressures can be calculated. In turn, when crystallization temperatures are independently constrained, Ti-in-quartz can be used as a geobarometer. Here we explore the application of this technique to impact lithologies. Quartz is ubiquitous in terrestrial impact structures in upper crustal settings and can also form as a post-impact hydrothermal mineral. Together with other geothermometers, such as Ti-in-zircon, Ti-in-quartz can potentially help constrain the temperature-pressure conditions during the formation of the pre-impact target rock at terrestrial impact structures, as well as impact-produced and hydrothermally-altered lithologies. This work presents the first systematic Ti-in-quartz study of impactites and granitoid target rocks from the approximately180-kilometer-diameter, end-Cretaceous Chicxulub crater on the Yucatan Peninsula, Mexico, thereby placing new constraints on the emplacement of felsic plutons within the Maya Block in the Paleozoic, impact melt crystallization at approximately 66 Ma (million years ago), and post-impact hydrothermal overprint inside the Chicxulub crater.

Schmieder, Martin↗

Durability of YSZ Coated Ti2AlC in 1300 °C Mach 0.3 Burner Rig Tests

A thermal barrier coating system survived burner rig testing at 1300 °C for 500 h. A 160 µm thick yttria stabilized zirconia (YSZ) coating was applied to a Ti2AlC MAX phase bar sample by plasma spray physical vapor deposition (PS-PVD) and tested face-on in an atmospheric Mach 0.3 jet fuel burner, using 5-h thermal cycles. No thermal barrier coating (TBC) spallation or recession was observed, only a 2.4 mg/cm2 mass gain. The modest weight gain precluded severe volatility losses under high velocity burner conditions. The coating surface exhibited colonies of (111)flourite fiber-textured columns separated by craze patterns, with no visible moisture attack. The metastable tetragonal t' YSZ phase was obtained initially, transitioning to equilibrium teq and cubic YSZ, but with little detrimental monoclinic. The thickness of the alumina TGO was ~21 to 23 μm under the heated YSZ face and ~13 to 15 μm on the uncoated, cooler backside. The backside exhibited removal of initial transient TiO2 nodules and partial etching of the underlying Al2O3 scale by volatile hydroxides formed in high temperature, high velocity water vapor. Aerodynamic forces produced some bending of the cantilevered sample via creep. The test indicated exceptional stability of YSZ coatings on Ti2AlC under turbine conditions, with thermal expansion matching playing a key role. The purpose of this study was to demonstrate long term durability of YSZ/MAX phase system in aggressive high temperature burner rig testing. MAX phases have been keenly studied because of their unique crystal structure and intriguing properties (Refs. 1 and 2). Having Mn+1(Al,Si)(C,N)n general composition, they are defined as ceramics, but possess unusual desirable attributes such as high conductivity, thermal shock resistance, easy machinability, and deformation tolerance. The mechanical properties derive from weak M-(Al,Si) bonding in the basal plane that leads to sliding and kinking in preference to catastrophic crack growth. Like most ceramics they are phase stable at high temperatures, generally up to 1500 °C. High temperature oxidation resistance is excellent for alumina-forming Ti3AlC2, Ti2AlC, and Cr2AlC, as reviewed by Tallman, et al. (Ref. 3). Compatibility with α-Al2O3 scales is further enhanced in cyclic exposures by a close matching of thermal expansion coefficients, (Ref. 4) i.e., (~9.3, 10.2, 11.3×10–6/K for Al2O3, Ti2AlC, and YSZ, to be discussed). Turbine environments generally contain 10 percent water vapor in the combustion gases, therefore moisture effects can be a concern for some materials (Ref. 5). Furnace tests of MAX phases in high temperature steam generally showed little effect on Al2O3 scale growth (Ref. 6). However, high velocity and high pressure gas can influence scale losses by the formation of volatile reaction products, such as TiO(OH)2 and Al(OH)3 (Refs. 7 to 10). This phenomenon had been discussed for 1100 to 1300 °C high pressure burner rig tests of Ti2AlC (Ref. 11). A single cubic growth rate parameter kcubic was measurably lower than comparable furnace TGA data, but it could be matched reasonably well if corrected for a slight volatility term. In general, a two-parameter cubic-linear growth-volatility law was believed to apply. Corresponding scale volatility loss rates, directly measured at 1300 °C on a pre-oxidized sample, were moderate (0.012 mg/cm2/h) and largely attributed to removal of the initial TiO2 transient scale. A related CH4 burner study of high purity Cr2AlC MAX phase demonstrated 1200 °C durability after 500 rapid (5 min. heat and 2 min. cool) thermal shock cycling (29 h hot time) (Ref. 12). Heating and cooling rates were ~1000 and 500 °C per minute, with a gas velocity of 5 m/s, producing a 75 °C/mm gradient. A 7 μm Al2O3 surface scale and a 13 μm Cr7C3 depletion zone formed with no signs of failure. No evidence of scale volatility was evident, although weight change was not provided, the velocity was moderate, and the total hot time was not extensive. The same high gradient BRT was used to produce 1400 °C surface temperatures for a YSZ/Cr2AlC/IN738 system in the first study of MAX phases used as bond coats for thermal barrier coatings (TBC) (Ref. 25). Here TBC failure was reported after 745 cycles, with only a 1.5 μm Al2O3 scale entrained within a porous, Cr7C3 bondcoat depletion phase. YSZ thermal barrier coatings have been considered to be a compatible complement to Al-MAX phases because of thermal expansion matching and extremely low volatility in water vapor. Initial studies showed superior oxidative stability up to 1300 °C, for long times (at least 500 h) for Ti2AlC substrates and less (268 h) for Cr2AlC, while withstanding large alumina TGO scale thickness (~35 to 40 μm) (Refs. 13 and 14). By comparison, typical superalloy systems can only survive 1150 °C maximum interface temperatures for extended periods, with a maximum sustained TGO below 10 μm (Ref. 15). High temperature SiC based systems are known to form slow-growing SiO2 scales. But these are subject to rate enhancement and volatile Si(OH)4 products in the presence of water vapor, as described comprehensively by Opila, et al. (Refs. 5, 16 to 19). Net weight losses are generally observed in high velocity, high pressure burner rig studies (e.g., 0.084 mg/cm2/h at 1300 °C) (Ref. 20). Furthermore, the loss rates have been shown from chemical physics to scale with v1/2 and pH2O 2 (Ref. 16). Low activity, moisture-resistant environmental barrier coatings (EBC), such as rare earth silicates, are needed to prevent substrate recession under turbine conditions (Refs. 21 to 23).

