Crystalline TiO2 Research Articles

Review of Bio-Inspired Green Synthesis of Titanium Dioxide for Photocatalytic Applications

Titanium dioxide (TiO2) is an important photocatalyst that is widely studied for environmental applications, especially for water treatment by degradation of pollutants. A range of methods have been developed to produce TiO2 in the form of nanoparticles and thin films. Solution-based synthesis methods offer the opportunity to tune the synthesis through a choice of reagents, additives and reaction media. In particular, the use of biomolecules, such as proteins and amino acids, as bio-inspired additives in TiO2 synthesis has grown over the last decade. This review provides a discussion of the key factors in the solution-based synthesis of titania, with a focus on bio-inspired additives and their interaction with Ti precursors. In particular, the role of bio-inspired molecular and biomolecular additives in promoting the low-temperature synthesis of titania and controlling the phase and morphology of the synthesised TiO2 is discussed, with a particular focus on the interaction of TiO2 with amino acids as model bio-inspired additives. Understanding these interactions will help address the key challenges of obtaining the crystalline TiO2 phase at low temperatures, with fast kinetics and under mild reaction conditions. We review examples of photocatalytic applications of TiO2 synthesised using bio-inspired methods and discuss the ways in which bio-inspired additives enhance photocatalytic activity of TiO2 nanomaterials. Finally, we give a perspective of the current challenges in green synthesis of TiO2, and possible solutions based on multi-criteria discovery, design and manufacturing framework.

One-Step Magneton Sputtering of Crystalline Cu-Doped TiO2 Coatings: Characterization and Antibacterial Activity

Early biofilm formation could be inhibited by applying a thin biocompatible copper coating to reduce periprosthetic infections. In this study, we deposited crystalline Cu-doped TiO2 films using one-step DC magnetron sputtering in an oxygen atmosphere on a biased Ti6Al4V alloy without external heating. The bias voltage varied from −25 V to −100 V, and the resultant substrate temperature was measured. The deposited coatings were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), microhardness, scratch and hydrophilicity tests, potentiodynamic polarization measurements, and antibacterial assays against S. aureus and E. coli. The findings demonstrated that when a higher negative bias is applied, the substrate temperature drops, and the anatase to rutile transformation is initiated without indicating obvious Cu-containing phases. The SEM images of the films showed spherical agglomerates with homogeneously distributed Cu with decreasing Cu content as the bias value increased. Higher bias results in the grain refinement of the thinning coatings with more lattice microstrain and more defects, together with an increase in water contact angles and hardness values. Samples biased at −75 V exhibited the highest adhesive strength between coatings and substrate, whereas the specimen biased at −50 V demonstrated higher corrosion resistance. Cu-containing TiO2 coatings with pure anatase phase composition and Cu concentrations of 2.62 wt.% demonstrated excellent bactericidal activity against both S. aureus and E. coli. The layers containing 2.34 wt.% Cu exhibited very good antibacterial properties against S. aureus, only. According to these findings, the produced copper-doped TiO2 coatings have high bactericidal qualities in vitro and may be used to prepare orthopaedic and dental implants in the future.

In-situ and ex-situ preparation of Bi2S3 on the BiVO4/TiO2 to construct Bi2S3/BiVO4/TiO2 heterojunction for efficient Cr(VI) reduction

