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At least 91 records · Page 5

Self-Cleaning Highly Porous TiO 2 Coating Designed by Swelling-Assisted Sequential Infiltration Synthesis (SIS) of a Block Copolymer Template

Photocatalytic self-cleaning coatings with a high surface area are important for a wide range of applications, including optical coatings, solar panels, mirrors, etc. Here, we designed a highly porous TiO 2 coating with photoinduced self-cleaning characteristics and very high hydrophilicity. This was achieved using the swelling-assisted sequential infiltration synthesis (SIS) of a block copolymer (BCP) template, which was followed by polymer removal via oxidative thermal annealing. The quartz crystal microbalance (QCM) was employed to optimize the infiltration process by estimating the mass of material infiltrated into the polymer template as a function of the number of SIS cycles. This adopted swelling-assisted SIS approach resulted in a smooth uniform TiO 2 film with an interconnected network of pores. The synthesized film exhibited good crystallinity in the anatase phase. The resulting nanoporous TiO 2 coatings were tested for their functional characteristics. Exposure to UV irradiation for 1 h induced an improvement in the hydrophilicity of coatings with wetting angle reducing to unmeasurable values upon contact with water droplets. Furthermore, their self-cleaning characteristics were tested by measuring the photocatalytic degradation of methylene blue (MB). The synthesized porous TiO 2 nanostructures displayed promising photocatalytic activity, demonstrating the degradation of approximately 92% of MB after 180 min under ultraviolet (UV) light irradiation. Thus, the level of performance was comparable to the photoactivity of commercial anatase TiO 2 nanoparticles of the same quantity. Our results highlight a new robust approach for designing hydrophilic self-cleaning coatings with controlled porosity and composition.

36 MATERIALS SCIENCE↗

Search for TiO and Optical Nightside Emission from the Exoplanet WASP-33b

With a temperature akin to an M dwarf, WASP-33b is among the hottest Jupiters known, making it an ideal target for high-resolution optical spectroscopy. By analyzing both transmission and emission spectra, we aim to substantiate previous reports of atmospheric TiO and a thermal inversion within the planet’s atmosphere. We observed two transits and six arcs of the phase curve with the Echelle SpectroPolarimetric Device for the Observation of Stars (ESPaDOnS) on the Canada–France–Hawaii Telescope and High Resolution Echelle Spectrometer (HIRES) on the Keck telescope, which provide high spectral resolution and ample wavelength coverage. We employ the Doppler cross-correlation technique to search for the molecular signatures of TiO and H{sub 2}O in these spectra, using models based on the TiO line list of Plez. Though we cannot exclude line-list-dependent effects, our data do not corroborate previous indications of a thermal inversion. Instead we place a 3σ upper limit of 10{sup −9} on the volume mixing ratio of TiO for the T–P profile we consider. While we are unable to constrain the volume mixing ratio of water, our strongest constraint on TiO comes from dayside emission spectra. This apparent absence of a stratosphere sits in stark contrast to previous observations of WASP-33b as well as theoretical predictions for the atmospheres of highly irradiated planets. The discrepancy could be due to variances between line lists, and we stress that detection limits are only as good as the line list employed, and are only valid for the specific T–P profile considered due to the strong degeneracy between lapse rate (dT/dlogP) and molecular abundance.

79 ASTRONOMY AND ASTROPHYSICS↗

Application of ultrathin TiO 2 layers in solar energy conversion devices

Abstract A vital pursuit in solar energy research is to achieve high efficiency and long‐term stability in energy conversion devices. Coating or sandwiching an ultrathin layer of TiO 2 onto active solar components has been demonstrated to be a remarkably effective and facile strategy to improve their stability. The TiO 2 film acts as a protection layer and enhances solar energy conversion efficiency by passivating surface recombination sites or facilitating electron transport. To date, numerous efforts have been devoted to applying ultrathin TiO 2 layers in various kinds of solar energy conversion devices. In this study, we review deposition techniques, characterization methods of the resulting ultrathin TiO 2 layer, as well as its applications in dye‐sensitized solar cells, organic–inorganic hybrid solar cells, and photoelectrochemical cells.