Smialek, James L.↗

Calcined Polyethyleneimine-Coated Optical Fibers for Distributed pH Monitoring at High Pressures and Temperatures

In the oil and gas, CO2 sequestration, H2 subsurface storage, and geothermal energy sectors, subsurface pH measurements are critical for monitoring the geochemical conditions and estimating potential corrosion rates of wellbore systems. Real-time pH measurements in these conditions are vital for detecting and predicting corrosion deterioration of wellbore components that may jeopardize the safety and continued operation of wellbore systems. Previous tests using metal oxide-based coatings (TiO2) provided strong responses at elevated temperatures and moderate pressure stability but provided poor differentiation between acidic and alkaline solutions. Building off the pH responsiveness of the TiO2 surface and known pH sensitivity of amine-based polymers, a coating based on the secondary amine polymer polyethyleneimine (PEI) was developed. As the polymer itself is highly water soluble and easily removed by aqueous solutions, the sensor coating was treated with a high temperature (500 °C) calcination procedure in air to convert it into a more stable oxidized coating capable of withstanding hot aqueous solutions without dissolving while retaining linear pH sensitivity from pH values between 2 and 11. The sensor performance was measured using optical transmission measurements in solutions of various pHs and using optical backscatter reflectometry for distributed pH sensing demonstration in wellbore-relevant pressures (up to 1,000 psi) and temperatures (80 °C).

Shumski, Alexander↗

Insights into the Reactivity of Brookite TiO 2 Nanorods in Liquid Water from Ab Initio Molecular Dynamics Simulations

