The effect of titanium dioxide exposure on the thermal properties of Zebrafish (<Emphasis Type="Italic">Danio rerio</Emphasis>) bones

This article presents the changes in the thermal properties of the control and titanium dioxide (TiO₂), both nano and bulk exposed Zebrafish bones by using thermo analytical techniques. The result shows that the mass loss due to the thermal decomposition occurs in three distinct steps due to loss of water, organic and inorganic materials. The titanium dioxide exposed bones present a different thermal behaviour compared to the control bones. The residue masses are found to be increased due to titanium dioxide exposure. In particular, nano titanium dioxide exposure increases the residue mass level significantly (three fold) when compared to titanium dioxide bulk exposure. These thermal characteristics can be used as a qualitative method to check the metal oxide intoxication in biological samples.     

CO2在纳米SiO2/TiO2悬浮体系中的光催化还原

用水热法合成了氧化硅改性的具有高比表面积、高催化活性的锐钛型二氧化钛, 并在其悬浮体系中将CO₂光催化还原合成甲醇. 采用XRD, TEM, 物理吸附, UV-Vis吸收光谱和FTIR等表征手段对催化剂结构特征进行了研究. 结果表明: 添加氧化硅后, 氧化硅和二氧化钛之间形成Si—O—Ti键, 抑制了TiO₂晶粒生长, 提高了锐钛型TiO₂的比表面积, 且随着含硅量的增加, SiO₂/TiO₂的UV吸收逐步蓝移, 禁带宽度增加. 还原反应结果表明: SiO₂/TiO₂具有光催化还原活性, 且随着含硅量的增加先增加后减小, 当SiO₂质量分数为3.5%时, SiO₂/TiO₂复合催化剂反应活性最强, 5 h内甲醇产量可达到21.0 mg/L, 并有少量甲醛生成.     

Nb-doped rutile titanium dioxide nanorods for lithium-ion batteries

Rutile titanium dioxide is a promising negative electrode material for lithium-ion batteries due to low volume change on lithium-ion insertion, fast ion diffusion, and large surface area. However, the low theoretical capacity and conductivity of titanium dioxide has limited its application. In this work, rutile TiO₂ was synthesized using a batch hydrothermal method, and doped with Nb⁵⁺ (3.5 at%). <Potentiodynamic/galvanostatic > cycling in the range 1.0–3.0 V vs Li/Li⁺ was used to determine the Li-ion capacity of the doped and pristine TiO₂ material, and electrochemical cycling was used to measure the extent of conversion from the lithiated to de-lithiated state. The nanoscale structures of the pristine and doped materials were determined by powder X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy and Brunauer-Emmett-Teller surface area measurements. Cycling in the range 1.0–3.0 V vs Li/Li⁺ showed that Nb⁵⁺ doping into the structure resulted in higher charge capacities. After 100 cycles at 100 mA g⁻¹, the Nb-doped rutile TiO₂ maintained a capacity of ca. 390 mAh g⁻¹, 64% higher than undoped TiO₂. For electrochemical cycling in the range 0.05–3.0 V vs Li/Li⁺, the introduction of Nb⁵⁺ resulted in a higher conversion of rutile TiO₂ from the lithiated to de-lithiated state. The higher capacity of the doped TiO₂ is shown to be mainly due to the smaller particle size, optimized surface area, and orientation of the nanorods.     

Nano Au/TiO2 hollow microsphere membranes for the improved sensitivity of detecting specific DNA sequences related to transgenes in transgenic plants

Gold nanoparticles (nano Au)/titanium dioxide (TiO₂) hollow microsphere membranes were prepared on the carbon paste electrode (CPE) for enhancing the sensitivity of DNA hybridization detection. The immobilization of nano Au and TiO₂ microsphere was investigated with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The hybridization events were monitored with EIS using [Fe(CN)₆]^3?/4? as indicator. The sequence-specific DNA of the 35S promoter from cauliflower mosaic virus (CaMV35S) gene was detected with this DNA electrochemical sensor. The dynamic detection range was from 1.0×10^?12 to 1.0×10^?8 mol/L DNA and a detection limit of 2.3×10^?13 mol/L could be obtained. The polymerase chain reaction (PCR) amplification of the terminator of nopaline synthase (NOS) gene from the real sample of a kind of transgenic soybean was also satisfactorily detected.     

