Effect of amines on the peroxo-titanates and photoactivity of annealed TiO2

The aim of this study was to explore the influence of various n-propylamines (mono, di, and tri) and tert-butylamine on the properties of prepared peroxo-titanates and annealed TiO₂. Detailed structural characterization (SEM, TEM with EDX, XRD) confirmed the 2D-foil morphology of TiO₂ nanocrystals and the CHNS analysis together with XPS showed presence of carbon (under 1 wt%). The annealed TiO₂ showed excellent photocatalytic activity and up to four times higher decomposition rate constant upon UV irradiation than the P25. Favourable growth of TiO₂ crystals was observed especially when propylamine and tert-butylamine were used (as precursors for the peroxo-titanates). Increased photocatalytic efficiency of the highly crystalline nano-TiO₂ was confirmed due to high-reactive anatase facets and the morphology composed of microsheets formed by interconnected nanocrystals. The photoinduced electron transfer was confirmed via EPR spectroscopy. This synthesis’ procedure offers a novel preparation method of highly photoactive C-doped TiO₂ achieved relatively easily after annealing of lyophilized amino-peroxo-titanate.     

高度有序的二氧化钛纳米管阵列的制备及其光催化活性的研究

采用电化学阳极氧化法在钛表面构筑了一种结构有序、微米级的TiO₂纳米管阵列膜层. 考察了制备电压、氧化时间、溶液搅拌等实验参数对TiO₂纳米管阵列形貌和尺寸的影响. 应用SEM和XRD对膜层的形貌和晶型进行了分析和表征, 并通过TiO₂纳米管阵列膜对甲基橙的光催化降解, 研究了TiO₂纳米管阵列膜层结构与光催化活性的关系. 结果表明: 阳极电压和溶液搅拌对制备TiO₂纳米管阵列的结构起到关键的作用. 控制20 V电压制备的TiO₂纳米管阵列膜, 管长达2.6～3.3 μm, 经500 ℃热处理后具有最高的光催化活性, 其光催化性能明显优于一般的TiO₂纳米颗粒膜.     

Influence of sputter power on structural and electrical properties of TiO2 films for Al/TiO2/Si gate capacitors

Titanium dioxide (TiO₂) thin films were deposited onto p‐Si substrates held at room temperature by reactive Direct Current (DC) magnetron sputtering at various sputter powers in the range 80–200 W. The as‐deposited TiO₂ films were annealed at a temperature of 1023 K. The post‐annealed films were characterized for crystallographic structure, chemical binding configuration, surface morphology and optical absorption. The electrical and dielectric properties of Al/TiO₂/p‐Si structure were determined from the capacitance–voltage and current–voltage characteristics. X‐ray diffraction studies confirmed that the as‐deposited films were amorphous in nature. After post‐annealing at 1023 K, the films formed at lower powers exhibited anatase phase, where as those deposited at sputter powers > 160 W showed the mixed anatase and rutile phases of TiO₂. The surface morphology of the films varied significantly with the increase of sputter power. The electrical and dielectric properties on the air‐annealed Al/TiO₂/p‐Si structures were studied. The effect of sputter power on the electrical and dielectric characteristics of the structure of Al/TiO₂/p‐Si (metal‐insulator‐semiconductor) was systematically investigated. Copyright © 2014 John Wiley & Sons, Ltd.     

Preparation and properties of polysulfone/TiO2 composite ultrafiltration membranes

The influence of inorganic filler TiO₂ nanoparticles on the morphology and properties of polysulfone (PS) ultrafiltration membranes was investigated. PS/TiO₂ composite membranes were prepared by a phase‐inversion method. TiO₂ nanoparticles modified by sodium dodecyl sulfate were uniformly dispersed in an 18 wt % PS casting solution. The addition of TiO₂ resulted in an increase in the pore density and porosity of the membrane skin layer. The pore size distribution changed from the log‐normal distribution to the bimodal distribution because of the presence of TiO₂ nanoparticles, and some large pores were observed when the concentration of the filler was over 3 wt %. The skin layer was gradually thickened; meanwhile, the morphology sublayer changed from macrovoids to spongelike pores, in comparison with PS membranes without the filler. The addition of TiO₂ also induced increases in the hydrophilicity, mechanical strength, and thermal stability. The ultrafiltration experiments showed when the concentration of TiO₂ was less than 2 wt %, the permeability and rejection of the membrane was enhanced and then decreased drastically with a higher filler concentration (>3%). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 879–887, 2006     