The environmentally friendly and rapid removal of hexavalent chromium (Cr(VI)) from wastewater has garnered significant attention, driven by the severe acute toxicity and carcinogenic properties associated with Cr(VI). The design and synthesis of heterojunctions are recognized as effective solutions for enhancing the photocatalytic performance of TiO2 based materials. BiVO4/TiO2 and Bi2S3/BiVO4/TiO2 composite films (BVT) were prepared via a simple hydrothermal method. The influence of Bi2S3 preparation methods (In-situ and Ex-situ) on the morphology, structure and properties of BVT was studied. The relative crystallinity of TiO2, BiVO4/TiO2, BVT(In-situ) and BVT(Ex-situ) were 50 %, 62 %, 72 % and 92 %, respectively. SEM shows that the morphology of Bi2S3 in BVT(In-situ) was nanoribbon and that of Bi2S3 in BVT(Ex-situ) was radioactive sphere. Compared with pure TiO2 and BiVO4/TiO2, the light absorption range of BVT composite material has been expanded from the ultraviolet light region to the visible region, the bandgap has been significantly narrowed, and the photocurrent density has been increased. The BVT(In-situ) shows stronger photoelectrical performance and reduction efficiency of Cr (VI) compared to BVT(Ex-situ), reaching 93.9 %. The photocatalytic reaction rate of BVT(In-situ) and BVT(Ex-situ) are 0.0291 min−1 and 0.0266 min−1, respectively. Density functional theory (DFT) calculations indicate that the work function of BiVO4 is higher than that of Bi2S3, and electrons will transfer from Bi2S3 to BiVO4 at the heterojunction interface. The BVT(In-situ) heterojunction constructed in this experiment greatly improves the separation and transport efficiency of photo-generated carriers, laying the foundation for the wide application of BVT heterojunction in the field of optoelectronics and providing a strategy for photocatalytic reduction of Cr(VI). The BVT(In-situ) with FTO conductive glass, it also can be applied to photovoltaic fields such as solar cells, photocatalysis and photodetectors.

Ultrafast Electron Dynamics at the P‐rich Indium Phosphide/TiO2 Interface

AbstractThe current efficiency records for generating green hydrogen via solar water splitting are held by indium phosphide (InP)‐based photo‐absorbers, protected by TiO2 layers grown through atomic layer deposition (ALD). InP is also a leading material for photonic integrated circuits and computing, where ultrafast near‐surface behavior is key. A previous study described electronic pathways at the phosphorus‐rich (P‐rich) surface of p‐doped InP(100) using time‐resolved two‐photon photoemission (tr‐2PPE) spectroscopy. Here, the intricate electron pathways of the P‐rich InP surface modified with ALD‐deposited TiO2 are explored. Photoexcited bulk InP electrons migrate through a bulk‐to‐surface transition cluster of states and surface states and inject into the TiO2 conduction band (CB). Energy levels and occupation dynamics of CB states in P‐rich InP and TiO2 adlayers are observed, with discrete states preserved up to 10 nm TiO2 deposition. Thermalization lifetimes of excited electrons > 0.8 eV above the InP conduction band minimum (CBM) are preserved for layer thicknesses up to 2.5 nm. Annealing at 300 °C to achieve crystalline TiO2 reconstructions destroys interfacial states, affecting charge transfer. These observations enable innovative engineering of the P‐rich InP/TiO2 heterointerface, opening new possibilities for studying hot‐carrier extraction, adsorbate effects, surface plasmons, and improving photovoltaic and PEC water‐splitting devices.

Amorphous to Crystalline Transition in Nanoimprinted Sol-Gel Titanium Oxide Metasurfaces.

Crystalline titanium dioxide (TiO2) (anatase and rutile) possesses a higher refractive index than amorphous TiO2 and near-zero absorption in the visible region, making them an ideal material for visible metasurfaces. However, fabrication limitations hinder their implementation into flat optics. In this work, a wafer-scale manufacturing platform is proposed for crystalline TiO2 metasurfaces. Sol-gel TiO2 is developed as a printable material in which its material phase can be precisely controlled to produce amorphous, anatase, or rutile, depending on the crystallization temperature. Therefore, anatase or rutile metalenses can be fabricated on a wafer scale using thermal nanoimprint lithography and sintering process. The high refractive index of the crystalline TiO2 contributes to the enhanced conversion efficiency of the fabricated metalenses. The fabricated metalenses exhibit diffraction-limited focusing and imaging capabilities, comparable to the theoretically ideal lenses.

An Amorphous-to-Anatase Phase Transition Study of TiO2 Nanotubes by Temperature-Dependent Synchrotron-Based In Situ X-ray Diffraction.