Raman spectroscopic study of dye adsorption on TiO2 electrodes of dye-sensitized solar cells

The state of dye adsorption on TiO₂ electrodes in dye-sensitized solar-cell (DSSC) systems is important for its power-conversion efficiency (PCE). We propose a non-destructive and quantitative method to evaluate the amount of adsorbed dye on TiO₂ electrodes by using micro-Raman spectroscopy. The Raman peak intensity ratio of adsorbed dye to TiO₂, I_d/I_t, is defined as a dye adsorption parameter. Based on a comparison between I_d/I_t and the amount of dye evaluated from UV–vis absorption, the quantitativity and reproducibility of our method are verified.We investigated the change of I_d/I_t spatial distribution of TiO₂ electrodes immersed in a dye solution for different time scales. The statistical analysis of I_d/I_t distribution suggests that dyes adsorbed on TiO₂ electrodes with chemical coordination increase at first, and after their saturation, dye aggregations are formed over the chemisorption layer. We also describe the effect of the I_d/I_t distribution on PCE. From a comparison of PCE and I_d/I_t distribution obtained from various immersion processes, it was considered that the PCE of DSSCs can be optimized by minimizing the I_d/I_t dispersion.     

Significant effect of lanthanide doping on the texture and properties of nanocrystalline mesoporous TiO2

A systematic study of microstructure and photocatalytic properties of lanthanide doping of nanocrystalline mesoporous titanium dioxide is performed. The anatase-to-rutile (A-R) phase transformation of nanosized TiO₂ was significantly inhibited by lanthanide doping and the inhibitory effect was enhanced with the increase of the rare earth radius, i.e., La³⁺>Gd³⁺>Yb³⁺ for different lanthanide dopants. At high calcination temperatures, different texture lanthanide titanium oxides of Ln₄Ti₉O₂₄ (La³⁺, Pr³⁺, Nd³⁺), Ln₂Ti₂O₇ (Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺, Er³⁺), and Yb₂TiO₅ were developed, respectively, revealing that the structures of lanthanide titanium oxide developed in Ln/TiO₂ depend on the lanthanide radius. Larger radius lanthanides prefer to form higher coordination number lanthanide titanium oxide. In addition, the thermal stability of mesoporous structures of TiO₂ was remarkable improved by lanthanide doping. The photocatalytic properties were studied by employing the photodegradation of Rhodamine B (RB) as a probe reaction. The results indicate that the lanthanide doping could bring about significant improvement to the photoreactivity of TiO₂, and the improvement was sensitive to the atomic electronic configuration.     

Solid-State and Solution FT-Raman Spectra of the Tetraiodine Dication I4 2+

Abstract

I₄ ²⁺ is the only known cyclic homopolyatomic cation or anion of iodine. It has a rectangular planar structure which may be thought of as containing two I₂ ⁺ units joined by a weak π?-π? 4 centre 2 electron bond.¹ In this paper we report our FT-Raman spectra of I₄ ²⁺, which conflict with those published by Gillespie et al. ¹ and present evidence that the peaks attributed to a species containing iodine in the +1 oxidation state are in fact due to I₄ ²⁺.     

Silane grafting of TiO2 nanoparticles: dispersibility and photoactivity in aqueous solutions

Titania nano‐sized particles were treated by various amounts of tetraethyl orthosilicate precursor. The extent of grafting was characterized using Fourier transform infrared (FTIR) and ultraviolet‐visible (UV‐Vis) spectroscopy techniques, thermal gravimetric analysis, X‐ray fluorescence and zeta potential measurements. Sedimentation behaviour of titanium dioxide (TiO₂) nanoparticles in aqueous solutions was evaluated visually and using a separation analyser. Photocatalytic activity of nanoparticles was studied by photo‐activated degradation reaction of Rhodamine B dyestuff in aqueous solutions. The results showed that grafted particles had acquired enhanced dispersion stability and lower photocatalytic activity in aqueous solutions. Untreated TiO₂ dispersions settled rapidly and sedimentation completed within 24 h through the coagulation mechanism, whereas that of the silica‐treated nanoparticles, depending on the silica content, showed different degrees of stability by flocculation mechanism. Photodebleaching of Rhodamine B in the presence of treated nanoparticles is evident by weaker intensity of UV absorption peak of 554 nm due to lowering concentration of Rhodamine B accompanied with the blue shift in UV absorption peaks. However, untreated TiO₂ nanoparticles showed only weaker intensity of UV absorption peak. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of anatase TiO2 in a vinyl-containing ionic liquid and its enhanced photocatalytic activity

TiO₂ microspheres were synthesized by the sol–gel method using the ionic liquid (IL) 1-vinyl-3-propylimidazolium iodide (VPIM⁺I^?) as a reaction medium, then calcined at 500 °C. The samples were characterized by X-ray diffraction, scanning electron microscopy, and ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy. The phase of TiO₂ microspheres is anatase, and VPIM⁺I^? is able to favor the growth of anatase phase and prevents the collapse of small pores. The photocatalytic activity of TiO₂-IL was tested by degradation of 2-nitrophenol under UV light illumination. The photocatalytic activity of TiO₂-IL was higher than that of samples prepared in the reaction medium without VPIM⁺I^?.     

