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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Visualization of the surface distribution of photocatalytic activity at the anatase/rutile TiO2 interface using X-ray photoelectron emission microscopy

We applied X-ray photoelectron emission microscopy (XPEEM) to visualize the surface distribution of photocatalytic activity at the anatase/rutile (A/R) interface of titanium dioxide. Acetic acid was adsorbed on the surface, and its decomposition and desorption reactions under ultraviolet light irradiation were monitored by observing C 1s spectra, enabling direct observation of the spatial distribution of photocatalytic activity. Complementary crystal structure information was obtained using spatially resolved low-energy electron diffraction, low-energy electron microscopy, X-ray absorption spectroscopy, and micro-focused Raman spectroscopy. Comparison with these structural data allowed for the evaluation of the photocatalytic activity as a function of the distance from the A/R interface. The activity is enhanced in the vicinity of the interface and gradually decreases toward both the anatase and rutile regions. These results demonstrate that XPEEM is an effective technique for spatially resolved mapping of photocatalytic activity, which has\\r\\npreviously been inaccessible using conventional characterization techniques.

25 ENERGY STORAGE↗
DOE OSTI2024

Morphological Modulation of TiO 2 Nanotube via Optimal Anodization Condition for Solar Water Oxidation

With the depletion of fossil fuels and the rising global demand for energy, photoelectrochemical (PEC) water splitting presents a promising solution to avert an energy crisis. Titanium dioxide (TiO 2 ), an n -type semiconductor, has gained popularity as a photoanode due to its remarkable PEC properties. Nevertheless, inherent challenges such as a wide band gap (~3.2 eV), charge recombination, and slow oxygen evolution reaction (OER) rates at the surface limit its practical application by constraining light absorption. To overcome these limitations, we have developed TiO 2 nanotubes (NTs) using a facile anodization method. This study examines the impact of anodization growth parameters on solar water oxidation performance. Specifically, TiO 2 NTs with modified anodization time (referred to as TiO 2 -6) showed a 3.5-fold increase in photocurrent density compared to the as-grown TiO 2 NTs. Furthermore, electrochemical analyses, such as electrochemical impedance spectroscopy (EIS), indicated a significant decrease in charge transfer resistance following the adjustment of on-off anodization time. Additionally, the TiO 2 -6 photoanode demonstrated a higher electrochemically active surface area (ECSA) than other samples. Therefore, optimal nanostructuring parameters are crucial for enhancing the PEC properties of TiO 2 NTs. Overall, our findings offer valuable insights for fabricating high-quality TiO 2 NTs photoanodes, contributing to developing efficient PEC systems for sustainable energy production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Laser-engraved defects in TiO 2 support: Enhancing reducibility and redox capability of Pt/TiO 2 catalyst for reactive and selective hydrogenation

Titanium dioxide (TiO 2 ) has been studied as catalyst or catalyst support in catalysis. Its synthesis or modification approach controls the structural, optical, and electronic properties. Here, in this work, we applied laser engraving to the anatase TiO 2 and studied the consequent changes in its structure and property as well as the properties of TiO 2 supported platinum (i.e., Pt/TiO 2 ) catalyst. The laser engraving enlarged the particle size, formed rutile phase and created defects (i.e., oxygen vacancy (O v ) and Ti 3+ ) in anatase TiO 2 . This induced band gap change and enhanced visible light absorption. The defects created by laser engraving are stable and more reducible than those existed in the pristine TiO 2 . The defective TiO 2 is structurally stable and has great redox properties. The metal-support interaction in the Pt/defective TiO 2 catalyst is stronger than that of the pristine Pt/TiO 2 catalyst, which enabled higher reactivity and selectivity in hydrogenation of 3-nitrostyrene and furfuryl alcohol. Laser-engraved TiO 2 has been rarely studied for thermal catalysis. This work provides basic understanding of material properties and catalysis application of laser-engraved catalyst supports and catalysts in field of thermal catalysis.

