Effects of TiO2 doping on the defect chemistry and thermo-physical properties of Yb2O3 stabilized ZrO2

Yb₂O₃ stabilized ZrO₂ (YbSZ) doped with different TiO₂ contents were produced, and their phase structure, thermal conductivities and thermal expansion coefficients were investigated. A new solid-solution model is proposed, i.e. Ti⁴⁺ would take the interstitial sites when its content is below a critical value (≤2.5 mol%) and then substitute for Zr⁴⁺. The abnormal lattice volume and thermo-physical properties of 2.5 mol% TiO₂ doped YbSZ, and the positive effects of TiO₂ doping on the thermal conductivity at moderate doping level are consistent with the new defect model. However, monoclinic phase is formed when the TiO₂ content reaches to 10 mol% and its content increases with doping content, which have negative influence on the thermo-physical properties. Considering the comprehensive properties, 10 mol% TiO₂ doped YbSZ is considered as a promising thermal barrier coating ceramic.     

Ultrafine Cu nanoparticles decorated porous TiO2 for high-efficient electrocatalytic reduction of NO to synthesize NH3

Low-temperature electrocatalytic reduction of nitric oxide (NORR) is promising for the low-cost, high-efficiency removal and utilization of nitric oxide (NO), which couples the two crucial industrial processes of denitration and synthetic ammonia. We reported a binary catalyst of Cu/P–TiO₂ for NORR process, which took advantages of the Cu electrocatalysts and porous TiO₂. The increase of surface areas and channels can improve the adsorption of NO molecules. The decoration of the ultrafine Cu nanoparticles on the porous TiO₂ may prevent the agglomeration of ultrafine Cu nanoparticles. The as-prepared Cu/P–TiO₂ electrode exhibits excellent electrocatalytic activity with a Faraday efficiency of 86.49% and NH₃ yield of 3520.80 μg·h^?1·mg^?1 in 0.1 M K₂SO₄ at ?0.3 V vs. RHE. The mechanism of the NORR reaction process with Cu/P–TiO2 catalysts was also discussed. This research may broaden the application areas of TiO₂-based materials in the electrocatalysis and provide a new sight in the treatment of NO pollutants.     

A biotemplate synthesized hierarchical Sn-doped TiO2 with superior photocatalytic capacity under simulated solar light

Despite a number of studies have been carried out on TiO₂ based materials as photocatalysts for water pollutant treatment, it still needs sustained effort to extend the optical range of the photocatalysts and inhibit the recombination of photo-induced carriers to improve their catalytic activities under solar light. In this work, a series of Sn-doped TiO₂ with different amounts of Sn doping (1, 5, 10 and 20 mol%) were biomimetically synthesized by a facile sol–gel method using cellulosic cotton as biotemplate. The Sn-doped TiO₂ materials possess a typical three-dimensional hierarchical structure of microtubes consisting of interwoven nanofibers. The photocatalytic performance was evaluated via the degradation of methylene blue (MB) (10.0 mg L^?1) under Xenon lamp simulated solar irradiation. The results show that Sn(5)-TiO₂ (5 mol% Sn doping) sample exhibits an outstanding photocatalytic capacity with a superior degradation rate of higher than 98% within 30 min and a good reusability without significant decrease of activity after reused for four cycles. The most significantly improved photocatalytic capacity of TiO₂ is ascribed to more extra surface hydroxyl groups and accessible active sites provided by the relatively high surface area, and a higher light capturing and utilization efficiency with less recombination of the photogenerated electron-hole pairs endowed by the good synergistic effect of the special hierarchically porous microstructure and the appropriate amount of Sn doping. Whereas, the excessive Sn doping reduces the photocatalytic activity obviously, resulting from the phase transformation of TiO₂ generating more rutile phase with less reactivity, the phase separation with clear grain boundary blocking the active sites, and the extra Sn⁴⁺ acting as the recombination center. This research presents a facile biomimetic synthesis strategy combined with the traditional sol–gel method to develop various ion doped metal oxides as photocatalysts with enhanced activity.     