TiO2 nanotubes (NTs) with amorphous and crystalline structures have attracted interest due to their wide range of applications, particularly black TiO2, which addresses the limitations of conventional TiO2 (a wide band gap of 3.0-3.2 eV). Understanding the amorphous-to-anatase phase transition is crucial for phase control of crystalline TiO2. This study investigates the size-dependent phase transition behavior of TiO2 and black TiO2 NTs using temperature-dependent synchrotron-based X-ray diffraction. Thermal treatments reveal that phase transitions occur in the ranges of 210-240 °C for normal NTs and 270-300 °C for black NTs. The onset temperature and crystallization growth are dependent on size, especially NT length, at least in the system under investigation. We observe anisotropic crystallization in quantum confinement, with the unit cell undergoing compression in the a-axis and expansion in the c-axis during crystallization. The longest black NTs (BV50T4) show a significant difference in the c/a ratio. Defects, such as oxygen vacancies, localize on specific NT planes.

H2O2-assisted room temperature preparation of crystalline TiO2 and Ti3C2Tx-derived C-doped amorphous TiOx homojunction for photocatalytic degradation of tetracycline

The light absorption, active sites, and charge carriers separation of photocatalysts are extremely important factors in the field of photocatalysis. Near-perfect lattice-matched homojunction constructed using disorder engineering and doping strategies is an effective strategy to improve photocatalytic activity. Herein, we developed crystalline TiO2 nanoparticles (NPs) and Ti3C2Tx MXene-derived C-doped amorphous TiOx homojunction (TCT) at room temperature. In this homojunction, TiO2 NPs are evenly distributed on the surface of the C-TiOx nanosheet to form a type-II structure, which promotes the separation of photogenerated carriers. The light absorption range of TCT extends to 550 nm due to the presence of intermediate energy levels in C-TiOx, which increases its photon absorption capacity. Moreover, TCT possesses a large number of oxygen vacancies, which are beneficial for improving the adsorption and degradation of pollutants. These characteristics of TCT could significantly improve its photodegradation performance for tetracycline. Interestingly, the precursor mass ratio of TCT with the best degradation efficiency is different under different illumination conditions, which is attributed to the different band gaps of C-TiOx and TiO2 NPs resulting in different light absorption ranges. This work provides a new approach to rationally designing crystalline and amorphous homojunction for photocatalytic applications.

Effect of crystalline TiO2 on V2O5WO3/TiO2 as tunable low-temperature shift De-NOx catalyst

Based on the crystalline size of anatase TiO2, a series of tunable low-temperature shift V2O5-WO3/TiO2 (VW/Ti) catalysts for NH3 selective catalytic reduction (NH3-SCR) of NOx were prepared by impregnation process. These catalysts contained a loading amount of 2 wt% WO3 and either 2 or 5 wt% V2O5. The tunable low-temperature shift De-NOx performance of the VW/Ti catalysts was significantly enhanced and dramatically decreased after heat treatment of TiO2 from 100 °C to 700 °C (Ti100 ∼ Ti700). Nearly 100 % De-NOx efficiency was achieved at a gas hourly space velocity (GHSV) of 60,000 h−1. A notable shift from higher to lower temperatures was observed from V2W2/Ti100 to V2W2/Ti600; however, the activity was lost for V2W2/Ti650 to V2W2/Ti700. When the V2O5 loading increased from 2 wt% to 5 wt%, the V5W2/Ti600 showed the highest De-NOx efficiency at 225 °C, demonstrating a remarkable synergistic effect compared to the V2W2/Ti100 catalyst, which achieved maximum efficiency at 375 °C. The De-NOx performance and low-temperature shift effect of these catalysts were elucidated by considering TiO2 crystalline size, the synergistic effect between V2O5 content and TiO2, and the V4+/V5+ oxidation state of V2O5 in the catalyst. Additionally, the high crystalline TiO2-based V2W2/Ti600 catalyst prepared in this study is expected to effectively decompose NOx at low temperatures, in contrast to the low crystalline TiO2-based V2W2/Ti100 catalyst.