36 MATERIALS SCIENCE↗

Materials Data on TiO by Materials Project

TiO crystallizes in the tetragonal I4/mmm space group. The structure is two-dimensional and consists of six TiO sheets oriented in the (0, 0, 1) direction. In two of the TiO sheets, there are two inequivalent Ti2+ sites. In the first Ti2+ site, Ti2+ is bonded in a 5-coordinate geometry to five O2- atoms. There are four shorter (2.09 Å) and one longer (2.32 Å) Ti–O bond lengths. In the second Ti2+ site, Ti2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Ti–O bond distances ranging from 2.07–2.77 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 5-coordinate geometry to six Ti2+ atoms. In the second O2- site, O2- is bonded in a 5-coordinate geometry to five Ti2+ atoms. In four of the TiO sheets, Ti2+ is bonded in a distorted square co-planar geometry to four equivalent O2- atoms. All Ti–O bond lengths are 2.07 Å. O2- is bonded in a 4-coordinate geometry to four equivalent Ti2+ atoms.

36 MATERIALS SCIENCE↗

TiO2 Nanocrystal-Framed Li 2 TiSiO 5 Platelets for Low-Voltage Lithium Battery Anode

Titanium-based anode materials are attracting considerable attention for use in high-performance lithium-ion batteries, but the compromised energy density caused by high voltage plateaus and unsatisfactory capacities severely retards their practical applications. Herein, a molten-salt synthesis of Li 2 TiSiO 5 crystalline platelets and a subsequent selective facet modification by in situ growth of TiO 2 nanocrystal frames are facilely achieved. The discharge voltage plateau at around 0.5 V renders the Li 2 TiSiO 5 anode safe compared with graphite and confers a high energy density compared with zero-strain Li 4 Ti 5 O 12 anode. With the optimized size, structure, and content of modified TiO2 nanocrystals associated with the exposed (001) plane of Li 2 TiSiO 5 , the Li 2 TiSiO 5 -based anodes can deliver a capacity of above 300 mAh g -1 , enhanced rate performance, and a capacity retention of 66% after 10 000 cycles. In situ X-ray diffraction and ex situ transmission electron microscopy have demonstrated the structural stability of the anodes upon charge/discharge. Further theoretical calculation reveals 3D migration paths of Li + ions in Li 2 TiSiO 5 . The selective modification of in situ grown TiO2 nanocrystals on certain facets of crystallites opens a new door for the development of electrode materials possessing superior electrochemical properties.

anodes↗

Polarity‐Driven Atomic Displacements at the 2D Mg 2 TiO 4 ‐MgO (001) Oxide Interface for Hosting Potential Interlayer Excitons

Abstract Interlayer excitons in solid‐state systems have emerged as candidates for realizing novel platforms ranging from excitonic transistors and optical qubits to exciton condensates. Interlayer excitons have been discovered in 2D transition metal dichalcogenides, with large exciton binding energies and the ability to form various van der Waals heterostructures. Here, an oxide system consisting of a single unit cell of Mg 2 TiO 4 on MgO (001) is proposed as a platform for hosting interlayer excitons. Using a combination of density functional theory (DFT) calculations, molecular beam epitaxy growth, and in situ crystal truncation rod measurements, it is shown that the Mg 2 TiO 4 ‐MgO interface can be precisely controlled to yield an internal electric field suitable for hosting interlayer excitons. The atoms in the polar Mg 2 TiO 4 layers are observed to be displaced to reduce polarity at the interface with the non‐polar MgO (001) surface. Such polarity‐driven atomic displacements strongly affect electrostatics of the film and the interface, resulting in localization of filled and empty band‐edge states in different layers of the Mg 2 TiO 4 film. The DFT calculations suggest that the electronic structure is favorable for localization of photoexcited electrons in the bottom layer and holes in the top layer, which may bind to form interlayer exciton states.