Significantly improved dielectric properties of TiO2 ceramics through acceptor-doping and Ar/H2 annealing

The acceptor-doped rutile TiO₂ ceramics, x mol% M₂O₃-(1-x) mol% TiO₂ (M = Al³⁺, Ga³⁺, and In³⁺), were prepared by solid state reaction method. The influence of Ar/H₂ annealing on the structural and dielectric properties of the ceramics were systematically investigated. Our results reveal that the dielectric properties of the ceramics can be significantly improved by the Ar/H₂ annealing. Ga³⁺ is found to be the most suitable dopant with the best doping level of 5 mol%. Excellent dielectric properties of colossal and flat dielectric permittivity (~1.2 × 10⁵ (@1 kHz and 25 °C), low dielectric loss (~0.1), and good frequency stability were achieved over the temperature range of -70–150 °C in the Ar/H₂-annealed 5 mol% Ga₂O₃-95 mol% TiO₂ ceramic. This approach of acceptor-doping and Ar/H₂ annealing leads to two thermally activated relaxations in the sample. The low-temperature relaxation is argued to be a Maxwell-Wagner relaxation caused by frozen electrons, while the high-temperature relaxation is a glass-transition-like relaxation associated with the freezing process of the electrons. This work highlights that engineering low-temperature Maxwell-Wagner relaxation paves a new way other than the frequently used acceptor-donor dual doping to design superior dielectric properties in the TiO₂ system.     

Effect of Pt or Pd doping on stability of TiO2 nanoparticle suspension in water

Stability of suspensions of TiO₂ nanoparticles synthesized by the flame aerosol reactor (FLAR) could be altered by doping TiO₂ nanoparticles with Pt, Pd, or Pt–Pd dopants. It was found that doping of TiO₂ with Pd or Pt could contribute to the control of the agglomeration of TiO₂ suspended in water. With the change of doping content, the isoelectric point (IEP) of stable TiO₂ suspension decreased gradually from 5 to 3.6 while the specific surface area was increased from 43.27 to 60.84 m²/g. With pH > 6.0, 2 wt% Pt–Pd/TiO₂ suspension exhibited the lowest agglomeration behavior. The plausible intrinsic structures of Pt, Pd, and Pt–Pd doped TiO₂ nanoparticles were proposed and discussed with respect to their IEP based on the DLVO theory.     

Effect of silver (Ag) ions irradiation on the structural,optical and photovoltaic properties of Mn doped TiO2 thin films based dye sensitized solar cells

Dye sensitized solar cell (DSSC) is an emerging energy harvesting tool which converts direct sunlight into electrical energy. These cells have much better properties in contrast with silicon based solar cells because of their flexible nature, light weight, low cost, environment friendly nature, and involvement of a simple manufacturing process. Since, a photoanode is the backbone of DSSC, we synthesized a pure and 1% manganese (Mn) doped titanium dioxide (TiO₂) films by sol-gel method which are irradiated with silver (Ag) ions at two different concentrations (2 × 10¹⁴ and 4 × 10¹⁴) ions-cm^?2. X-ray diffraction revealed that Mn doping followed by Ag irradiation transformed TiO₂ from pure anatase to rutile phase. Ultraviolet–visible spectroscopy exposed the reduction in band gap of TiO₂ film during this doping and irradiation process. Therefore, absorption is enhanced with red shift in UV-range. When these films are used as a photoanode in DSSC, 1% Mn doped TiO₂ film exposed with Ag at the concentration of (2 × 10¹⁴) ions-cm^?2 exhibited maximum efficiency of 2.40%.     