25 ENERGY STORAGE↗
DOE OSTI2025

Machine‐Learning‐Driven Exploration of Surface Reconstructions of Reduced Rutile TiO 2

Titanium dioxide (TiO 2 ) is widely used as a catalyst support due to its stability, tunable electronic properties, and surface oxygen vacancies, which are crucial for catalytic processes such as the reverse water-gas shift (RWGS) reaction. Reduced TiO 2 surfaces undergo complex surface reconstructions that endow unique properties but are computationally challenging to describe. In this study, we utilize machine-learning interatomic potentials (MLIPs) integrated with an active-learning workflow to efficiently explore reduced rutile TiO 2 surfaces. This approach enabled the prediction of a phase diagram as a function of oxygen chemical potential, revealing a variety of reconstructed phases, including a previously unreported subsurface shear plane structure. We further investigate the electronic properties of these surfaces and validate our results by comparing experimental and theoretical high-resolution transmission electron microscopy (HRTEM). Our findings provide new insights into how extreme surface reductions influence the structural and electronic properties of TiO 2 , with potential implications for catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Annealing temperature variation and its influence on the self-cleaning properties of TiO 2 thin films

Titanium dioxide (TiO 2 ) is an important material in science and engineering because of its basic and synthetic properties. Nevertheless, there is a dearth of reports in the open literature focusing on its ability to self-clean under temperature changes. In this study, we used the spin coating technique to produce TiO 2 thin films to evaluate its self-cleaning ability after annealing at different temperatures. The TiO 2 sol was obtained through an endothermal sol-gel process, and the gel was coated on a glass substrate using a spin coater. The deposited films were then annealed at 400 °C, 600 °C, and 800 °C for 1 h. The influence of annealing temperature variation on the self-cleaning properties of the thin film was characterized using X-ray diffraction, scanning electron microscope; Fourier transformed infrared spectrometric analysis and UV-vis spectrophotometer. A test to ascertain self-cleaning was conducted using the degradation of methylene blue, and the different films were tested for durability. The durability test confirmed the connection between solid coating and substrate at all annealing temperatures. Thin films annealed at 600 °C revealed the best self-cleaning properties. The morphological analysis revealed snowflake shapes uniformly distributed over the substrate at 400 °C, and agglomeration improved as the annealing temperature increased. Structural analysis showed an increase in crystallinity with an increase in annealing temperature for both rutile and anatase phases. At three different temperatures, the chemical bond and the absorption band pattern followed the same path, although the peak intensity declined with temperature rise. Finally, the optical bandgap of the thin coated TiO 2 declined from 3.39 eV to 3.20 eV as the binding temperature increased from 400 to 800 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Light-Induced Transformation of Virus-Like Particles on TiO 2

Titanium dioxide (TiO 2 ) shows significant potential as a self-cleaning material to inactivate severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and prevent virus transmission. This study provides insights into the impact of UV-A light on the photocatalytic inactivation of adsorbed SARS-CoV-2 virus-like particles (VLPs) on a TiO 2 surface at the molecular and atomic levels. X-ray photoelectron spectroscopy, combined with density functional theory calculations, reveals that spike proteins can adsorb on TiO 2 predominantly via their amine and amide functional groups in their amino acids blocks. We employ atomic force microscopy and grazing-incidence small-angle X-ray scattering (GISAXS) to investigate the molecular-scale morphological changes during the inactivation of VLPs on TiO 2 under light irradiation. Notably, in situ measurements reveal photoinduced morphological changes of VLPs, resulting in increased particle diameters. These results suggest that the denaturation of structural proteins induced by UV irradiation and oxidation of the virus structure through photocatalytic reactions can take place on the TiO 2 surface. The in situ GISAXS measurements under an N 2 atmosphere reveal that the virus morphology remains intact under UV light. This provides evidence that the presence of both oxygen and UV light is necessary to initiate photocatalytic reactions on the surface and subsequently inactivate the adsorbed viruses. The chemical insights into the virus inactivation process obtained in this study contribute significantly to the development of solid materials for the inactivation of enveloped viruses.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Inhibition of atomic layer deposition of TiO 2 by functionalizing silicon surface with 4-fluorophenylboronic acid

As the size of the components in electronic devices decreases, new approaches and chemical modification schemes are needed to produce nanometer-size features with bottom-up manufacturing. Organic monolayers can be used as effective resists to block the growth of materials on non-growth substrates in area-selective deposition methods. However, choosing the appropriate surface modification requires knowledge of the corresponding chemistry and also a detailed investigation of the behavior of the functionalized surface in realistic deposition schemes. This study aims to investigate the chemistry of boronic acids that can be used to prepare such non-growth areas on elemental semiconductors. 4-Fluorophenylboronic acid is used as a model to investigate the possibility to utilize the Si(100) surface functionalized with this compound as a non-growth substrate in a titanium dioxide (TiO 2 ) deposition scheme based on sequential doses of tetrakis(dimethylamido)titanium and water. Here, a combination of X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry allows for a better understanding of the process. The resulting surface is shown to be an effective non-growth area to TiO 2 deposition when compared to currently used H-terminated silicon surfaces but to exhibit much higher stability in ambient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Oxides and Nitrides with Asymmetric Pore Structure from Block Copolymer Co–Assembly and Non–Solvent Induced Phase Separation