36 MATERIALS SCIENCE↗

In Situ Dispersion of Palladium on TiO 2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium

The application of single-atom catalysts (SACs) to high-temperature hydrogenation requires materials that thermodynamically favor metal atom isolation over cluster formation. Here, we show that Pd can be predominantly dispersed as isolated atoms onto TiO 2 during the reverse water-gas shift (rWGS) reaction at 400 °C. Achieving atomic dispersion requires an artificial increase of the absolute TiO 2 surface area by an order of magnitude and can be accomplished by physically mixing a precatalyst (Pd/TiO 2 ) with neat TiO 2 prior to the rWGS reaction. Furthermore, the in situ dispersion of Pd was reflected through a continuous increase of rWGS activity over 92 h and supported by kinetic analysis, infrared and X-ray absorption spectroscopies and scanning transmission electron microscopy. The thermodynamic stability of Pd under high-temperature rWGS conditions is associated with Pd-Ti coordination, which manifests upon O-vacancy formation and the artificial increase in TiO 2 surface area.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

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↗

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↗

Biopolymer‐assisted Synthesis of P‐doped TiO 2 Nanoparticles for High‐performance Lithium‐ion Batteries: A Comprehensive Study

Abstract TiO 2 material has gained significant attention for large‐scale energy storage due to its abundant, low‐cost, and environmentally friendly properties, as well as the availability of various nanostructures. Phosphorus doping has been established as an effective technique for improving electronic conductivity and managing the slow ionic diffusion kinetics of TiO 2 . In this study, non‐doped and phosphorus doped TiO 2 materials were synthesized using sodium alginate biopolymer as chelating agent. The prepared materials were evaluated as anode materials for lithium‐ion batteries (LIBs). The electrodes exhibit remarkable electrochemical performance, including a high reversible capacity of 235 mAh g −1 at 0.1 C and excellent first coulombic efficiency of 99 %. An integrated approach, combining operando XRD and ex‐situ XAS, comprehensively investigates the relationship between phosphorus doping, material structure, and electrochemical performance, reinforced by analytical tools and first principles calculations. Furthermore, a full cell was designed using 2 %P‐doped TiO 2 anode and LiFePO 4 cathode. The output voltage was about 1.6 V with high initial specific capacity of 148 mAh g −1 , high rate‐capability of 120 mAh g −1 at 1 C, and high‐capacity retention of 96 % after 1000 cycles at 1 C.

El Halya, Nabil↗

Consequences of Intrapore Liquids on Reactivity, Selectivity, and Stability for Aldol Condensation Reactions on Anatase TiO 2 Catalysts

Abstract This study provides evidence and mechanistic interpretations for the significant consequences of intrapore non‐polar liquids on acetone aldol condensation turnover rates, selectivity to primary dimer products, and catalyst stability for reactions at Lewis acid‐base site pairs on TiO 2 surfaces. These non‐polar liquids confer such benefits through the preferential stabilization of transition states (TS) for adsorption (“entry”) and desorption (“exit”) steps, which place their respective reactants or products within a solvating outer sphere environment. The extent to which non‐polar fluids ( n ‐heptane) form an intrapore liquid phase within TiO 2 voids was obtained from N 2 uptakes using established formalisms that consider the different molal volume, surface tension, and volatility between N 2 and n ‐heptane. Acetone condensation rates are limited by C−H activation, an “entry” step that forms bound prop‐1‐en‐2‐olates via a TS stabilized by intrapore liquids, leading to higher aldol condensation turnover rates as n ‐heptane pressure increases and active TiO 2 surfaces become increasingly immersed within a non‐polar liquid phase. These liquids solvate the late TS structures that mediate the desorption of primary C 6 condensation products even more effectively than those involved in prop‐1‐en‐2‐olate formation or in nucleophilic attack events that later form C−C bonds. Such preferential solvation favors desorption over C−C coupling events, thus disfavoring the formation of larger oligomers that become stranded at active sites, thus leading to much slower deactivation. Moreover, solvation by non‐polar liquids also leads to C 6 alkanones as the sole products formed in a single surface sojourn. These effects of a non‐polar dense phase circumvent the inherent stability, reactivity, and selectivity hurdles that have precluded practical aldol condensation catalysis on Lewis acid‐base pairs at oxide surfaces; these consequences are demonstrated here for TiO 2 catalysts, acetone aldol condensation reactions, and n ‐heptane as the non‐polar liquid but through strategies, concepts, and mechanistic features that extend to other systems. More generally, these observations and their mechanistic origins demonstrate how a contacting liquid preferentially solvates TS structures for elementary steps that involve either reactants arriving from or products entering into an outer sphere environment that contains a dense non‐polar phase.