Structural and optical characterization of Zn0.95−xMg0.05AlxO nanoparticles

The structural and optical properties of ZnO nanoparticles doped simultaneously with Mg and Al were investigated. XRD results revealed the hexagonal wurtzite crystalline structure of ZnO. The FE-SEM study confirmed the formation of nano-sized homogeneous grains whose sizes decreased monotonously with increasing doping concentrations of Mg and Al. The absorption spectra showed that band gap increased from 3.20 to 3.31 eV with Mg doping. As the Al concentration changed from x=0.01 to x=0.06 mol% at constant Mg concentration the band gap observed to be decreased. Particle sizes estimated from effective mass approximation using absorption data and these values are in good agreement with the crystallite sizes calculated from XRD data. Raman spectra of ZnO showed a characteristic peak at 436 cm⁻¹ correspond to a non-polar optical phonon E₂ (high). With increase of the Al doping concentrations, E₂ (high) phonon frequency shifted to 439 cm⁻¹ from to 436 cm⁻¹. The origin of E₂ (high) peak shift in ZnO nanoparticles is attributed to optical phonon confinement effects or the presence of intrinsic defects on the nanoparticles. PL spectra indicated that with increase of Al co-doping along with Mg into ZnO, intensity of the peak positioned at 395 nm was initially increased at x=0 and then decreased with increase of the Al concentrations from x=0.01 to x=0.06 mol%.     

TiO2–SnO2 nanomaterials for gas sensing and photocatalysis

Nanopowders of TiO₂–SnO₂ over a full composition range extending from 100 mol% TiO₂ to 100 mol% SnO₂ are obtained by the sol–gel method from TTIP and SnCl₂·5H₂O precursors of Ti and Sn, respectively followed by calcination at 400 °C. The samples are characterized by means of BET, XRD and TEM. Optical properties of the prepared nanomaterials are studied as well. TEM images indicate that the nanoparticles are regular in shape. The specific surface area, SSA of TiO₂ is 95 m²/g while that of SnO₂ amounts to 129 m²/g. The highest SSA of 156 m²/g is achieved at 20 mol% of TiO₂. Occurrence of rutile, anatase and brookite polymorphic forms depends on the chemical composition of nanopowders. Formation of rutile-type solid solution of TiO₂–SnO₂ over the range of 0–80 mol% TiO₂ is confirmed by Vegard rule applied to lattice constants. Electronic band gap decreases with Ti content from 3.84 eV (100 mol% SnO₂) to 3.18 eV (100 mol% TiO₂).     

Plasmonic Effects of Infiltrated Silver Nanoparticles Inside TiO2 Film: Enhanced Photovoltaic Performance in DSSCs

The plasmonic effects of infiltrated silver (Ag) nanoparticles, with different contents, inside a nanostructured TiO₂ film on the photovoltaic performance of dye‐sensitized solar cells (DSSCs) are explored. The synthesized Ag nanoparticles are immobilized onto deposited TiO₂ nanoparticles by a new strategy using 3‐mercaptopropionic acid (MPA), a bifunctional linker molecule. Transmission electron microscope (TEM) images show that monodispersed Ag and polydispersed TiO₂ nanoparticles have an average diameter of 12 ± 3 nm and 5 ± 1 nm, respectively. Moreover, Fourier transform infrared spectroscopy (FTIR) analysis reveals that Ag nanoparticles were successfully functionalized and capped with MPA. Optical studies on the MPA‐capped Ag nanoparticles inside TiO₂ film show an increase in the total absorbance of the electrode. Moreover, EIS measurements confirm that MPA‐capped Ag nanoparticles inhibit the charge recombination and improve the stability of nanoparticles in I₃^?/I^? electrolyte. The DSSC assembled with optimal content of MPA‐capped Ag nanoparticles demonstrated an enhanced power conversion efficiency (8.82% ± 0.07%) compared with the pure TiO₂ (7.30% ± 0.05%). The increase in cell efficiency was attributed to the enhanced dye light absorption in strength and spectral range due to the surface plasmon resonance of MPA‐capped Ag nanoparticles in the photoanode.     

Electrocatalytic activity of Pt nanoparticles deposited on porous TiO2 supports toward methanol oxidation

Porous TiO₂ thin films were prepared on the Si substrate by hydrothermal method, and used as the Pt electrocatalyst support for methanol oxidation study. Well-dispersed Pt nanoparticles with a particle size of 5–7 nm were pulse-electrodeposited on the porous TiO₂ support, which was mainly composed of the anatase phase after an annealing at 600 °C in vacuum. Cyclic voltammetry (CV) and CO stripping measurements showed that the Pt/TiO₂ electrode had a high electrocatalytic activity toward methanol oxidation and an excellent CO tolerance. The excellent electrocatalytic performance of the electrode is ascribed to the synergistic effect of Pt nanoparticles and the porous TiO₂ support on CO oxidation. The strong electronic interaction between Pt and the TiO₂ support may modify CO chemisorption properties on Pt nanoparticles, thereby facilitating CO oxidation on Pt nanoparticles via the bifunctional mechanism and thus improving the electrocatalytic activity of the Pt catalyst toward methanol oxidation.     