Materials combining an asymmetric pore structure with mesopores everywhere enable high surface area accessibility and fast transport, making them attractive for e.g., energy conversion and storage applications. Block copolymer (BCP)/inorganic precursor co-assembly combined with non-solvent induced phase separation (NIPS) provides a route to materials in which a mesoporous top surface layer merges into an asymmetric support with graded porosity along the film normal and mesopores throughout. Here, the co-assembly and non-solvent-induced phase separation (CNIPS) of poly(isoprene)-b-poly(styrene)-b-poly(4-vinylpyridine) (ISV) triblock terpolymer and titanium dioxide (TiO 2 ) sol-gel nanoparticlesare reported. Heat-treatment in air results in free-standing asymmetric porous TiO 2 . Further thermal processing in ammonia results in free-standing asymmetric porous titanium nitride (TiN). processing changes alter structural membrane characteristics is demonstrated. Changing the CNIPS evaporation time results in various membrane cross-sections ( finger-like to sponge-like). Further, oxide and nitride material composition, crystallinity, and porosity are tuned by varying thermal processing conditions. Finally, thermal processing condition effects are probed on phase-pure asymmetric nitride membrane behavior using cyclic voltammetry to elucidate their influence, e.g., on specific capacitance. Results provide further insights into improving asymmetric and porous materials for applications including energy conversion and storage, separation, and catalysis and motivate a further expansion of CNIPS to other (in)organic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Hydroxyapatite/TiO 2 Nanomaterial with Defined Microstructural and Good Antimicrobial Properties

Due to the growing number of people infected with the new coronavirus globally, which weakens immunity, there has been an increase in bacterial infections. Hence, knowledge about simple and low-cost synthesis methods of materials with good structural and antimicrobial properties is of great importance. A material obtained through the combination of a nanoscale hydroxyapatite material (with good biocompatibility) and titanium dioxide (with good degradation properties of organic molecules) can absorb and decompose bacteria. In this investigation, three different synthesis routes used to prepare hydroxyapatite/titanium dioxide nanomaterials are examined. The morphology and semiquantitative chemical composition are characterized by scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDX). The obtained materials’ phase and structural characterization are determined using the X-ray powder diffraction method (XRD). The crystallite sizes of the obtained materials are in the range of 8 nm to 15 nm. Based on XRD peak positions, the hexagonal hydroxyapatite phases are formed in all samples along with TiO 2 anatase and rutile phases. According to SEM and TEM analyses, the morphology of the prepared samples differs depending on the synthesis route. The EDX analysis confirmed the presence of Ti, Ca, P, and O in the obtained materials. The IR spectroscopy verified the vibration bands characteristic for HAp and titanium. The investigated materials show excellent antimicrobial and photocatalytic properties.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Solvent effects on the heterogeneous growth of TiO 2 nanostructure arrays by solvothermal synthesis

One-dimensional titanium dioxide (TiO 2 ) nanostructure arrays (nanoarrays) are important metal oxide nanomaterials that can be synthesized via facile solvothermal methods. The properties of the organic solvents can impose significant effects on the microstructures and properties of the final products. However, the discussions were limited to the homogeneously nucleated TiO 2 nanomaterials in free-standing powder form, while the solvent effects are less understood during the heterogeneous growth of TiO 2 nanoarrays on a substrate surface. In this work, six organic compounds, namely 2-butanone, n-decane, n-hexane, toluene, ethylene glycol and ethanol, were selected as the solvents for the solvothermal synthesis of TiO 2 nanoarrays on the cordierite monolithic substrates. Special attentions are paid to the morphology, crystallinity, specific surface area, and porosity of the samples. The heterogeneous growth of TiO 2 nanoarrays on substrate surfaces is found to favor the solvents with moderate dielectric constants, which can be partially dissolved in the aqueous solution and modulate the reaction rate during the solvothermal synthesis. Organic solvents with low dielectric constants may result in a complete separation between the precursors and aqueous solution, and therefore slow down the overall reaction, causing the insufficient growth of the nanoarrays. The TiO 2 nanoarrays are obtained with optimum morphology from the combination of 2-butanone and titanium (IV) butoxide as solvent and precusor, respectively, with a high specific surface area up to 56 m 2 /g including cordierite substrate given a micron thickness. When loaded with Pt catalyst, the TiO 2 nanoarray-based monolithic catalysts show excellent low-temperature catalytic activity and hydrothermal stability for the CO and hydrocarbon oxidation under the simulated exhausted conditions. This article shall shed light on a better understanding of the growth mechanism and rational design of TiO 2 nanoarrays for high-performance catalytic converters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Oxygen Atom Transfer Reactions of Colloidal Metal Oxide Nanoparticles

