Annealing impact on the structural and optical properties of electrospun SnO2 nanofibers for TCOs

Tin oxide (SnO₂) nanofibers were fabricated by electrospinning technique and subsequent annealed at different temperatures. The structure, morphology and optical properties of the annealed samples were characterized by X-ray diffraction (XRD), Raman, scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS), transmission electron microscopy (TEM), Fourier transformed infrared (FTIR),and optical absorption techniques. The phase of SnO₂ of all samples is rutile (tetragonal), and at higher annealing temperatures, good crystallinity and lower absorption were obtained. Annealing of the samples at 600 °C caused the lower absorption and higher optical band gap, and the decrease of the absorption was probably because the fiber structure changed from solid to hollow structure. From PL spectra, it was observed that the SnO₂ hollow nanofibers annealed at 600 °C revealed green emission at 530 nm.     

Durable superhydrophobic Zn/ZnO/TiO2 surfaces on Ti6Al4V substrate with self-cleaning property and switchable wettability

Durable superhydrophobic (SHP) Zn/ZnO/TiO₂ surfaces with dendritic structures on Ti₆Al₄V substrate were obtained by chemical etching, electrodeposition and following annealing process. The resultant coatings electrodeposited at ?1.5 V for 10 min and annealed at 190 °C for 60 min showed fine superhydrophobicity with a water contact angle of 160° and a rolling angle less than 1°, showing excellent rolling-off and self-cleaning properties. The morphology, chemical components and growth mechanism of samples were investigated by scanning electron microscopy (SEM), X-ray diffraction pattern (XRD), Energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Surface tribological properties were characterized by a universal mechanical tester (UMT). The as-prepared Zn/ZnO/TiO₂ surface still kept excellent SHP stability after exposure to the air, buried in soil and cold storage at 5 °C in the fridge for one year, as well as excellent repellence to some daily-used liquids such as coke, coffee, red wine, milk and tea. The surface can be reversibly switched between superhydrophobicity and superhydrophilicity by alternating UV illumination and dark storage or heating, which offer possibilities to widen future applications.     

Structural,thermal, dielectric and ferroelectric properties of K0.5Bi0.5TiO3 ceramics

Dense K_0.5Bi_0.5TiO₃ (KBT) lead-free ceramics were prepared by conventional solid reaction route. Their temperature behavior (up to 600 °C) was investigated by X-ray diffraction, DSC, dielectric spectroscopy and electric field-polarization technique. The first temperature dependent Raman scattering studies were also performed. X-ray and Raman scattering results show that samples exhibit a single perovskite structure with cubic symmetry at temperatures higher than approximately 400 °C and with coexistence of the cubic and tetragonal phases below this temperature. Two structural phase transitions between tetragonal phases in temperature range 200–225 °C and between tetragonal and cubic ones near 400 °C are observed. The content of the tetragonal phase increases with decreasing temperature and at room temperature it reaches more than 70%. Temperature- dependent P-E loops and pyroelectric data revealed a polar behavior in KBT up to about 400 °C, which means that the intermediate phase (～270–380 °C) is rather ferroelectric than antiferroelectric.     

Preparation and characterization of poly-hydrogen cyanide nanofibers with high visible light photocatalytic activity

Poly-hydrogen cyanide (PHC) nanofibers were prepared by directly heating the formamide (HCONH₂) in a stainless-steel autoclave at 200 °C. The composition and structure of the products were characterized by X-ray diffraction, transmission electron microscopy, UV–vis diffuse reflectance spectrum, thermogravimetric analysis, Fourier transform IR, Raman and X-ray photoelectron spectroscopy. The results showed that the as-prepared nanofibers are graphite-like structure C/N ratio of 1.23. The as-prepared nanofibers exhibited higher photocatalytic activities by degradation of methyl orange (MO) than N-TiO₂ under visible light irradiation.     