Interface excess on Sb-doped TiO2 photocatalysts and its influence on photocatalytic activity

Titanium dioxide (TiO₂) is a well-known photocatalyst that has been used in photocatalysis and has been studied as an alternative for artificial photosynthesis cells. Many works have tried doping this material with different elements to increase its photoactivity; however, a consequence of doping that has not received much attention is the segregation at the nanoparticle interfaces, such as the surface and the grain boundary (GB). In this study, Sb-doped TiO₂ nanoparticles have been produced by the polymeric precursor method, with the compositional range varying from 0 to 2 mol% Sb. The surface excess was measured by the surface lixiviation method, and the GB excess was calculated considering the total amount of Sb and its solubility in the TiO₂ bulk. The results showed that Sb interfacial segregation at both surface and GB increased the specific surface areas, reduced the crystallite sizes, increased the presence of the rutile phase, and changed the CO₂ adsorption, evidenced by DRIFT spectroscopy. The photoactivity was tested by the degradation of acetaminophen (ACT) under UV irradiation, revealing an increase of ~53% of activity for 0.05 mol% Sb-doped TiO₂ compared to undoped TiO₂.     

Visible light induced self-cleaning performance of iron-doped TiO2 nanoparticles for surface applications

This study aimed to enhance the visible light photosensitivity of TiO₂ nanoparticles for self-cleaning applications by doping with Fe³⁺. Nanocrystalline undoped and Fe-doped TiO₂ (Ti_1 − xFe_xO₂, x = .01–.04) were synthesized via sol–gel method. The results demonstrated that Fe-doped TiO₂ nanoparticles exhibited visible light sensitivity and self-cleaning properties. An increased Fe concentration resulted in a red shift in the absorption band edge. Fe_0.03-doped TiO₂ with an average particle size of ∼21 nm, a crystallite size of ∼12 nm, and a band gap of ∼2.86 eV showed the highest photocatalytic activity (60% methylene blue degradation) and super-hydrophilicity (water droplet contact angle 9°) under visible light radiation. These findings highlight the potential of Fe-doped TiO₂ nanoparticles as a promising material for self-cleaning applications.     

Structural and spectral properties of red light emitting Eu3+ activated TiO2 nanophosphor for white LED application

The structural and luminescent properties of Eu³⁺ doped TiO₂ nanophosphors synthesized by low cost combustion method were investigated. The X-ray diffraction analysis revealed that crystallite size decreases with doping concentration. Lattice volume expansion occurred due to the substitution of Ti⁴⁺ ions by larger ionic radii ions Eu³⁺. FESEM images showed prepared phosphors to be nano size spherical shaped particles. Energy band gap of 3 mol% Eu³⁺ doped samples decreased to 3.15 eV due to doping effect. The Eu³⁺ doped TiO₂ nanophosphors exhibited main red emission peak centered at 616 nm under 395 nm UV light excitation. Concentration quenching was observed at 3 mol% doping, that has been ascribed to dipole-dipole interaction. The covalent nature of Eu-O bond and environment around Eu³⁺ ions were discussed using Judd-Ofelt (J-O) intensity parameters. Internal quantum efficiency was calculated using excited state lifetime ⁵D₀ state of Eu³⁺ ion and J-O theory. The CIE colour coordinates and colour purity were calculated using the spectral energy distribution function. Low excited state life time indicated that Eu³⁺ doped TiO₂ can be used as red emitting phosphor for white light emitting diode applications.     