硼铈共掺杂纳米TiO2光催化降解三氯杀螨醇和菊酯类农药

采用溶胶-凝胶法在钛酸丁酯水解过程引入硼酸、硝酸铈,制备具有光催化活性的硼铈共掺杂纳米二氧化钛（TiO2）,经XRD、TEM、FT-IR、UV-Vis-DRS表征晶体结构,在日光灯照射下,光催化降解三氯杀螨醇、高氟氯氰菊酯、氟戊菊酯农药。结果表明：硼铈共掺杂的TiO2只有锐钛矿型,而纯的或掺铈的TiO2有含有锐钛矿型、金红石相和少量板钛矿型,UV-Vis-DRS测定结果表明硼铈共掺杂的TiO2禁带宽度变小,硼铈共掺杂的TiO2在可见光区吸光度高于掺杂铈和不掺杂的TiO2,在420nm~850nm有强的吸收;在同样光照下对三氯杀螨醇、高氟氯氰菊酯、氟戊菊酯的降解试验证明硼铈共掺杂纳米TiO2的光催化活性高于不掺杂或只掺杂铈的TiO2。     

Synthesis,characterization and photocatalytic application of TiO2/magnetic graphene for efficient photodegradation of crystal violet

A magnetized nano‐photocatalyst based on TiO₂/magnetic graphene was developed for efficient photodegradation of crystal violet (CV). Scanning electron microscopy, X‐ray diffraction, energy‐dispersive X‐ray spectroscopy and elemental mapping were used to characterize the prepared magnetic nano‐photocatalyst. The photocatalytic activity of the synthesized magnetic nano‐photocatalyst was evaluated using the decomposition of CV as a model organic pollutant under UV light irradiation. The obtained results showed that TiO₂/magnetic graphene exhibited much higher photocatalytic performance than bare TiO₂. Incorporation of graphene enhanced the activity of the prepared magnetic nano‐photocatalyst. TiO₂/magnetic graphene can be easily separated from an aqueous solution by applying an external magnetic field. Effects of pH, magnetized nano‐photocatalyst dosage, UV light irradiation time, H₂O₂ amount and initial concentration of dye on the photodegradation efficiency were evaluated and optimized. Efficient photodegradation (>98%) of the selected dye under optimized conditions using the synthesized nano‐photocatalyst under UV light irradiation was achieved in 25 min. The prepared magnetic nano‐photocatalyst can be used in a wide pH range (4–10) for degradation of CV. The effects of scavengers, namely methanol (OH^? scavenger), p‐benzoquinone (O₂^?? scavenger) and disodium ethylenediaminetetraacetate (hole scavenger), on CV photodegradation were investigated.     

Electrospinning fabrication of mesoporous nano Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript>@activated carbon fiber membrane for hybrid removal of phenol from waste water

A mesoporous iron–titanium mixed-oxides@activated carbon(AC) fiber membrane was fabricated by an electrospinning method and applied to the treatment of phenol waste water. The physical and chemical properties of the composite fiber membrane were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption/desorption, UV–Vis light diffuse reflectance spectroscopy (DRS), Raman spectroscopy, respectively. The results indicate that the composite nanofiber membrane is composed of α-Fe₂O₃, anatase TiO₂ and activated carbon phases with a specific surface area of 231 m² g^–1 and narrow pore size distribution of 3–6 nm. DRS reveals that the composite membrane has high photons absorption from both ultraviolet light and visible light irradiation owing to the combination of Fe₂O₃, TiO₂ and carbon. The prepared nano Fe₂O₃–TiO₂@AC fiber membrane can act as an efficient reusable photocatalyst and adsorbent for 100% remo val of phenol pollutant. This hybrid technique is hopeful to be widely used in the treatment of various organic waste waters.     