Brookite TiO 2 , a rare natural polymorph of TiO 2 , has been reported to be an excellent photocatalyst for the production of hydrogen from water and aqueous alcohol solutions, especially when it is reduced and synthesized in the form of nanorods. Here, we investigate the reactivity of stoichiometric and reduced brookite nanorods in liquid water using ab initio molecular dynamics and hybrid density functional theory calculations. Our simulations show a much higher water dissociation fraction on reduced nanorods than on stoichiometric ones, with an accumulation of the resulting bridging hydroxyls (O br H) and terminal hydroxyls (Ti –OH) on different facets of the nanorod. ObrH groups accumulate preferentially on low-energy (210) facets, where they are stabilized by adjacent reduced Ti (Ti 3+ ) sites, while Ti –OH groups prefer to form at the four-fold coordinated Ti atoms on high-energy (010) facets. This hydroxylation pattern also favors the spatial localization of excited holes on the (010) facets. This coupling between water-induced surface chemistry and charge separation underpins the enhanced photocatalytic activity of brookite nanorods, providing useful information for the design of more efficient TiO2-based nanostructures for solar-driven hydrogen evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pt Nanoparticle Disintegration at Oxide Interfaces Enhances CO Oxidation Catalysis

Understanding how supported metal nanoparticles dynamically evolve under reaction conditions is critical for controlling their catalytic function. Here, the mechanism behind the dynamic disintegration of Pt nanoparticles (NPs) supported on CeOx-TiO2 (CT) during CO oxidation is elucidated, leading to the formation of single atoms (SAs) and/or sub-nanometer clusters. Density functional theory (DFT) calculations reveal that strong Pt-CO interactions weaken Pt─Pt cohesion, while electronic coupling between Pt and Ce ions stabilizes Pt-CO* intermediates at the oxide interface. Surface oxygen vacancies kinetically trap Pt-CO*, but the vacancies are replenished under oxygen-rich conditions, enabling Pt-CO* surface diffusion and subsequent structural reorganization. In situ spectroscopic analyses confirm the oxygen-driven transformation of Pt NPs, correlating with a threefold increase in mass-specific activity at 150 °C. These findings demonstrate that interfacial oxygen dynamics and metal-support interactions can be leveraged to induce nanoparticle disintegration and optimize catalytic performance, highlighting the catalytic potential of interface-engineered Pt nanostructures.

CO oxidation↗

Efficient Synthetic Natural Gas Production from Direct Air Capture Using Titania-Based Dual Function Materials

Converting atmospheric CO2 into methane offers a compelling pathway to store intermittent renewable electricity and enhance energy security using existing natural gas infrastructure. However, current CO2 utilization approaches remain energy- and capital-intensive, largely due to the need for separate capture, purification, and conversion steps. Integrating CO2 capture with catalytic methanation represents a transformative strategy for process intensification on both the unit operation and molecular levels. We report a series of Ru-Na/TiO2 dual function materials (DFMs) for a reactive carbon capture (RCC) process consisting of simulated direct air capture and subsequent CO2 methanation (DACM). Superior methane desorption purity was observed on TiO2-based DFMs (>94 %) relative to state-of-the-art Al2O3-supported DFMs (77 %). Modifying the process to begin CO2 adsorption immediately following the methanation stage, rather than beginning adsorption near ambient temperature, resulted in >97 % methane desorption purity, suitable for injection into the natural gas pipeline without additional CO2 separation steps.

organic↗

Sol-gel derived silicate-phosphate glass SiO 2 –P 2 O 5 –CaO–TiO 2 : The effect of titanium isopropoxide on porosity and thermomechanical stability

Despite of several decades lasting extensive research of bioactive and bioresorbable glasses the systematic parametrization and determination of the key factors affecting porosity and thermomechanical characteristics still remains challenging. Here, we present silica-phosphate glasses, with the composition 70SiO 2 - 20P 2 O 5 - (10-x)CaO-xTiO 2 (mol%; x = 0, 2.5, 5, and 7.5), prepared by sol -gel method and reinforced by titanium dioxide via titanium isopropoxide (TTIP) incorporation which demonstrated tunable variation of porosity from micro-to macro -region and superb mechanical integrity during the calcination process. The presence of 7.5 mol% TiO 2 promotes dimensional stability up to 1000°C as investigated by thermomechanical analysis. The XRD showed the dominant presence of silicon phosphate [Si(P 2 O 7 )], titanium phosphate [Ti(P 2 O 7 )] and calcium phosphates [β-Ca(P 2 O 6 ) and γ- Ca 2 (P 2 O 7 )]. The effect of TiO 2 doping on the multiscale morphology and porosity was investigated by means of SEM, MIP, μCT, N 2 adsorption and USAXS/SAXS. Increasing TiO 2 content leads to the formation of open porosity up to 70vol% and drives the formation of a refined interconnected macroporosity of 2-30 μm. In contrast, mesoporosity with a dominance of 3-6nm pores decreases in all samples with increasing TiO 2 content. USAXS/SAXS revealed an increase in primary particle size with increasing TiO 2 content which is in good agreement with the nitrogen physisorption analysis showing that microporosity decreases with increasing TiO2 content.