Redox transformations at metal oxide (MO x )/solution interfaces are broadly important, and oxygen atom transfer (OAT) is one of the simplest and most fundamental examples of such reactivity. OAT is a two-electron transfer process, well-known in gas/solid reactions and catalysis. However, OAT is rarely directly observed at oxide/water interfaces, whose redox reactions are typically proposed to occur in one-electron steps. Reported here are stoichiometric OAT reactions of organic molecules with aqueous colloidal titanium dioxide and iridium oxide nanoparticles (TiO 2 and IrO x NPs). Me 2 SO (DMSO) oxidizes reduced TiO 2 NPs with the formation of Me 2 S, and IrO x NPs transfer O atoms to a water-soluble phosphine and a thioether. The reaction stoichiometries were established and the chemical mechanisms were probed using typical solution spectroscopic techniques, exploiting the high surface areas and transparency of the colloids. Furthermore, these OAT reactions, including a catalytic example, utilize the ability of the individual NPs to accumulate many electrons and/or holes. Observing OAT reactions of two different materials, in opposite directions, is a step toward harnessing oxide nanoparticles for valuable multi-electron and multi-hole transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Coupling Interfacial Redox‐Reactions with In Situ Proton Generation for the Photoelectrochemical Separation of Rare‐Earth Elements

Abstract A dual‐function photoelectrochemical (PEC) separation system is demonstrated for rare‐earth element (REE) recovery. The sustainable release of the captured REEs is promoted through the synergistic integration of a redox‐reaction for electrostatic repulsion, and in situ proton generation for ion‐exchange, all driven by photoelectrochemistry. The platform consists of a redox‐copolymer, poly(ferrocenylpropyl methacrylamide‐ co ‐methacrylic acid) (P(FPMAm‐ co ‐MAA)) (PFM), conjugated with carbon nanotubes (CNTs) and coated onto titanium dioxide nanorods (TNRs). The (PFM‐CNT)/TNR spontaneously adsorbs up to 214.2 mg of Yttrium/g PFM by ion‐exchange, and demonstrates broad applicability for other REEs. The adsorbed REEs are released through the PEC oxidation of ferrocene (Fc) to ferrocenium (Fc + ), and the simultaneous PEC water splitting reactions at the TNRs that protonate the carboxylate binding groups. This dual photoelectrochemically‐driven mechanism for REE release is investigated by in situ pH measurements, as well as vibrational and X‐ray photoelectron spectroscopy. Through PEC approaches, a 68.8% reduction in energy consumption during REE recovery has been achieved compared to purely electrochemical systems, with a regeneration efficiency close to 100%. For NdFeB magnets from waste hard disk drives, Nd and Dy recovery efficiencies of 59.2 and 61.1% are achieved. The dual‐functionality of these copolymer PEC systems offers a sustainable platform for modulating critical element recovery.

Cho, Ki‐Hyun [Department of Chemical and Biomolecu↗
DOE OSTI2025

Imaging Photonic Resonances within an All‐Dielectric Metasurface via Photoelectron Emission Microscopy

Dielectric metasurfaces, through volume‐type photonic resonances, enable precise control of light‐matter interactions for applications including imaging, holography, and sensing. The application space of dielectric metasurfaces has extended from infrared to visible wavelengths by incorporating high refractive index materials, such as titanium dioxide (TiO 2 ). Understanding the fundamental and fabrication limits for these applications requires metrology with nanoscale resolution, sensitivity to electromagnetic fields within the meta‐atom volume, and far‐field excitation. In this work, photoelectron emission microscopy (PEEM) is used to image field distributions of photonic resonances in a TiO 2 metasurface excited with far‐field, visible‐wavelength illumination. The local volumetric field variations within the meta‐atoms are analyzed as a function of illumination angle and polarization by comparing photoelectron images to finite‐difference time‐domain simulations. This study determines the inelastic mean free path of very low‐energy (<1 eV) photoelectrons to be 35 ± 10 nm, which is comparable to the meta‐atom height thereby highlighting PEEM sensitivity to resonances within the volume. Additionally, the simulations reveal high sensitivity of PEEM images to an in‐plane component of the illumination k ‐vector. These results demonstrate that photoelectron imaging with subwavelength resolution offers unique advantages for examining light‐matter interactions in volume‐type (as opposed to surface) photonic modes within dielectric nanophotonic structures.