TiO2 nanofibers doped with rare earth elements and their photocatalytic activity

In the present study rare earth doped (Ln³⁺–TiO₂, Ln = La, Ce and Nd) TiO₂ nanofibers were prepared by the sol–gel electrospinning method and characterized by XRD, SEM, EDX, TEM, and UV-DRS. The photocatalytic activity of the samples was evaluated by Rhodamine 6G (R6G) dye degradation under UV light irradiation. XRD analysis showed that all the synthesized pure and doped titania nanofibers contain pure anatase phase at 500 °C but at 700 °C it shows both anatase and rutile phase. XRD result also shows that Ln³⁺-doped titania probably inhibits the phase transformation. The diameter of nanofibers for all samples ranges from 200 to 700 nm. It was also observed that the presence of rare-earth oxides in the host TiO₂ could decrease the band gap and accelerate the separation of photogenerated electron–hole pairs, which eventually led to higher photocatalytic activity. To sum up, our study demonstrates that Ln³⁺-doped TiO₂ samples exhibit higher photocatalytic activity than pure TiO₂ whereas Nd³⁺-doped TiO₂ catalyst showed the highest photocatalytic activity among the rare earth doped samples.     

Combustion synthesis of graphene oxide–TiO2 hybrid materials for photodegradation of methyl orange

Graphene oxide (GO)–TiO₂ hybrid materials with enhanced photocatalytic properties were synthesized by a one-step combustion method using urea and titanyl nitrate as the fuel and oxidizer, respectively. During the synthesis procedure, the precursors containing GO, fuel, and oxidizer were maintained at different combustion temperatures (300–450 °C) for 10 min to ignite the combustion reaction. The effects of combustion temperatures on the weight loss, chemical status and photocatalytic properties were studied by thermogravimetry and differential scanning calorimetry, X-ray photoelectron spectroscopy, Raman, and photoluminescence. GO in the GO–TiO₂ hybrids were not oxidized, but thermally reduced by decomposition of partial oxygen-containing groups. Meantime, the nitrogen doping of GO was achieved. Compared to the neat TiO₂ obtained at same condition, GO–TiO₂ hybrid obtained at 350 °C exhibited enhanced photodegradation performance, which is attributed to the effective photo-generated electron transferring from TiO₂ to partially reduced GO, which confirmed by the photoluminescence quenching of TiO₂.     

The photo-catalytic activities of neodymium and fluorine doped TiO2 nanoparticles

A series of photo-catalysts were synthesized by neodymium and fluorine doped TiO₂, and their characteristics evaluated by X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (UV–vis), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). Neodymium and fluorine doped TiO₂ has obvious absorption in the visible light and the absorption edge shifts toward red wavelength. In addition, compared with pure TiO₂, the doped catalyst has intense absorption at 528, 587, 750, 808, and 881 nm. The catalytic efficiency was tested by monitoring the photo-catalytic degradation of methylene blue (MB) in visible light and ultraviolet light. The results showed that the optimum doping content was Nd:F:TiO₂ = 0.5:5:100 (molar ratio) heat treated at 500 °C, and the reaction rates of MB degradation were estimated to be about 1.76 times and 1.45 times higher than undoped TiO₂ in ultraviolet light and visible light.     

SnS2/TiO2 nanocomposites with enhanced visible light-driven photoreduction of aqueous Cr(VI)

SnS₂/TiO₂ nanocomposites have been synthesized via microwave assisted hydrothermal treatment of tetrabutyl titanate in the presence of SnS₂ nanoplates in the solvent of ethanol at 160 °C for 1 h. The physical and chemical properties of SnS₂/TiO₂ were studied by XRD, FESEM, EDS, TEM, XPS and UV–vis diffuse reflectance spectra (DRS). The photocatalytic activity of SnS₂/TiO₂ nanocomposites were evaluated by photoreduction of aqueous Cr(VI) under visible light (λ>420 nm) irradiation. The experimental results showed that the SnS₂/TiO₂ nanocomposites exhibited excellent reduction efficiency of Cr(VI) (~87%) than that of pure TiO₂ and SnS₂. The SnS₂/TiO₂ nanocomposites were expected to be a promising candidate as effective photocatalysts in the treatment of Cr(VI) wastewater.     

TiO2 nanofibers assembled on graphene-silver platform as a visible-light photo and bio-active nanostructure