36 MATERIALS SCIENCE↗

Local Electric Field Effects on Water Dissociation in Bipolar Membranes Studied Using Core–Shell Catalysts

The local electric field strength is thought to affect the rate of water dissociation (WD) in bipolar membranes (BPMs) at the catalyst–nanoparticle surfaces. Here, we study core–shell nanoparticles, where the core is metallic, semiconducting, or insulating, to understand this effect. The nanoparticle cores were coated with a WD catalyst layer (TiO2 or HfO2) via atomic layer deposition (ALD), and the morphology was imaged with transmission electron microscopy. Irrespective of the core material, these core–shell catalysts displayed comparable WD overpotentials at optimal mass loading, despite the hypothesized differences in the electric field strength across the catalyst particle suggested by continuum electrostatic simulations. Substantial atomic interdiffusion between the core and shell was ruled out by X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and diffuse reflectance optical measurements. However, the optimal mass loading of catalyst was roughly 1 order of magnitude higher for the conductive and high dielectric core materials than for the low dielectric insulating cores. These findings are consistent with the hypothesis that electric field screening within the core material focuses the electric field drop between particles such that larger film thicknesses can be tolerated. Collectively, these data support the idea that it is the local electric field at the molecular level that controls proton-transfer rates and that the metal core/dielectric-shell constructs introduced here modulate that field. Further materials and synthetic design may enable optimization of the electric field strength across the proton-transfer trajectory at the material surface.

Sarma, Prasad V↗

Computational Insights into Phase Equilibria Between Wide-Gap Semiconductors and Contact Materials

Novel wide-band-gap semiconductors are needed for next-generation power electronics, but there is a gap between a promising material and a functional device. Finding stable (metal) contacts is one of the major challenges that is currently dealt with mainly via trial and error. Herein, we computationally investigate the thermochemistry and phase coexistence at the junction between three wide-gap semiconductors, ..beta..-Ga2O3, GeO2, and GaN, and possible contact materials. The pool of possible contacts includes 47 elemental metals and a set of 4 common, n-type transparent conducting oxides (ZnO, TiO2, SnO2, and In2O3). We use first-principles thermodynamics to model the Gibbs free energies of chemical reactions as a function of gas pressure (pO2/pN2) and equilibrium temperature. We deduce whether a semiconductor/contact interface will be stable at relevant conditions or a chemical reaction between them is to be expected, possibly influencing the long-term reliability and performance of devices. We generally find that most elemental metals tend to oxidize or nitridize and form various interface oxide/nitride layers. Exceptions include select late- and post-transition metals and, in the case of GaN, also the alkali metals, which are predicted to exhibit stable coexistence, although in many cases at relatively low gas partial pressures. Similar is true for the transparent conducting oxides, for which, in most cases, we predict a preference toward forming ternary oxides when in contact with ..beta..-Ga2O3 and GeO2. The only exception is SnO2, which we find to form stable contacts with both oxides. Finally, we show how the same approach can be used to predict gas partial pressure vs temperature phase diagrams to help direct synthesis of ternary compounds. We believe these results provide a valuable guidance in selecting contact materials to wide-gap semiconductors and suitable growth conditions.

contact materials↗

Fabrication of Catalytic Distillation Membranes with Atomic Layer Deposition

The integration of catalysts onto the surface of membranes enables simultaneous physical separation and catalytic transformation of constituents in a feed stream, facilitating improved contaminant removal and fouling mitigation. Distillation membranes are a particularly attractive platform for catalytic membranes because they reject nonvolatile species and exhibit exceptional resistance to oxidative and radical-driven degradation. However, imparting catalytic functionality onto hydrophobic, porous distillation membranes has proven challenging since the membranes used are chemically inert and difficult to modify. Furthermore, catalysts on the membrane surface can decrease hydrophobicity and increase the membrane’s susceptibility to pore wetting and failure. In this work, we create a catalytic distillation membrane by coating a polytetrafluoroethylene membrane surface with titanium dioxide (TiO 2 ) via plasma-assisted atomic layer deposition (ALD). By precisely tuning the ALD parameters, we demonstrate localized growth of TiO 2 near (within approximately 1 μm) the surface of polytetrafluoroethylene membranes, forming a catalytically active interface while preserving the underlying hydrophobic pore structure. Localized growth of TiO 2 is confirmed by electron microscopy and spectroscopy techniques, and membranes coated with 500 cycles of ALD show pressure tolerance up to 12.8 bar and higher than 95% salt rejection in pressure-driven distillation. Photocatalytic activity is demonstrated via the degradation of methylene blue dye under UV irradiation, where increasing TiO2 loading leads to an enhancement in dye degradation. These results establish a general strategy for integrating catalytic functionality into chemically inert, hydrophobic membranes without compromising distillation performance, providing a pathway toward multifunctional membranes that couple advanced oxidation with membrane separation for water treatment.