Effect of substitution of SnO2 for TiO2 on the surface and electrocatalytic properties of RuO2+TiO2 electrodes

The effect of substituting SnO₂ for TiO₂ in RuO₂+TiO₂ electrodes has been studied by varying the SnO₂ content systematically in a series of oxides of general composition 30 mol% RuO₂+x mol% SnO₂+(70-x) mol% TiO₂. The surface properties have been investigated by voltammetric curves, the electrocatalytic activity by using O₂ evolution from 1 mol dm^–3 HClO₄ solutions as a test reaction. It has been observed that only the surface area changes at intermediate compositions as a result of morphological modifications, while the electrocatalytic activity increases dramatically as the substitution of SnO₂ for TiO₂ becomes complete. Reasons for that are discussed. The present results do not support the claim that SnO₂ depresses the electrocatalytic activity of oxide electrodes for oxygen evolution.Dedicated to Professor Dr Fritz Beck on the occasion of his 60th birthday.     

Electrospun porous carbon nanofibers/TiO2 composite coated over carbon cloth- A flexible electrode for capacitive deionization

The combination of porous carbon matrix and metal oxide is trending for capacitive deionization (CDI) due to their synergistic electrochemical behaviour and properties. In this research, a flexible electrode based on electrospun porous carbon nanofibers and TiO₂ nanoparticles (particle size ～7 nm) i.e., PCNFs/TiO₂ composite coated over carbon cloth is developed. A facile in-situ activation procedure using sacrificial polymer is adopted over typical chemical activation treatment to synthesize PCNFs/TiO₂ composite. PCNFs/TiO₂ composite is prepared in two steps, possessing a high specific surface area of ～343 m² g^?1 and pore volume of 0.038 cm³ g^?1. Interestingly, CDI unit assembled with PCNFs/TiO₂ composite based flexible electrodes delivers the large salt electrosorption capacity of 204.8 mg g^?1 at voltage 1.2 V in a salt solution of concentration 500 ppm and conductivity 880 μS cm^?1. The excellent adsorption capacity retention of 96.4% up to ten adsorption-regeneration cycles can be a tempting option for future flexible CDI applications.     

Characterizations of TiO2/SiO2/Ni–Cu–Zn Ferrite Composite for Magnetic Photocatalysts

The TiO₂/SiO₂/Ni–Cu–Zn ferrite composite for magnetic photocatalysts with high photocatalytic activity is successfully prepared in this study. The composite are composed of spherical or elliptical Ni–Cu–Zn ferrite nanoparticles about 20–60 nm as magnetic cores, silica as barrier layers with thickness of 15 nm between the magnetic cores and titania shells with thickness approximately 1.5 nm. Photodegradation examination of TiO₂/SiO₂/ Ni–Cu–Zn ferrite composite was carried out in methylene blue (MB) solutions illuminated under a Xe arc lamp with 35 W and color temperature of 6000 K. The results indicated that about 47.1% of MB molecules adsorbed on the TiO₂/SiO₂/Ni–Cu–Zn ferrite composite within 30 min mixing due to it higher pore volume of 0.034 cm³/g, and after 6 h Xe lamp irradiation, 83.9% of MB 16.1% was photodegraded. Compared with the TiO₂ /Ni–Cu–Zn ferrite composite, the TiO₂/SiO₂/Ni–Cu–Zn ferrite composite with silica barrier layer prohibited the photodissolution and enhanced the photocatalytic ability. The magnetic photocatalyst shows high photocatalytic efficiency that the apparent first‐order rate constant k_obs is 0.18427 h^?1, and good magnetic property that the saturation magnetization (M_s) of is 37.45 emu/g, suggesting the magnetic photocatalyst can be easily recovered by the application of an external magnetic field.     

UV–Visible Light Driven Photocatalytic Degradation of Ciprofloxacin by N,S Co-doped TiO2: The Effect of Operational Parameters