Fabrication of Electrospun Porous TiO2 Dielectric Film in a Ti–TiO2–Si Heterostructure for Metal–Insulator–Semiconductor Capacitors

The development of metal–insulator–semiconductor (MIS) capacitors requires device miniaturization and excellent electrical properties. Traditional SiO2 gate dielectrics have reached their physical limits. In this context, high-k materials such as TiO2 are emerging as promising alternatives to SiO2. However, the deposition of dielectric layers in MIS capacitors typically requires high-vacuum equipment and challenging processing conditions. Therefore, in this study, we present a new method to effectively fabricate a poly(vinylidene fluoride) (PVDF)-based TiO2 dielectric layer via electrospinning. Nano-microscale layers were formed via electrospinning by applying a high voltage to a polymer solution, and electrical properties were analyzed as a function of the TiO2 crystalline phase and residual amount of PVDF at different annealing temperatures. Improved electrical properties were observed with increasing TiO2 anatase content, and the residual amount of PVDF decreased with increasing annealing temperature. The sample annealed at 600 °C showed a lower leakage current than those annealed at 300 and 450 °C, with a leakage current density of 7.5 × 10−13 A/cm2 when Vg = 0 V. Thus, electrospinning-based coating is a cost-effective method to fabricate dielectric thin films. Further studies will show that it is flexible and dielectric tunable, thus contributing to improve the performance of next-generation electronic devices.

Impact of titanium dioxide/graphene in polyvinylidene fluoride nanocomposite membrane to intensify methylene blue dye removal, antifouling performance, and reusability

AbstractThe development of efficient water purification technologies is a critical research focus driven by the crucial role of clean water sources for ecological sustainability. This study explores the strategic incorporation of nanoparticles within polyvinylidene fluoride (PVDF) membranes as a promising approach to enhance membrane performance for wastewater remediation. PVDF membranes containing varying ratios of graphene (GR) and titanium dioxide (TiO2) nanocomposites were fabricated via phase inversion method. Characterization techniques including XRD, FTIR, and FESEM‐EDX revealed that the 80% GR nanocomposite membrane exhibited desirable structural and functional properties with pronounced sponge‐like morphology and homogenous nanoparticle distribution. Fourier‐transform infrared spectroscopy and x‐ray diffraction analysis confirmed the 80% GR membrane retained PVDF crystallinity while uniquely eliminating TiO2 crystallinity. Subsequently, performance testing demonstrated the 80% GR nanocomposite membrane had the highest water flux and methylene blue dye rejection rates compared to other ratios and the pristine PVDF membrane. Both fabricated membranes exhibited sufficient reusability and antifouling properties. However, 80% GR ratio exhibited superior antifouling properties, indicating its potential as an optimal material for improving membrane hydrophilicity and overall water purification technologies. These findings underscore the strategic utility of GR‐TiO2 nanocomposites for enhancing PVDF membrane performance in sustainable wastewater treatment applications.

Sunlight-driven charge separation for a heterojunction of nano-pyramidal CuWO4-MOF modified TiO2 nanoflakes for photocatalytic degradation of ciprofloxacin

The study presents a breakthrough of a balanced charge separation for heterojunction CuWO4-TiO2 cocatalyst to efficiently enhance visible light photocatalytic degradation of ciprofloxacin (CIP). A solvothermal-synthesized nanopyramid-like CuWO4 semiconductor was assembled before sol–gel treatment with TiO2 precursors to generate CuWO4-TiO2 nanocomposites. The optical, structural, and morphological properties of CuWO4-TiO2 were elucidated using UV–Vis DRS, XRD, FTIR, Raman spectroscopy, and TEM/SEM techniques. The UV–Vis DRS spectroscopy of as-synthesized CuWO4-TiO2 cocatalyst demonstrated enhanced visible light absorbance. The XRD patterns of CuWO4-TiO2 revealed a triclinic phase nanocrystal. The O-Ti–O functionality was confirmed by FTIR spectroscopy. The photoactive bands corresponding to anatase redshift were observed from Raman spectroscopy of CuWO4-TiO2 nanocomposite. The PL studies attributed this redshift to the elevated extra energy bands that aid electron/hole pair charge separation in a co-catalyst heterojunction CuWO4-TiO2 nanocomposite afforded by embedding CuWO4-MOF within TiO2 crystalline. The TEM showed that un-sintered CuWO4.MOF mimicked a pyramidal shape and converted to nanoflakes upon sintering, while TiO2 and CuWO4-TiO2 retained a tetragonal shape. The photocatalytic activity of CuWO4-TiO2 cocatalyst was studied using CIP, as a model pollutant. The innovative design of 5CuWO4-TiO2 charge separation nanocomposite completely degraded 10 mg L−1 CIP solution at pH = 6.31 (natural pH) and 9 under 120 min of sunlight irradiation.