atomic layer deposition↗

Metal–Oxide Interface Sites Created Using Atomic Layer Deposition and Tested for CO Oxidation

The performance of catalysts made out of Pt supported on TiO 2 thin films grown on SBA-15 (a silica mesoporous material) by atomic layer deposition (ALD) was characterized systematically by combining in situ infrared absorption spectroscopy (IR) with other techniques including electron microscopy and adsorption−desorption isothermal measurements. The titania films in the resulting high-surface-area catalysts were evenly distributed throughout the inner surface of the SBA-15 mesopores, and their thickness could be controlled at a submonolayer level, with 3 to 4 TiO 2 ALD cycles needed for the complete coverage of the silica sites. The titania films could be deposited either before or after adding the metal (Pt), which was dispersed in the form of small nanoparticles (NPs) approximately 4−6 nm in diameter, in order to exert some control on the density and nature of the Pt/TiO 2 interface sites. One important lesson deriving from this work is that such an order of deposition leads to significantly different catalysts in spite of the fact that most of their structural properties are similar. If the Pt is deposited on the titania films, the resulting metal NPs are slightly smaller than those grown on silica and display CO adsorption sites with lower surface Pt coordination numbers. On the other hand, when TiO 2 is deposited on the Pt/SBA-15 starting material, some titania grows on the metal and partially blocks its surface while also creating new interface sites where CO binds more weakly and displays lower C−O stretching frequencies. In terms of catalytic performance, the results from in situ IR CO site titration and kinetic measurements combined suggest a mechanism where CO first adsorbs on Pt atop sites and then migrates to Pt/TiO 2 interface sites, where oxidation takes place. Both types of sites appear to be similar in all the catalysts tested, but catalytic performance could be optimized by tuning their surface densities. Maximum catalytic activity was obtained when the TiO2 films were deposited first and with TiO 2 coverages of at least half a monolayer, that is, after at least 2 ALD cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxygen Evolution on Mechanically Strained TiO2/NiTi: Implications of Compositional Heterogeneity at (Photo)Electrocatalytic Interfaces

The adsorption and activation energetics underpinning small molecule conversion on heterogeneous (photo)electrocatalysts are intrinsically tied to catalyst surface properties. Absent compositional characterization techniques with sufficient interface sensitivity, however, (photo)electrochemical performance can be misinterpreted in the context of bulk or near-surface material properties. Here we provide a fundamental investigation of the convoluting role of near-surface compositional heterogeneity in the interpretation of (photo)electrochemical alkaline oxygen evolution reaction (OER) activity, highlighting challenges in correlating composition measured by surface- and near-surface-sensitive probes. TiO2 thin films grown by air-annealing the superelastic alloy Nitinol (TiO2/NiTi) crack under tensile mechanical strain, increasing the number of electrochemically active Ni sites (Ni site density) that are probed via voltammetric features corresponding to Ni3+/Ni2+ redox events. (Photo)electrochemical OER kinetics trend with Ni site density, with overpotentials and Tafel slopes decreasing for Ni site densities < 1013 Ni/cm2geo and asymptotically approaching the performance of the base NiTi substrate for Ni site densities > 1013 Ni/cm2geo. Photoelectrochemical fill factors follow similar Ni site density dependent trends. When probing unstrained TiO2/NiTi, Ni site densities are two orders of magnitude higher when comparing near-surface-sensitive techniques (e.g., X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectrometry (TOF-SIMS), and scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDS)) to surface-sensitive electrochemical measurements. This result highlights the challenge of correlating kinetic performance with intrinsic surface properties of electrochemical interfaces in the presence of near-surface compositional heterogeneity. Further, it reinforces the importance of fundamental investigations of surfaces with well-controlled composition and structure and the need for physically grounded and self-consistent interpretation of multiple near-surface characterization techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Leveraging Hydration Forces for Size-Specific Nanoparticle Enrichment with a Redox-Responsive Silica-Binding Elastin-Like Polypeptide