The heterogeneous titanium oxide-reduced graphene oxide-silver (TiO₂/RGO/Ag) nanocomposites were successfully prepared by incorporation of two dimensional (2D) RGO nanosheets and spherical silver nanoparticles (NPs) into the 1D TiO₂ nanofibers. The novel TiO₂/RGO/Ag nanocomposites were synthesized by loading TiO₂ nanofibers, prepared via electrospinning technique, on the RGO/Ag platform. The resulting nanocomposites have been characterized using various techniques containing transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and ultra-violet-visible (UV–vis) spectroscopy. Microscopic studies clearly verified the existence of TiO₂ nanofibers with Ag NPs on the surface of RGO sheet and formation of TiO₂/RGO/Ag nanocomposites. Moreover, the results of UV–vis spectroscopy demonstrated that TiO₂/RGO/Ag nanocomposites extended the light absorption spectrum toward the visible region and significantly enhanced the visible-light photocatalytic performance of the prepared samples on degradation of rhodamine B (Rh. B) as a model dye. It was found that, incorporation of 50 µl RGO/Ag into the TiO₂ nanofibers lead to a maximum photocatalytic performance. Also, the improvement of the inactivation of Escherichia coli (E. coli) bacteria under visible-light irradiation was revealed by introduction of RGO/Ag into the TiO₂ matrix. The significant enhancement in the photo and bio-activity of TiO₂/RGO/Ag nanocomposites under visible-light irradiation can be ascribed to the RGO/Ag content by acting as electron traps in TiO₂ band gap.     

Preparation of graphene film decorated TiO2 nano-tube array photoelectrode and its enhanced visible light photocatalytic mechanism

Graphene film decorated TiO₂ nano-tube array (GF/TiO₂ NTA) photoelectrodes were prepared through anodization, followed by electrodeposition strategy. Morphologies and structures of the resulting GF/TiO₂ NTA samples were characterized by scanning electrons microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. In addition, the optical and photoelectrochemical properties were investigated through UV–visible light diffuse reflection spectroscopy, photocurrent response and Mott–Schottky analysis. Furthermore, the photodecomposition performances were investigated through yield of hydroxyl radicals and photocatalytic (PC) degradation of methyl blue (MB) under visible light irradiation. It was found that GF/TiO₂ NTA photoelectrode exhibited intense light absorption both in UV light and visible region, higher transient photoinduced current of 0.107 mA cm⁻² and charge carrier concentration of 0.84 × 10¹⁹ cm⁻³, as well as effective PC performance of 65.9% for the degradation of MB. Furthermore, contribution of several reactive species to the PC efficiency of GF/TiO₂ NTA photoelectrode was distinguished. Moreover, the enhanced visible light PC mechanism was proposed and confirmed in detail.     

Preparation and photocatalytic activity of silver and TiO2 nanoparticles/montmorillonite composites

Ag–TiO₂/montmorillonite (Ag–TiO₂/MMT) was synthesized as photocatalyst using TiCl₄ hydrolysis to introduce nanosized TiO₂ into the interlayer space of the montmorillonite (MMT). Stable pillared TiO₂/MMT was obtained by calcination at 500 °C, then silver was loaded by reduction of silver nitrate. The physico–chemical properties of the photocatalyst were determined by X-ray diffraction (XRD), infrared spectroscopy (IR), atomic absorption spectrophotometer (AAS), nitrogen gas adsorption (BET method) and UV–Visible spectra. The photooxidation activity for methylene blue (M.B.) degradation was as follows: Ag–TiO₂/MMT > TiO₂/MMT > TiO₂(P25). Among them Ag–TiO₂/MMT had the highest photooxidation activity because of its larger specific surface caused by pillaring and loading of silver for improving its light absorption.     

Template-assisted hydrothermal synthesis and photocatalytic activity of novel TiO2 hollow nanostructures

TiO₂ hollow nanostructures were successfully synthesized by a controlled hydrothermal precipitation reaction using Resorcinol–Formaldehyde resin spheres as templates in aqueous solution, and then removal of the RF resins spheres by calcination in air at 450 °C for 4 h. The obtained TiO₂ hollow spheres were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N₂ adsorption–desorption analysis, and UV–visible diffuse reflectance spectroscopy. The photocatalytic activity of the as-prepared samples was evaluated by photocatalytic decolorization of rhodamine B aqueous solution at ambient temperature under UV illumination. The results indicated TiO₂ hollow nanostructures exhibit the excellent photocatalytic activity probably due to the unique hollow micro-architectures.     

Physical properties of V-doped TiO2 nanoparticles synthesized by sonochemical-assisted process

V-doped TiO₂ nanoparticles were synthesized by sonochemical process using titanium isopropoxide as a titanium source, vanadyl acetylacetonate as a dopant source. Sonication was conducted using sonic horn operated at 20 kHz for 20 min until the completely precipitated product was reached. The as-synthesized precipitates with various vanadium dopant (1–5 mol %) were calcined at 500–1000 °C for 4 h. The relevant physical properties of the nanoparticles were characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and transmission electron microscope (TEM). The anatase phase TiO₂ nanoparticles can be synthesized by sonochemical process. Post calcinations process results in the anatase-to-rutile phase transformation and the enhancement in crystallinity with increasing temperature. The results also indicate good incorporation of V ions in TiO₂ lattices and significant effect of V dopant on alternation of interplanar spacing of TiO₂.     