Structural connectivity and bioactivity in sol–gel silicate glass design

Bioactive glasses (BGs) bond with bone by forming hydroxy carbonate apatite (HCA) upon reaction in physiological fluid, a phenomenon known as bioactivity. BGs structural network connectivity determines their bioactivity. Sol–gel BGs are synthesized through the hydrolysis and condensation of metal alkoxide precursors in the presence of a catalyst, in aqueous environments. Several sol–gel synthesis parameters directly impact BG network connectivity: pH (i.e. acid or basic catalysis), water to alkoxide ratio (Rw), alkoxide type and presence of dopant ions. However, the relationship between bioactivity and these parameters remains surprisingly unexplored.This study highlights the relationship between synthesis pH, Rw, network connectivity and bioactivity in silica-based sol-gel BGs and BGs doped with titanium (Ti) ions (TiBGs), the latter selected for their known ability to enhance network connectivity. BGs and TiBGs are synthesized with various Rw values under acidic and basic conditions, and their bioactivity is assessed in simulated body fluid for 7 days.Increasing Rw decreases network connectivity and increases bioactivity of BGs with high network connectivity, as observed for base-catalyzed BGs and for both acid and base catalyzed TiBGs, but not in BGs with lower connectivity as evidenced in acid-catalyzed BGs. Basic catalysis of TiBGs prevents crystalline TiO2 domain formation, which was instead consistently observed in TiBGs synthesized under acidic catalysis.These findings help the design of BGs for applications where ion release needs to be enhanced even in the presence of dopants that slow down HCA formation, and of BGs with specific properties, e.g. TiO2-containing BGs with potential bactericidal activity. Statement of significanceBioactive glasses (BGs) bond with bone by dissolving and forming hydroxycarbonate apatite (HCA) on their surface, offering applications in medicine and dentistry. BG's network connectivity influences its dissolution rate, and hence HCA formation. While solution-gelation (sol-gel) is commonly used for BG production, the effect of sol gel synthesis parameters on HCA formation remains unexplored. We studied the relationship between synthesis parameters (water-to-alkoxide ratio (Rw), catalyst, and dopant ions, particularly titanium), BG network connectivity, and HCA formation. We find that increasing Rw with any catalyst enhances HCA formation, particularly in glasses with high network connectivity. This understanding allows tailoring BG synthesis for different applications, e.g. those requiring doping with ions that increase network connectivity and fills a crucial gap in BG literature.

Ultrathin ZrO2 thickness control on TiO2/ZrO2 core/shell nanoparticles using ZrO2 atomic layer deposition and etching

Atomic layer deposition (ALD) and atomic layer etching (ALE) techniques were used to control the ZrO2 shell thickness on TiO2/ZrO2 core/shell nanoparticles. ALD and ALE were performed at 200 °C while the nanoparticles were agitated using a rotary reactor. To increase the ZrO2 shell thickness, ZrO2 ALD films were deposited using sequential exposures of tetrakis(dimethylamino) zirconium and H2O. Ex situ analysis using transmission electron microscopy (TEM) observed the growth of the ZrO2 shells. The ZrO2 ALD led to more spherical ZrO2 shells on the crystalline and irregular TiO2 cores. The ZrO2 ALD on the nanoparticles had a growth rate of 0.9 ± 0.1 Å/cycle. Tunable ZrO2 coatings were observed with thicknesses ranging from 5.9 to 27.1 nm after 240 ZrO2 ALD cycles. To demonstrate the decrease in the ZrO2 shell thickness, the ZrO2 film was then etched using sequential hydrogen fluoride (HF) and TiCl4 exposures. Quadrupole mass spectrometry experiments performed in a separate reactor identified the volatile products during ZrO2 ALE. H2O was monitored during HF exposures, and ZrCl4 etch products and TiFxCly ligand-exchange products were observed during TiCl4 exposures. Ex situ TEM studies revealed that the ZrO2 shells remained spherical during ZrO2 ALE. The ZrO2 ALE on the nanoparticles had an etch rate of 6.5 ± 0.2 Å/cycle. Tunable ZrO2 coatings were produced from 27.1 down to 7.6 nm using 30 ZrO2 ALE cycles. This study demonstrated that ZrO2 ALD and ZrO2 ALE can control the thickness of ZrO2 shells on TiO2/ZrO2 core/shell nanoparticles without inducing nanoparticle agglomeration.