Elastin-like polypeptides (ELPs) are low-complexity proteins that coacervate above a characteristic lower critical solution temperature (LCST). While the thermoresponsiveness of ELPs has been widely exploited in the biomedical and biomaterials fields, their ability to mediate nanoparticle assembly below their transition temperature remains largely unexplored. Here, we show that unmodified ELPs induce the reversible flocculation of silica nanoparticles (SiNPs) by forming backbone hydrogen bonds with surface silanols. Interparticle bridging is modulated by ELP length and concentration and by the presence of N- and C-terminal anchoring groups such as a cysteine residue and a Car9 silica-binding peptide. Using a redox-responsive fusion protein consisting of disulfide-bonded ELP domains terminated by Car9 segments, we stabilize 20 nm SiNPs under oxidizing conditions while triggering particle flocculation upon addition of reductant. We find that SiNP sedimentation under reducing conditions exhibits a sharp dependency on particle size that arises from the curvature-dependent structure of surface silanols. While the isolated silanols of SiNPs smaller than 30 nm are efficiently engaged by the ELP domains of Car9-anchored proteins, repulsion forces associated with the presence of a layer of molecular water together with increased electrostatic repulsion preclude efficient engagement of H-bonded silanols displayed on the surface of SiNPs larger than 60 nm. We harness these findings to selectively enrich SiNPs based on size and expand the concept to titania (TiO2) by demonstrating that rutile nanoparticles can be stabilized or sedimented with solid-binding ELPs by adjusting the solution pH to promote or discourage the formation of a hydration layer. These strategies should prove broadly useful for the separation of other oxides and their polymorphs and provide a tunable strategy for nanoparticle assembly and bioinspired colloidal design.

ELP↗

Electrospun Ti–Zr Oxide Heterostructures Enable Strongly Anchored Ultralow-Ir Anodes for Durable Acidic Oxygen Evolution

Proton-exchange-membrane water electrolysis (PEMWE) requires acidic oxygen-evolution-reaction (OER) anodes that combine high activity, high durability, and low Ir loading. Here, we report a Ti-Zr composite electrospun oxide (ESO) nanorod support that enables ultralow-Ir anodes for high-performance PEMWE. Zr-containing Ti oxide heterostructures stabilize anatase-rich TiO2, tune the local oxygen-coordination environment, and strengthen interfacial anchoring of IrOx under acidic anodic conditions. The electrospun nanorod network further creates an open, mechanically coherent catalyst layer that improves Ir utilization, ionomer penetration, and mass transport. At an anode loading of 0.2 mgIr cm-2, the optimized Ir/TiZr20-ESO anode delivers a PEMWE mass activity of 0.99 A mgIr-1 at 1.45 V, 28.3 and 43.0 times higher than commercial Ir black and commercial IrO2/TiO2, respectively. The same anode reaches 3.0 and 4.0 A cm-2 at 1.75 and 1.83 V, respectively, and sustains 2000 h operation at 2.0 A cm-2. Also, accelerated stress tests up to 525 hours over 31,500 cycles confirm promising long-term durability, with an insignificant performance decay of 0.4 μV per cycle. Density functional theory indicates that the Ti-Zr oxide heterostructure suppresses Ti demetallation and strengthens IrO2 interfacial binding, rationalizing the improved high-current-density stability.

25 ENERGY STORAGE↗

Ion correlations explain kinetic selectivity in diffusion-limited solid-state synthesis reactions

Establishing viable solid-state synthesis pathways for novel inorganic materials remains a major challenge in materials science. Previous pathway design methods using pairwise reaction approaches have navigated the thermodynamic landscape with first-principles data but lack kinetic information, limiting their effectiveness. This gap leads to suboptimal precursor selection and predictions, especially for reactions forming competing phases with similar formation energies, where ion diffusion is a critical influence. Here we demonstrate an inorganic synthesis framework by incorporating machine learning-derived transport properties through ‘liquid-like’ product layers into a thermodynamic cellular reaction model. In the Ba–Ti–O system, known for its competitive polymorphism, we obtain accurate predictions of phase formation with varying BaO:TiO2 ratios as a function of time and temperature. We find that diffusion–thermodynamics interplay governs phase compositions, with cross-ion transport coefficients critical for predicting diffusion-limited selectivity. This work bridges length scales and timescales by integrating solid-state reaction kinetics with first-principles thermodynamics and spatial reactivity.