The role of graphene and europium on TiO2 performance for photocatalytic hydrogen evolution

Highly efficient Eu-TiO₂/graphene composites were synthesized by a two-step method such as sol-gel and hydrothermal process. The synthesized photocatalysts were characterized by XRD, TEM, XPS, UV–vis diffuse reflectance spectroscopy and photoluminescence (PL) spectroscopy. The results confirmed that anatase Eu-TiO₂ nanoparticles with average 10 nm sizes were successfully deposited on two-dimensional graphene sheets. The UV–visible spectroscopy showed a red shift in the absorption edge of TiO₂ due to Eu doping and graphene incorporation. Moreover, effective charge separation in Eu-TiO₂/graphene composites was confirmed by PL emission spectroscopy compared to TiO₂/graphene, Eu-TiO₂ and pure TiO₂. The photocatalytic activity for H₂ evolution over prepared composites was studied under visible light irradiation (λ ≥ 400 nm). The results demonstrate that photocatalytic performance of the photocatalysts for hydrogen production increases with increasing doping concentration of Eu upto 2 at%. However, further increase in doping content above this optimum level has decreased the performance of photocatalyst. The enhanced photocatalytic performance for H₂ evolution is attributed to extended visible light absorption, suppressed recombination of electron-hole pairs due to synergistic effects of Eu and graphene.     

Microstructure and elastic modulus of electrospun Al2O3-SiO2-B2O3 composite nanofibers with mullite-type structure prepared at elevated temperatures

In the present work, Al₂O₃-SiO₂-B₂O₃ composite nanofibers with mullite-type structure were prepared using electrospinning technique. The microstructure and elastic modulus of the composite nanofibers obtained at elevated temperatures were studied. The results showed that Al₄B₂O₉ phase formed at 900 °C and then transformed to Al₁₈B₄O₃₃ at 1100 °C. Mullite was also detected in the nanofibers prepared at 1100 °C. Amorphous SiO₂ existed in all samples even the calcination temperature reached up to 1400 °C. The continuous and uniform structure of the composite nanofibers was kept after calcining at different temperatures, while rougher surface was evident due to the growth of the grain caused by the elevated temperature. An increase of elastic modulus of the samples from 9.47 ± 1.91 GPa to 27.30 ± 2.61 GPa was observed when calcination temperatures increased from 800 °C to 1400 °C.     

Impact of acceptor-type substitution on electrical transport properties of zircon-type EuVO4

Magnesium-substituted europium vanadate ceramics, Mg_xEuVO_4 ± δ (x = 0–0.5), were prepared by solid state method and characterized by XRD, SEM/EDS, dilatometry, UV–vis spectroscopy, impedance spectroscopy, and measurements of oxygen-ion transference numbers ($\overline{{\text{t}}_{\text{o}}}$). Magnesium was found to substitute preferentially into vanadium sublattice of zircon-type EuVO₄ with limited solubility of ～5 at.%. Additions of magnesium increase slightly coefficients of thermal expansion (3.2–6.0 ppm/K at 150–400 °C) and have negligible effect on the optical properties. Undoped EuVO₄ is predominantly an oxygen-ionic conductor with $\overline{{\text{t}}_{\text{o}}}$ = 0.96–0.99 at 700–900 °C under oxidizing conditions. Acceptor-type substitution suppresses total conductivity and oxygen-ionic transport. The variations of electrical transport properties are discussed in terms of interstitial oxygen diffusion in the parent EuVO₄ and oxygen vacancy diffusion in Mg-substituted vanadate. Humidified atmosphere has negligible impact on the electrical properties of substituted ceramics but results in increased electrical conductivity of EuVO₄ indicating a protonic contribution to the total electrical transport.     