Kadam, Shashikant A.↗

Degradation-resistant TiO 2 @Sn anodes for high-capacity lithium-ion batteries

As the demand for higher-performance batteries has increased, so has the body of research on theoretical high-capacity anode materials. However, the research has been hindered because the high-capacity anode material properties and interactions are not well understood, largely due to the difficulty of observing cycling in situ. Using electrochemical scanning transmission electron microscopy (ec-STEM), we report the real-time observation and electrochemical analysis of pristine tin (Sn) and titanium dioxide-coated Sn (TiO 2 @Sn) electrodes during lithiation/delithiation. As expected, we observed a volume expansion of the pristine Sn electrodes during lithiation, but we further observed that the expansion was followed by Sn detachment from the current collector. Remarkably, although the TiO 2 @Sn electrodes also exhibited similar volume expansion during lithiation, they showed no evidence of Sn detachment. We found that the TiO 2 surface layer acted as an electrochemically activated artificial solid-electrolyte interphase that serves to conduct Li ions. As a physical coating, it mechanically prevented Sn detachment following volume changes during cycling, providing significant degradation resistance and 80% Coulombic efficiency for a complete lithiation/delithiation cycle. Interestingly, upon delithiation, TiO 2 @Sn electrode displayed a self-healing mechanism of small pore formation in the Sn particle followed by agglomeration into several larger pores as delithiation continued.

25 ENERGY STORAGE↗

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↗

Influence of Domain Size and Support Composition on the Reducibility of SiO 2 and TiO 2 Supported Tungsten Oxide Clusters

Supported tungsten oxides are widely used in a variety of catalytic reactions. Depending on the support, the cluster size, oxidation state, reducibility and speciation of the tungsten oxides can widely differ. When promoted with a platinum group metal, the resulting spillover of hydrogen may facilitate the reduction of supported tungsten oxide species, depending on the support. High resolution scanning transmission electron microscopy imaging showed nanometer scale WO x clusters were synthesized on SiO 2 whereas highly dispersed species were formed on TiO 2 . Results from H 2 -temperature-programmed reduction showed the presence of Pd lowered the initial reduction temperature of SiO 2 -supported WO x species but interestingly did not affect that of TiO 2 -supported WO x . X-ray photoelectron and absorption spectroscopies showed the W atoms in SiO 2 -supported WO x species reduce from a +6 oxidation state to primarily +5 after thermal treatment in 5% H 2 , while the fraction of W in the +5 oxidation state was relatively unaffected by reduction treatment of TiO 2 -supported WO x . The unusual behavior of TiO 2 -supported WO x was explained by quantum chemical calculations that reveal the lack of change in the oxidation state of W is attributed to charge delocalization on the surface atoms of the titania support, which does not occur on silica. Moreover, modeling results at <600 K in the presence of H 2 suggest the formation of Brønsted acid sites, and the absence of Lewis acid sites, on larger aggregates of WO x on silica and all cluster sizes on titania. These results provide experimental and theoretical insights into the nature of supported tungsten oxide clusters under conditions relevant to various catalytic reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stable Supercapacity of Binder-Free TiO 2 (B) Epitaxial Electrodes for All-Solid-State Nanobatteries

Owing to its pseudocapacitive, unidimensional, rapid ion channels, TiO 2 (B) is a promising material for application to battery electrodes. In this study, we align these channels by epitaxially growing TiO 2 (B) films with the assistance of an isostructural VO 2 (B) template layer. In a liquid electrolyte, binder-free TiO 2 (B) epitaxial electrodes exhibit a supercapacity near the theoretical value of 335 mA h g –1 and an excellent charge–discharge reproducibility for ≥200 cycles, which outperform those of other TiO 2 (B) nanostructures. For the all-solid-state configuration employing the LiPON solid electrolyte, excellent stability persists. Our findings suggest excellent potential for miniaturizing all-solid-state nanobatteries in self-powered integrated circuits.