Fabrication of Silica–Titanium Composite Film on Wood Surface and Optimization of Its Structure and Properties

In this thesis, wood loaded with a silica–titanium (Si-Ti) composite film was prepared using the sol–gel method in order to achieve improved wood with high hydrophobicity and photocatalytic activity under visible light. The factors affecting the structure and properties of the composite film, as well as the optimization process, were discussed. Infrared analysis revealed that the vibrational intensity of Si-O-Si, Ti-O-Ti, and Ti-O-Si telescopic vibration peaks increased with an increase in vinyltriethoxysilane (VETS). Additionally, the number of Ti-O-Ti telescopic vibration peaks also increased with an increase in VETS. Furthermore, the intensity of -NO3, Si-O-Si, and Ti-O-Ti telescopic vibrational peaks was enhanced with a higher dosage of nitric acid. Conversely, the intensity of -OH telescopic vibrational peaks decreased with an increase in drying temperature. XRD analysis showed that nitric acid could promote the transformation of TiO2 from amorphous to anatase, while SiO2 would reduce the grain size of anatase TiO2 and promote the growth of rutile TiO2. Additionally, wood surfaces loaded with Si-Ti composite film changed from hydrophilic to hydrophobic, with significant differences observed between different levels of each factor. The photocatalytic activity of surface-loaded Si-Ti composite films on wood was most affected by the amount of nitric acid, which influenced crystallinity of TiO2 and thus impacted the photocatalytic activity. Furthermore, changes in VTES dosage not only affected the crystalline phase of TiO2 and the grain size of Si-Ti composite film but also influenced the crystallinity of TiO2 through generating SiO2. Finally, based on optimal preparation process (titanium–alcohol ratio of 1:5, titanium–silicon ratio of 1:0.2, titanium–acid ratio of 1:0.5, and drying temperature of 100 °C), wood surfaces loaded with Si-Ti composite film achieved a contact angle up to 125.9° and exhibited a decolorization rate for rhodamine B under UV light reaching 94% within 180 min.

Preparation of self-assembled graphene materials with assisted multi-structured TiO2: Internal three-phase heterojunction built by doping with Al3+

Conductive coatings provide electromagnetic shielding against interference and radiation from electromagnetic waves. This is critical for electronic devices, communications equipment, medical instruments, and other industries. In this paper, XRD and Raman proved that Al3+ doped anatase, rutile, and brookite coexisting mixed crystalline phase TiO2, which evolved into highly conductive powder materials after ultrasonically compounding graphene, are prepared by simply controlling the calcination temperature. Tauc spectra proved the three-phase heterojunction shortens the distance between the conduction and valence bands, and electron jumping becomes easy. XPS proves that with low-price Al3+, the high-price Ti4+ in the lattice will be replaced, forming oxygen vacancies. A fast charge transfer pathway (Al–O–C) is established between Al3+ and graphene, and the synergistic effect of the two greatly reduces the resistivity. Four-probe test material resistance learned the resistivity of TAl-G is 57 % lower than that of T-G. At the same time, the excellent electrical conductivity of the TAl-G composite makes it suitable for practical applications in antistatic coatings, while the significantly shorter bandgap gives it great potential for photoelectrocatalysis.