A novel SiCN@TiO2 core–shell ceramic microspheres derived from a polymeric precursor

A novel core–shell ceramic microspheres, composed of a SiCN inner core and TiO₂ nanoparticles outer shell, were prepared via emulsion technique and polymer-derived ceramics (PDCs) method. The forming process of SiCN@TiO₂ core–shell ceramic microspheres were controlled by adjusting the ratio of raw material, curing temperature and pyrolysis temperature. The morphology, chemical composition and phase transformation were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). PVSZ@TiO₂ microspheres with good spherical structure and uniform-dispersed TiO₂ surface were fabricated at 200 °C with raw material ratio of 25%. After pyrolyzed at 1400 °C, the obtained SiCN@TiO₂ core–shell ceramic microspheres retained spherical structure. The XRD showed that the products were mainly composed of rutile TiO₂, SiC and Si₃N₄ crystalline phase, which were generated by polyvinylsilazane.     

Decomposition of nonionic surfactant on a nitrogen-doped photocatalyst under visible-light irradiation

A visible-light-active N-containing TiO₂ photocatalysts were prepared from crude amorphous titanium dioxide by heating amorphous TiO₂ in gaseous NH₃ atmosphere. The calcination temperatures ranged from 200 to 1000 °C, respectively. UV–vis/DR spectra indicated that the N-doped catalysts prepared at temperatures <400 °C absorbed only UV light (E_g = 3.3 eV), whereas samples prepared at temperatures ≥400 °C absorbed both, UV (E_g = 3.10–3.31 eV) and vis (E_g = 2.54–2.66 eV) light. The chemical structure of the modified photocatalysts was investigated using FT-IR/DRS spectroscopy. All the spectra exhibited bands indicating nitrogen presence in the catalysts structure. The photocatalytic activity of the investigated catalysts was determined on a basis of a decomposition rate of nonionic surfactant (polyoxyethylenenonylphenol ether, Rokafenol N9). The most photoactive catalysts were those calcinated at 300, 500 and 600 °C. For the catalysts heated at temperatures of 500 and 600 °C Rokafenol N9 removal was equal to 61 and 60%, whereas TOC removal amounted to 40 and 35%, respectively. In case of the catalyst calcinated at 300 °C surfactant was degraded by 54% and TOC was removed by 35%. The phase composition of the most active photocatalysts was as follows: (a) catalyst calcinated at 300 °C—49.1% of amorphous TiO₂, 47.4% of anatase and 3.5% of rutile; (b) catalyst calcinated at 500 °C—7.1% of amorphous TiO₂, 89.4% of anatase and 3.5% of rutile; (c) catalyst calcinated at 600 °C—94.2% of anatase and 5.8% of rutile.     

Preparation of Li2TiO3 by hydrothermal synthesis and its structure evolution under high energy Ar+ irradiation

Ultrafine lithium titanate (Li₂TiO₃) powder was synthesized by hydrothermal method. The phase formation and transition condition among α, β, and γ-Li₂TiO₃ were discussed. XRD and ICP-AES showed the single α-phase was formed at 180 °C with 2 h hydrothermal reaction, and it transited into β-phase at 400 °C. SEM observation and EDS analysis confirmed the dissolution of TiO₂ and the formation of α-Li₂TiO₃ proceeded simultaneously with preferable growth direction of (-133) lattice. During the phase transition, the powder maintained the small crystallite, which facilitated the fabrication of Li₂TiO₃ bulk with small grain size. After the Ar⁺ irradiation, the surface region to the depth of 3 μm of Li₂TiO₃ ceramic was affected, where the decrease of crystallization and disturbance of short-range order were confirmed by GIXRD and Raman spectroscopy. In spite of the structure change at the surface area, the ceramic bulk maintained the same.     

Optical,thermal and dielectric properties of Bi4(TiO4)3 ceramic powders

Bismuth titanate (Bi₄(TiO₄)₃) ceramic powders have been synthesized by using a solid state reaction method. Prominently intense blue emission at 480 nm has been measured with an excitation at 418 nm. The reason for the observance of such a blue emission from this ceramic powder has been explained. The phase formation has been investigated by X-ray diffraction analysis (XRD). The morphology and composition of the ceramic powders have been studied from the measurement of SEM and EDS profiles. FTIR and Raman spectra have also been recorded to analyze the presence of functional groups and Raman active modes in the Bi₄(TiO₄)₃ ceramic powders. The sintering temperature has been optimized to be 1100 °C based on the measured TG–DTA profiles of the as prepared material. Besides these, dielectric properties of ceramic powder in the frequency range of 200 Hz–3 MHz at 300 K have also been carried out.