25 ENERGY STORAGE↗

Atomic Layer Deposition with TiO2 for Enhanced Reactivity and Stability of Aromatic Hydrogenation Catalysts

Hydrogenation of aromatic molecules in fossil- and bio-derived fuels is essential for decreasing emissions of harmful combustion products and addressing growing concerns around urban air pollution. In this work, we used atomic layer deposition to significantly enhance the hydrogenation performance of a conventional supported Pd catalyst by applying an ultrathin coating of TiO2 in a scalable powder coating process. The TiO2-coated catalyst showed substantial gains in the conversion of multiple aromatic molecules, including a 5-fold improvement in turnover frequency versus the uncoated catalyst in the hydrogenation of naphthalene. This activity enhancement was maintained upon scaling the coating synthesis process from 3 to 100 g. Based on the results from Xray photoelectron spectroscopy, X-ray absorption spectroscopy, and computational modeling, the activity enhancement was attributed to ensemble effects resulting from partial TiO2 coverage of the Pd surface rather than fundamental changes to the Pd electronic structure. Additional durability testing confirmed that the TiO2 coating improved the thermal and hydrothermal stability of the catalyst as well as tolerance toward sulfur impurities in the reactant stream. Using an economic model of an industrial deep hydrogenation process, we found that an increase in catalyst activity or lifetime of 2× would justify even a relatively high estimate for the cost of TiO2 atomic layer deposition coatings at scale

atomic layer↗

Observing Chemical and Morphological Changes in a Cu@TiO x Core@Shell Catalyst: Impact of Reversible Metal-Oxide Interactions on CO 2 Activation and Hydrogenation

A combination of several in-situ techniques (XRD, XAS, AP-XPS, E-TEM) was used to explore links between the structural and chemical properties of a Cu@TiO x catalyst under CO 2 hydrogenation conditions. The active phase of the catalyst involved an inverse oxide/metal configuration, but the initial core@shell motif was disrupted during the pre-treatment in H 2 . As a consequence of strong metal-support interactions, the titania shell cracked and Cu particles migrated from the core to on top of the oxide with the simultaneous formation of a Cu-Ti-O x phase. The generated Cu particles had a diameter of 20-40 nm and were decorated by small clusters of TiO x (< 5 nm in size). Results of in-situ XAS and XRD and images of E-TEM showed a very dynamic system, where the inverse oxide/metal configuration promoted the reactivity of the system towards CO 2 and H 2 . At room temperature, CO 2 oxidized the Cu nanoparticles (CO 2,gas → CO gas + O oxide ) inducing a redistribution of the TiO x clusters and big modifications in catalyst surface morphology. The generated oxide overlayer disappeared at elevated temperatures (> 180 °C) upon exposure to H 2 , producing a transient surface that was very active for the reverse water-gas shift reaction (CO 2 + H 2 → CO + H 2 O) but was not stable at 250 °C. When oxidation and reduction occurred at the same time, under a mixture of CO 2 and H 2 , the surface structure evolved toward a dynamic equilibrium that strongly depended on the temperature. Neither CO 2 nor H 2 can be considered as passive reactants. In the Cu@TiO x system, morphological changes were linked to variations in the composition of metal-oxide interfaces which were reversible with temperature or chemical environment and affected the catalytic activity of the system. Finally, the present study illustrates the dynamic nature of phenomena associated with the trapping and conversion of CO 2 .

36 MATERIALS SCIENCE↗