Impact of TiO2 nanoparticles on morphology and performance of crosslinked polyimide organic solvent nanofiltration (OSN) membranes

Chemically crosslinked polyimide organic–inorganic composite nanofiltration membranes suitable for application in harsh organic solvents were successfully prepared by phase inversion of dope solutions. TiO₂ nanoparticles were dispersed in these dope solutions, comprising polyimide (PI) in N,N-dimethylformamide/1,4-dioxane. The impact of TiO₂ on the resulting PI membranes was investigated using SEM, TGA, water contact angle, dope viscosity measurements and mechanical strength. The presence of TiO₂ nanoparticles within the membrane matrix was proved by the detection of a peak characteristic of TiO₂ in the WAXS pattern. SEM pictures of the cross-section of the PI/TiO₂ membranes showed dramatically changed morphology compared to reference membranes with no TiO₂ addition. Macrovoids present in reference membranes were suppressed by increasing loading of TiO₂ nanoparticles, and eventually disappeared completely at a TiO₂ loading above 3 wt.%. Decreasing water contact angle and an increase in ethanol flux indicated that hydrophilicity increased as nanoparticle loading increased. The effect of TiO₂ on the functional performance of the membranes was evaluated by measuring flux and rejection using cross-flow filtration. Perhaps surprisingly, the presence of TiO₂ improved the compaction resistance of the membranes, whereas rejection and steady flux were almost unaltered.     

总气压与Ar/O2流量比对直流对向靶磁控溅射TiO2薄膜光催化性能的影响

采用对向靶磁控溅射法在不同气压和Ar/O₂流量比条件下, 以氟化SnO₂ (FTO)导电玻璃为基底制备了多晶TiO₂薄膜. 台阶仪测量结果显示所制备TiO₂薄膜的平均厚度约为200 nm. 随着溅射气压的升高, TiO₂薄膜由锐钛矿与金红石混晶结构转变为纯锐钛矿结构. 分别采用场发射扫描电镜(FESEM)和原子力显微镜(AFM)分析了不同气压和Ar/O₂流量比对TiO₂薄膜表面形貌的影响, 结果显示TiO₂薄膜的表面粗糙度随溅射总气压和Ar/O₂流量比的增加而增大. 以初始浓度为100×10^-6 (体积分数)的异丙醇(IPA)气体为目标物检测所制备TiO₂薄膜的光催化性能, 并分析该气相光催化反应的机理, 在紫外照射条件下异丙醇先氧化为丙酮再被氧化为CO₂.当总溅射气压为2.0 Pa、Ar/O₂流量比为1:1时, 溅射所得TiO₂薄膜具备最优光催化活性并可在IPA降解反应中保持较高的催化活性和稳定性.     

Effects of synthesis parameters on the microstructure and phase structure of porous 316L stainless steel supported TiO2 membranes

Porous stainless steel (PSS) supported TiO₂ membrane was synthesized from colloidal TiO₂ sol by the sol–gel technique. Morphology and phase structure of the obtained membranes were regulated through optimizing the synthesis parameters including organic binders, aging periods of the parent sol and concentrations of the casting solutions as well as the sintering temperatures. Polyvinyl alcohol (PVA) 1750 was found to be feasible to fabricate TiO₂ membrane with relatively flat surface and homogeneous morphology without crack. The aging period of the parent sol, which was revealed to be very important to the morphology of the particles deposited in the membranes on PSS, was decided to be 24 h. The concentration, under which the membranes could avoid macro-pores and have a uniform thickness of approximately 8 μm, was regulated to 0.0036 mol/l. Besides, a homogeneous microstructure with grain sizes of 0.08–0.2 μm was obtained in the membrane with a pure rutile phase when sintered at 850 °C. The obtained PSS supported TiO₂ membrane with homogeneous microstructure and rutile phase may be very promising for practical applications.     