Nano Au/TiO2 hollow microsphere membranes for the improved sensitivity of detecting specific DNA sequences related to transgenes in transgenic plants

Gold nanoparticles (nano Au)/titanium dioxide (TiO₂) hollow microsphere membranes were prepared on the carbon paste electrode (CPE) for enhancing the sensitivity of DNA hybridization detection. The immobilization of nano Au and TiO₂ microsphere was investigated with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The hybridization events were monitored with EIS using [Fe(CN)₆]^3−/4− as indicator. The sequence-specific DNA of the 35S promoter from cauliflower mosaic virus (CaMV35S) gene was detected with this DNA electrochemical sensor. The dynamic detection range was from 1.0×10⁻¹² to 1.0×10⁻⁸ mol/L DNA and a detection limit of 2.3×10⁻¹³ mol/L could be obtained. The polymerase chain reaction (PCR) amplification of the terminator of nopaline synthase (NOS) gene from the real sample of a kind of transgenic soybean was also satisfactorily detected. Supported by the National Natural Science Foundation of China (Grant Nos. 20635020 and 20375020), Doctoral Foundation of the Ministry of Education of China (Grant No. 20060426001) and Natural Science Foundation of Qingdao City (Grant No. 04-2-JZP-8)     

Preparation and characterization of natural zeolite supported nano TiO2 photocatalysts by a modified electrostatic self‐assembly method

Natural zeolite supported nano TiO₂ photocatalysts were prepared by a modified electrostatic self‐assembly (ESA) method. First, γ‐mercaptopropyltrimethoxysilane with sulfhydryl (―SH) functional groups was modified on the zeolite powders by using a ‘dry process’. Second, silane with ―SH functional groups was oxidized to sulfonate (―SO₃H) groups by using a hydrogen peroxide/glacial acetic acid mixed solution, and the surface of ―SO₃H silane–zeolite was electronegative charged due to the ionization of ―SO₃H. Third, the hydrolytic titanium polycation from TiCl₄ solution assembled onto the electronegative charged zeolite under electrostatic attraction in the reaction solutions. Finally, zeolite supported nano TiO₂ photocatalysts can be obtained after the above compounds calcined at certain temperature. The samples were characterized by X‐ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface areas, Fourier transform infrared spectroscopy (FT‐IR), X‐ray photoelectron spectroscopy (XPS) and X‐ray fluorescence (XRF). The photocatalytic activities of the samples were evaluated by the degradation of methyl orange in aqueous solution. The results showed that ESA method effectively improved the composite efficiency of zeolite with TiO₂. The photocatalysts prepared by ESA method exhibited higher photocatalytic and recycling activities than that of traditional method. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrochemical application of titanium dioxide nanoparticle/gold nanoparticle/multiwalled carbon nanotube nanocomposites for nonenzymatic detection of ascorbic acid

Titanium dioxide nanoparticle/gold nanoparticle/carbon nanotube (TiO₂/Au/CNT) nanocomposites were synthesized, and then characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDX). A TiO₂/Au/CNT nanocomposite-modified glassy carbon (GC) electrode was prepared using the drop coating method and was investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometric current–time response (I-T). The modified material is redox-active. The nonenzymatically detected amount of ascorbic acid (AA) on the TiO₂/Au/CNT electrode showed a linear relationship with the AA concentration, for concentrations from 0.01 to 0.08 μM; the sensitivity was 117,776.36 μA?·?cm^?2?·?(mM)^?1, and the detection limit was 0.01 μM (S/N?=?3). The results indicated that the TiO₂/Au/CNT nanocomposite-modified GC electrode exhibited high electrocatalytic activity toward AA. This paper describes materials consisting of a network of TiO₂, Au, and MWCNTs, and the investigation of their synergistic effects in the detection of AA.     

Pressure-induced phase transition of Fe2TiO4: X-ray diffraction and Mössbauer spectroscopy

X-ray diffraction and Mössbauer spectroscopy were employed to investigate structural stability of Fe₂TiO₄ under high pressure. Measurements were performed up to about 24 GPa at room temperature using diamond anvil cell. Experimental results demonstrate that Fe₂TiO₄ undergoes a series of phase transitions from cubic (Fd3?m) to tetragonal (I4₁/amd) at 8.7 GPa, and then to orthorhombic structure (Cmcm) at 16.0 GPa. The high-pressure phase (Cmcm) of Fe₂TiO₄ is kept on decompression to ambient pressure. In all polymorphs of Fe₂TiO₄, iron cations present a high-spin ferrous property without electric charge exchange with titanium cations at high pressure supported by Mössbauer evidences.     