electron inelastic mean free path↗
DOE OSTI2022

Aqueous Photoelectrochemical CO 2 Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst

Abstract We report a precious‐metal‐free molecular catalyst‐based photocathode that is active for aqueous CO 2 reduction to CO and methanol. The photoelectrode is composed of cobalt phthalocyanine molecules anchored on graphene oxide which is integrated via a (3‐aminopropyl)triethoxysilane linker to p‐type silicon protected by a thin film of titanium dioxide. The photocathode reduces CO 2 to CO with high selectivity at potentials as mild as 0 V versus the reversible hydrogen electrode (vs RHE). Methanol production is observed at an onset potential of −0.36 V vs RHE, and reaches a peak turnover frequency of 0.18 s −1 . To date, this is the only molecular catalyst‐based photoelectrode that is active for the six‐electron reduction of CO 2 to methanol. This work puts forth a strategy for interfacing molecular catalysts to p‐type semiconductors and demonstrates state‐of‐the‐art performance for photoelectrochemical CO 2 reduction to CO and methanol.

Shang, Bo↗
DOE OSTI2025

Machine‐Learning‐Driven Exploration of Surface Reconstructions of Reduced Rutile TiO 2

Abstract Titanium dioxide (TiO 2 ) is widely used as a catalyst support due to its stability, tunable electronic properties, and surface oxygen vacancies, which are crucial for catalytic processes such as the reverse water‐gas shift (RWGS) reaction. Reduced TiO 2 surfaces undergo complex surface reconstructions that endow unique properties but are computationally challenging to describe. In this study, we utilize machine‐learning interatomic potentials (MLIPs) integrated with an active‐learning workflow to efficiently explore reduced rutile TiO 2 surfaces. This approach enabled the prediction of a phase diagram as a function of oxygen chemical potential, revealing a variety of reconstructed phases, including a previously unreported subsurface shear plane structure. We further investigate the electronic properties of these surfaces and validate our results by comparing experimental and theoretical high‐resolution transmission electron microscopy (HRTEM). Our findings provide new insights into how extreme surface reductions influence the structural and electronic properties of TiO 2 , with potential implications for catalyst design.

Lee, Yonghyuk [Chemistry and Biochemistry Universi↗
DOE OSTI2022

Aqueous Photoelectrochemical CO 2 Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst

We report a precious-metal-free molecular catalyst-based photocathode that is active for aqueous CO 2 reduction to CO and methanol. The photoelectrode is composed of cobalt phthalocyanine molecules anchored on graphene oxide which is integrated via a (3-aminopropyl)triethoxysilane linker to p-type silicon protected by a thin film of titanium dioxide. The photocathode reduces CO 2 to CO with high selectivity at potentials as mild as 0 V versus the reversible hydrogen electrode (vs RHE). Methanol production is observed at an onset potential of –0.36 V vs RHE, and reaches a peak turnover frequency of 0.18 s –1 . To date, this is the only molecular catalyst-based photoelectrode that is active for the six-electron reduction of CO 2 to methanol. Furthermore, this work puts forth a strategy for interfacing molecular catalysts to p-type semiconductors and demonstrates state-of-the-art performance for photoelectrochemical CO 2 reduction to CO and methanol.

14 SOLAR ENERGY↗
DOE OSTI2025

Effect of Ambient Organic Acids on the Water Structure at ${\rm TiO}_{2}$ Interfaces

A molecular-level understanding of the effects of ambient organic compounds on the wettability of titanium dioxide ( ${\rm TiO}_{2}$ ) surfaces is relevant to many of its energy-related and environmental applications. Herein, we focus on two common atmospheric carboxylic acids, formic and acetic acid, and characterize their adsorption/ desorption at the aqueous interfaces of anatase and rutile ${\rm TiO}_{2}$ using molecular dynamics with an ab initio deep neural network potential. Our simulations show that these acids prefer to be localized in the interfacial water layers close to the ${\rm TiO}_{2}$ surface where they are stabilized by the interaction/exchange of their acid proton with a surface oxygen, rather than chemisorb at the surface Ti sites by displacing the adsorbed water. Notably, these acids make the surface of anatase hydrophobic, whereas the larger fraction of adsorbed water dissociation can offset their effect on rutile. Furthermore, these results provide a picture where carboxylic acids control the wettability of ${\rm TiO}_{2}$ largely through acid-base chemistry at the interface rather than chemisorption on the oxide surface, a finding that can help improve the design of self-cleaning surfaces and photocatalytic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