Tailoring the crystalline and amorphous phase ratios of TiO2 through the use of organic additives during hydrothermal synthesis

The photocatalytic properties of TiO2 are primarily determined by its crystallinity and crystalline phase ratios. To improve the photocatalytic properties of TiO2, greater control over the formation of crystalline and amorphous phases during synthesis is therefore required. In this study, we demonstrate how the addition of minute amounts of three organic compounds (isopropanol, acetone and acetic acid) during hydrothermal treatment affects the amorphous and crystalline phase ratios: the addition of isopropanol or acetone accelerates the phase transition from anatase and brookite to rutile, whereas the addition of acetic acid inhibits the transformation of anatase to rutile, increasing the content of amorphous phase compared to samples where no organic compound was added. We show that the combination of the organic compound added, along with the duration of the hydrothermal treatment, can be used to tailor the phase composition of TiO2, so as to obtain either: i) TiO2 with a high content of both rutile and amorphous phase, ii) TiO2 with a high rutile content and iii) TiO2 with different ratios of all four phases, when the duration of synthesis is short (2–4 h). The materials synthesized exhibited high photocatalytic activity (in most cases higher than P25), which is attributed to the beneficial phase composition and high specific surface area.

Simultaneous determination of the phase boundary thermal resistance and thermal conductivity in phase-separated TiO2 thin films

Phase boundaries, most often between crystalline and amorphous phases of a material, are ubiquitous lattice imperfections in thin films, particularly deposited by low temperature processes such as atomic layer deposition (ALD). Thermal resistances from these boundaries may impede phonon transport and reduce thermal conductivity. However, to date, there have been no reports on the direct measurement of the phase boundary thermal resistance, due in part to challenges associated with fabricating an atomically flat yet geometrically planar interface between different phases within a film. Here, we present a systematic study to simultaneously determine the phase boundary thermal resistance and thermal conductivity in a series of phase-separated titanium oxide (TiO2) thin films prepared via plasma-enhanced ALD (PEALD). A precise implementation of per-cycle plasma treatment enables extremely localized crystallization—i.e., plasma-assisted atomic layer annealing (ALA)—and the fabrication of crystalline/amorphous layered structures with their respective thicknesses systematically varied. Frequency-domain thermoreflectance measures the effective thermal conductivity of each film and its top and bottom interfaces, confirmed independently using time-domain thermoreflectance. We simultaneously solve a system of linear equations generated by applying a series resistor model to each film, yielding the phase boundary thermal resistance of 5.1 m2 K GW–1 between crystalline and amorphous TiO2, as well as the thermal conductivities of 5.1 and 2.1 W m–1 K–1 for crystalline and amorphous TiO2, respectively. The results suggest that the crystalline/amorphous phase boundary acts like a layer of crystalline (amorphous) TiO2 with equivalent thickness ∼26 (∼11) nm.

Conductometric H2S Sensors Based on TiO2 Nanoparticles.

High-performance hydrogen sulfide (H2S) sensors are mandatory for many industrial applications. However, the development of H2S sensors still remains a challenge for researchers. In this work, we report the study of a TiO2-based conductometric sensor for H2S monitoring at low concentrations. TiO2 samples were first synthesized using the sol-gel route, annealed at different temperatures (400 and 600 °C), and thoroughly characterized to evaluate their morphological and microstructural properties. Scanning electronic microscopy, Raman scattering, X-ray diffraction, and FTIR spectroscopy have demonstrated the formation of clusters of pure anatase in the TiO2 phase. Increasing the calcination temperature to 600 °C enhanced TiO2 crystallinity and particle size (from 11 nm to 51 nm), accompanied by the transition to the rutile phase and a slight decrease in band gap (3.31 eV for 400 °C to 3.26 eV for 600 °C). Sensing tests demonstrate that TiO2 annealed at 400 °C displays good performances (sensor response Ra/Rg of ~3.3 at 2.5 ppm and fast response/recovery of 8 and 23 s, respectively) for the detection of H2S at low concentrations in air.

Effects of TiO2 Nanoparticles Synthesized via Microwave Assistance on Adsorption and Photocatalytic Degradation of Ciprofloxacin.