Effect of optical property of surfactant-treated TiO2 nanostructure on the performance of TiO2 photo-electrochemical cell

TiO₂ nanostructures have been treated using different kind of surfactant to modify its optical absorption and morphology. TiO₂ nanostructures were prepared via simple method on indium tin oxide (ITO) surface, namely, liquid-phase deposition technique (LPD) at 50°C. The TiO₂ nanostructures film with a thickness of about 236 nm was annealed at 400°C for 1 h in the air to enhance the interconnectivity of the particles. The dense and compact TiO₂ nanoparticle with different shape, particle size and surface morphology was used as a photovoltaic material in a photo-electrochemical cell of ITO/TiO₂/electrolyte/platinum. TiO₂ nanostructure films were treated with three different kinds of surfactants: cetyltrimethylammonium bromide (CTAB), hexamethylenetetramine (HMT) and polyvinylpyrrolidone (PVP). It was found that the film treated with HMT performed best, with a J _sc of 57.5 μA/cm². In conclusion, optical absorption, band gap and grain size of TiO₂ nanostructure influenced the performance of the cell.     

Nano/subnano-tuning of porous ceramic membranes for molecular separation

In sol–gel processing, porous ceramic membranes can be prepared by sol-coating porous substrates and drying for gelling, followed by a firing process. Ceramic membranes prepared by sol–gel processing can be categorized into amorphous materials such as silica, and crystalline materials such as alumina and titania. Amorphous silica networks, which can be prepared by the polymeric sol route, have ultra-microporous pores that allow small molecules such as helium and hydrogen to permeate. On the other hand, crystalline materials, which are mostly prepared by the colloidal sol route, have nano-sized pores in the range of one to several nanometers. In this article, sol–gel derived SiO₂ and TiO₂ membranes with controlled pore sizes in the range of sub-nano to nanometers will be reviewed with respect to membrane preparation and to their application in the separation of the gas and liquid phases. Ceramic membranes with high performance can be obtained by precise control of membrane structures (pore size, pore size distribution, thickness, pore shape, etc.) and membrane materials (SiO₂, TiO₂, composite oxide, hybrid materials, etc.). Nano/subnano-tuning of porous ceramic membranes is quite important for the improvement of membrane permeability and selectivity.     

Formation of appropriate sites on nanofiltration membrane surface for binding TiO2 photo-catalyst: Performance, characterization and fouling-resistant capability

Titanium dioxide (TiO₂) nanoparticles were assembled on the surface of nanofiltration blend membrane. For settling TiO₂ on the membrane surface, two membrane categories were used: (i) unmodified polyethersulfone (PES)/polyimide (PI) blend membrane, and (ii) –OH functionalized PES/PI blend membrane with different concentrations of diethanolamine (DEA). These membranes were radiated by UV light after TiO₂ depositing with different concentrations. 15 min immersion in colloidal suspension and 15 min UV irradiation with 160 W lamps were used for modification. The modification resulted in the formation of a photo-catalytic property with enhanced membrane hydrophilicity. The self-assembly of TiO₂ nanoparticles was established through coordinance bonds with –OH functional groups on the membrane surface. A comparison between the UV irradiated TiO₂ deposited blend membrane and deposited-functionalized blend membranes showed that –OH groups originate excellent adhesion of TiO₂ nanoparticles on the membrane surface, increase reversible deposition, and diminish irreversible fouling. The membranes were characterized using SEM, FTIR, EDX, contact angle, cross flow filtration, and antifouling measurements. SEM images show that the presence of –OH groups on the DEA-modified membrane surface is the main parameter for extra uniformly settlement of TiO₂ nanoparticles on the membrane surface. This procedure is a superior technique for modification of PES/PI nanofiltration membranes to enhance water flux and minimization membrane fouling.     