Photocatalytic degradation using TiO₂ is one of the most effective techniques for treating residual emerging compounds present in water. However, practical applications are limited since it only absorbs ultraviolet irradiation. Nitrogen and sulfur (N, S) co-doped TiO₂ nanomaterials (N,S-TiO₂) were prepared by a controlled sol–gel method; the characterization and photocatalytic activity have been studied for the removal of ciprofloxacin antibiotic under UV–Visible light. The interstitial doping of nitrogen and sulfur substitute oxygen and titanium into the TiO₂ lattice, which increases the valence band and decreases the conduction band, respectively. The lowest value band-gap of 2.5 eV and the crystallite size of 5.13 nm compared to other available synthesis methods was observed on N,S-TiO₂ which allowed to broaden the light absorption to the visible region. The low level electron and hole recombination was related by the N, S doping. The optimal ciprofloxacin removal was obtained at pH 5.5, a dosage of 0.05 g, initial concentration of 30 mg L^?1 with a removal efficiency of 78.7%. A comparison of the effectiveness of antibiotic treatment of N,S-TiO₂ with synthetic TiO₂ and commercial TiO₂ was also made, taking the potential for regeneration into account. The photocatalytic degradation of ciprofloxacin catalyzed by N,S-TiO₂ was described by pseudo-first-order kinetics.

     

Substantial reduction of leakage currents in La/Er/Zn/Ti multielement-doped BiFeO3 multiferroic thin films

Multi-element doping is an effective method to suppress the leakage of BiFeO₃ (BFO). A systematic study on the effect of various elements (La, Er, Zn, Ti) doping on the leakage performance, mechanism and other electrical properties of BFO films was performed As the kinds of doping elements increases, the leakage current density of the BFO film gradually decreases. The leakage current density is gradually reduced from 5.78 × 10^?2 A/cm² doped with one element (La) to 1.25 × 10^?2 A/cm² doped with two elements (La, Ti), 4.13 × 10^?3 A/cm² doped with three elements (La, Ti, Zn), and 4.53 × 10^?4 A/cm² doped with four elements (La, Er, Zn, Ti). Finally, compared with pure BFO films, the leakage current density in doped BFO films is reduced by two orders of magnitude. Moreover, the conduction mechanism in doped BFO films is gradually changed from space charge limited current to ohmic conduction. This work provides an effective method to ameliorate the leakage of ferroelectric materials and lays a foundation for the practical application of BFO-based films.     

A comparative study of the effect of Pd-doping on the structural,optical, and photocatalytic properties of sol–gel derived anatase TiO2 nanoparticles

Pd-doped anatase TiO₂ nanoparticles were synthesized by a modified sol–gel deposition technique. The synthetic strategy is applicable to other transition and post-transition metals to obtain phase-pure anatase titania nanoparticles. This is important in the sense that anatase titania forms the most hydroxyl radicals (compared to other polymorphs like rutile, brookite, etc.) for better photocatalytic performance. XRD and Raman data confirm the phase-pure anatase formation. Doping of Pd²⁺ into Ti⁴⁺ sites (for substitutional doping) or interstitial sites (for interstitial doping) creates strain within the nanoparticles and is reflected in the XRD peak broadening and Raman peak shifts. This is because of the ionic radii difference between Ti⁴⁺(∼68 pm) and Pd²⁺(∼86 pm). XPS data confirm the formation of high surface titanol groups at the nanoparticle surface and a large number of loosely bound Ti³⁺–O bonds, both of which considerably enhance the photocatalytic activity of the doped nanoparticles. A comparative study with other metal doping (Ga) shows that TiO₂: Pd nanoparticles have more Ti³⁺–O bonds, which enhance the charge transfer rate and hence improve the photocatalytic activity compared to other transition and post-transition metal-doped titania nanostructures.     

The relationship between photo-catalytic performance and optical property over Si-incorporated TiO2

This study focuses on the relationship between photo-catalytic performance and optical property over Si-incorporated TiO₂. The Si-incorporated TiO₂ particles exhibited a pure structure of anatase having a particle size of less than 20 nm and surface area of more than 190 m²/g. The absorbance did not shift to a higher wavelength in spite of the incorporation of the Si ions, but the intensity of the photoluminescence (PL) curve was the smallest in the case of the 2.0 mol% Si-TiO₂, which was related to the recombination between the excited electrons and holes. Based on these results, the photodecomposition of methyl orange in the liquid reaction was enhanced over the 2.0 mol% Si-incorporated TiO₂ compared with that over pure TiO₂: Methyl orange at 10.0 ppm was completely decomposed after 100 min when 1.0 g of the 2.0 mol% Si-incorporated TiO₂ was used.