In this study, the optimal microwave-assisted sol-gel synthesis parameters for achieving TiO2 nanoparticles with the highest specific surface area and photocatalytic activity were determined. Titanium isopropoxide was used as a precursor to prepare the sol (colloidal solution) of TiO2. Isopropanol was used as a solvent; acetylacetone was used as a complexation moderator; and nitric acid was used as a catalyst. Four samples of titanium dioxide were synthesized from the prepared colloidal solution in a microwave reactor at a temperature of 150 °C for 30 min and at a temperature of 200 °C for 10, 20, and 30 min. The phase composition of the TiO2 samples was determined by X-ray diffraction analysis (XRD) and Fourier-transform infrared spectroscopy (FTIR). Nitrogen adsorption/desorption isotherms were used to determine the specific surface area and pore size distributions using the Brunauer-Emmett-Teller (BET) method. The band-gap energy values of the TiO2 samples were determined by diffuse reflectance spectroscopy (DRS). The distribution of Ti and O in the TiO2 samples was determined by SEM-EDS analysis. The effects of adsorption and photocatalytic activity of the prepared TiO2 samples were evaluated by the degradation of ciprofloxacin (CIP) as an emerging organic pollutant (EOP) under UV-A light (365 nm). The results of the photocatalytic activity of the synthesized TiO2 nanoparticles were compared to the benchmark Degussa P25 TiO2. Kinetic parameters of adsorption and photocatalysis were determined and analyzed. It was found that crystalline TiO2 nanoparticles with the highest specific surface area, the lowest energy band gap, and the highest photocatalytic degradation were the samples synthesized at 200 °C for 10 min. The results indicate that CIP degradation by all TiO2 samples prepared at 200 °C show a synergistic effect of adsorption and photocatalytic degradation in the removal process.

Investigate the biological activities of Lawsonia inermis extract synthesized from TiO2 doped graphene oxide nanoparticles.

Nanoparticles of titanium dioxide (TiO2) were made by reacting graphene oxide (GO) with Lawsonia inermis leaf extract. X-ray diffraction (XRD) analysis revealed crystalline TiO2 doped GO nanoparticles composed of a variety of anatase phases. Initially, UV-vis spectroscopy was performed to confirm the biogenesis of TiO2 doped GO nanoparticles (NP's). Using SEM, the research showed that the biosynthesized TiO2 nanoparticles were mostly spherical, polydispersed, and of a nanoscale size. Because of the energy dispersive X-ray spectroscopy (EDS) pattern, distinct and robust peaks of titanium (Ti) and oxygen (O) were observed, which were supportive of the formation of TiO2 nanoparticles. By using fourier transform infrared (FTIR) spectroscopy, it was demonstrated that terpenoids, flavonoids, and proteins are involved in the biosynthesis and production of TiO2 doped GO nanoparticles. 2,2-diphenylpicrylhydrazyl (DPPH) assays were conducted to evaluate the free radical scavenging activity of TiO2 doped GO nanoparticles. Additionally, the TiO2 doped GO NPs had enhanced antioxidant activity when compared with the TiO2 matrix. A series of pure TiO2 and TiO2 doped GO nanoparticles (5, 10, 50, and 100 mg/mL) solutions were investigated for their antibacterial activities. In the current study, zebrafish embryos exposed to pure TiO2 and TiO2 doped GO nanoparticles were toxic and suffered a low survival rate based on concentration. During photocatalysis, O2˙ and ˙OH radicals are rapidly produced because of the reactive species trapping experiment. It was estimated that pure TiO2 nanoparticles and those doped with GO were 80% effective in degrading methyl orange(MO) after 120 min, respectively. RESEARCH HIGHLIGHTS: The UV-vis absorption spectra showed a maximum absorbance peak at 290 nm. SEM, the pure TiO2 doped GO NPs exhibit agglomeration and spherical shape. When tested in zebrafish embryos, TiO2 NPs are toxic at high concentrations. GO nanoparticles showed better antioxidant activity. NPs exhibited concentration dependent antioxidative activity.