Kinetic study of the poly(vinyl chloride)/titanium dioxide nanocomposites photodegradation under accelerated ultraviolet and visible light exposure

In the present study, poly(vinyl chloride)/titanium dioxide (PVC/TiO₂) nanocomposite films containing different amounts of synthesized TiO₂ nanoparticles and commercial rutile powder were irradiated for 5112 hr, under exposure of artificial ultraviolet and visible lights in three different intensities. The rate of degradation was determined by using weight loss data and was found to follow a pseudo‐first order kinetic model. To determine the overall rate constant of degradation, k, a possible mechanism of the photodegradation was considered. The rate equation demonstrated k as a function of TiO₂ concentration and irradiation intensity at each wavelength. The overall rate constant of PVC/TiO₂ samples were calculated to be varied in the range of 6–16 × 10^?7 hr^?1, at all investigated conditions. The kinetic study represented that by adding synthesized TiO₂ nanoparticles, even at low content, and with increasing their concentration, the photodegradation rate of nanocomposites decreased considerably compared with the composite samples. Likewise, by adding nanoparticles, a significant increase in the nanocomposites lifetime was achieved. The effect of irradiation intensity was investigated according to the reciprocity law experiments, and it was found that photodegradation occurred in two regimes with respect to irradiation intensity. The calculated overall rate constants were validated by the experimental data. Copyright © 2014 John Wiley & Sons, Ltd.     

Coating of anatase titania on clinoptilolite by metal organic chemical vapor deposition method: enhanced mesoporosity and photocatalytic activity

Clinoptilolite-supported TiO₂ (TiO₂/CP_MOCVD) has been synthesized by metal organic chemical vapor deposition method (MOCVD). Titanium precursor was evaporated at 110 °C under nitrogen flow rate to promote the surface interaction between titanium species and clinoptilolite. The effect of titanium precursor on the crystalline structure and the surface area of clinoptilolite were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), transformed infrared spectroscopy (FT-IR), Raman spectroscopy, and Brunauer–Emmett–Teller measurement. XRD and SEM results indicate that TiO₂ precursor interacted with the support, decreasing the crystallinity of the clinoptilolite. The analysis by FT-IR spectroscopy further confirms that the titanium species were bound to clinoptilolite through Ti–O–Si bonds. The TiO₂/CP_MOCVD catalyst showed a mesoporous structure with the distribution of pores in several dimensions 3.7–7.1 nm, with high specific surface area (~ 471 m²/g). MOCVD improved the adsorption capacity of the catalyst surface towards the pollutants. TiO₂/CP_MOCVD particles turn yellow after adsorption of salicylic acid. The development of the yellow color is a clear indication of the formation of charge transfer titanium (IV) salicylate surface complex. Photocatalytic decomposition of SA in aqueous solution was carried out using TiO₂/CP_MOCVD. Experimental results revealed that TiO₂/CP_MOCVD required shorter irradiation time (120 min) for complete decomposition of SA than commercial P25 Degussa and TiO₂/CP_imp (clinoptilolite-supported TiO₂ using impregnation method). The TiO₂/CP_MOCVD can be recycled at least four times without loss in activity, indicating their magnificent stability.     

Solgel-hydrothermal synthesis of Tb/Tourmaline/TiO2 nano tubes and enhanced photocatalytic activity

In this study, we synthesized Tb/Tourmaline/TiO₂ nano tubes (NTs) through a solgel-hydrothermal method. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectromicroscope, scanning electron microscopy, transmission electron microscopy and UV-vis diffuse reflectance spectroscopy. The resulting Tb/Tourmaline/TiO₂ NTs exhibited higher photocatalytic activity than pure TiO₂ and TiO₂ nano particles (NPs) in the degradation of menthyl orange under UV-light. Results revealed that doping rare earth element Tb could narrow the wide band gap of TiO₂ and tourmaline could trap the photogenerated electron of TiO₂ to inhibit the recombination of photogenerated electron-hole pairs.     

Morphological and phase evolution of TiO2 nanocrystals prepared from peroxotitanate complex aqueous solution: Influence of acetic acid

Nanosized anatase and rutile TiO₂ having different shape, phase and size have been prepared from aqueous solutions of peroxo titanium complex starting from titanium(IV) isopropoxide (TTIP), acetic acid and hydrogen peroxide (H₂O₂) in water/isopropanol media by a facile sol-gel process. The TiO₂ nanocrystals are characterized by powder X-ray diffraction (XRD), Raman spectroscopy, FT-IR spectroscopy, TEM, high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) techniques. The influence of pH and the sequence of addition of reaction contents on the phase and morphology of TiO₂ are studied. The reasons for the observation of only anatase and/or mixture of anatase and rutile are given.