Atomistic models↗

Optical functions of uniaxial rutile and anatase (TiO 2 ) revisited

In this study, the optical functions of uniaxial rutile and anatase (TiO2) were determined from 200 to 850 nm (6.2 to 1.46 eV) using several of four optical techniques: (1) standard spectroscopic two-modulator generalized ellipsometry (2-MGE), (2) near-normal-incidence two-modulator generalized ellipsometry microscopy (2-MGEM), (3) Mueller matrix transmission of rutile, and (4) polarized transmission of rutile. The 2-MGE measurements yielded highly accurate values of the dielectric functions and error estimates from 1.46 to 6.2 eV, whereas the polarization-dependent transmission yielded more accurate values of the absorption coefficient below the band edge of rutile. The 2-MGEM also measured the diattenuation, which is related to the birefringence, and other parameters but at near-normal incidence at a single wavelength (577 nm).

36 MATERIALS SCIENCE↗

Revisiting the assignment of atomic charges in metal oxides based on core-level x-ray photoelectron spectra: The case of Ti in SrTiO3(001)

We demonstrate that assigning formal charges to transition metal (TM) cations based on core-level (CL) x-ray photoemission binding energies in oxides leads to physically inconsistent pictures of electronic structure. O 2p–TM 3d hybridization is well known to result in significant covalency in TM–O bonds, thereby reducing TM cation charges from their fully ionic values. However, the ionic bonding model remains the working paradigm for assigning TM CL features, and the resulting cation charges are often taken to be representative of the material under study. Here, we show that a more physically meaningful way to assign charges is to extract information about charge distributions utilizing Dirac–Hartree–Fock theory to calculate CL spectra from first principles and then use the resulting wave functions to determine charges based on orbital occupancies. TM cation charges can also be determined using density functional theory and Bader population analysis. We illustrate these two methods using the Ti 2p spectrum for SrTiO3(001) and show that the agreement between them is excellent. Significantly, the resulting Ti charge is considerably lower than the formal charge. The high degree of similarity between the Ti 2p spectrum for SrTiO3 and those for the rutile and anatase polymorphs of TiO2 suggests that the charge densities surrounding Ti in the latter materials are similar to that in SrTiO3. Taking a broader perspective, oxides containing other first-row transition metals also exhibit covalent character, leading to TM cation charges lower than the analogous fully ionic values in these materials as well.

Chambers, Scott A. (ORCID:000000025415043X)↗

Machine-learning-enabled on-the-fly analysis of RHEED patterns during thin film deposition by molecular beam epitaxy

Thin film deposition is a fundamental technology for the discovery, optimization, and manufacturing of functional materials. Deposition by molecular beam epitaxy (MBE) typically employs reflection high-energy electron diffraction (RHEED) as a real-time in situ probe of the growing film. However, the state-of-the-art for RHEED analysis during deposition requires human observation. Here, we present an approach using machine learning (ML) methods to monitor, analyze, and interpret RHEED images on-the-fly during thin film deposition. In the analysis workflow, RHEED pattern images are collected at one frame per second and featurized using a pretrained deep convolutional neural network. The feature vectors are then statistically analyzed to identify changepoints; these changepoints can be related to changes in the deposition mode from initial film nucleation to a transition regime, smooth film deposition, and in some cases, an additional transition to a rough, islanded deposition regime. The feature vectors are additionally analyzed via graph analysis and community classification. The graph is quantified as a stabilization plot, and we show that inflection points in the stabilization plot correspond to changes in the growth regime. The full RHEED analysis workflow is termed RHAAPsody and includes data transfer and output to a visual dashboard. We demonstrate the functionality of RHAAPsody by analyzing the precaptured RHEED images from epitaxial depositions of anatase TiO2 on SrTiO3(001) and show that the analysis workflow can be executed in less than 1 s. Our approach shows promise as one component of ML-enabled real-time feedback control of the MBE deposition process.

36 MATERIALS SCIENCE↗