Crystallization behaviour of TiO2–ZrO2 composite nanoparticles

Nano-composite TiO₂?CZrO₂ materials were prepared via sol?Cgel processes by hydrolysis of mixtures of titanium- and zirconium-containing alkoxides with TiO₂:ZrO₂ ratios of 1:2, 1:1, 2:1, and 10:1. Precipitated powders were dried at room temperature and annealed in ambient air at temperatures between 350 and 500?°C for 4?h. Pure TiO₂ and ZrO₂ powders were synthesized for comparison. Samples were characterized with X-ray diffraction (XRD) and X-ray absorption near edge fine structure (XANES). The detailed analysis of those data provides the crystalline and amorphous phase composition as well as the crystallite particle size. According to XRD and XANES analysis, only the two pure oxide samples and one of the composite samples with a composition TiO₂:ZrO₂?=?10:1, crystallized. Both titania containing powders, the pure TiO₂ and the TiO₂:ZrO₂?=?10:1 composite, were found to crystallize in the anatase structure. ZrO₂ was found to stay amorphous in the composites but crystalline in the pure oxide. In the crystallized composite TiO₂:ZrO₂?=?10:1 sample, the concentration of the amorphous phase remains larger than in pure TiO₂ samples, but the crystallite size was found to be nearly constant with increasing annealing temperature in contrast to the increasing particle size of pure TiO₂-samples. Pure TiO₂ precipitates are amorphous directly after preparation, however they crystallize after 6?month storage at ambient conditions by aging. Such an aging was not observed for the TiO₂:ZrO₂ composites.     

Synthesis and Ex-situ Characterization of Nafion/TiO2 Composite Membranes for Direct Ethanol Fuel Cell

Nafion/TiO₂ composite membranes for different loadings of TiO₂ were prepared by casting method for the possible application in direct ethanol fuel cell (DEFC). The properties of the composite membranes were investigated by scanning electron microscopy (SEM), x-ray diffraction (XRD), thermogravimetric analyser (TGA), ion exchange capacity, water and alcohol uptake, swelling ratio, proton conductivity, and ethanol crossover. The observed characteristics of the membranes were evaluated for DEFC and compared with the direct methanol fuel cell (DMFC) membrane. The analysis reveales a significant influence on the TiO₂ surface characteristics, water and alcohol uptake, and swelling of the membrane. The TiO₂ composite membranes exhibited a sharp decrease in methanol and ethanol crossover for 5% TiO₂ and the proton conductivity was heighest for 1% TiO₂ loading. The best compromise between proton conductivity and crossover has been found out with the help of the characteristic factor ϕ. The optimum loading of 5% TiO₂ composite membrane has shown the maximum characteristic factor.     

Antibacterial photocatalytic self‐cleaning poly(vinylidene fluoride) membrane for dye wastewater treatment

Membrane technology has been successfully applied for the removal of dyes from wastewater in the textile industry. A novel poly(vinylidene fluoride) (PVDF) membrane was prepared via blending with different dosages of Ag‐TiO₂‐APTES composite for dyeing waste water treatment in our study. And the effect of Ag‐TiO₂‐APTES blended into the PVDF membrane was discussed, including the rejection rate of methylene blue (MB) dye, membrane morphology, surface hydrophilicity, antibacterial activity, and a certain photocatalytic self‐cleaning performance. X‐ray diffraction and Fourier transform infrared characterization confirmed that Ag‐TiO₂ was functionalized by amount of hydroxyl group (−OH) and amino group (NH−), which provided by APTES. Contact angle measurement certified that the hydrophilicity of the membrane surface increased, with the contact angle decrease to 61.4° compared with 81.8° of original PVDF membrane. MB rejection rate was also increased to 90.1% after addition of Ag‐TiO₂‐APTES, and the rejection of original membrane was only 74.3%. The morphologies of membranes were observed by scanning electron microscope, which indicated that Ag‐TiO₂‐APTES had a good dispersion in membrane matrix and also improved the microstructure of membranes. Besides, UV irradiation experiments were performed on the composite films contaminated by MB, and the result showed that Ag‐TiO₂‐APTES nanoparticle provided PVDF membrane with a certain photodegradation capacity under UV irradiation. Moreover, antibacterial activity of the composite membrane was also demonstrated through antibacterial experiment, Escherichia coli as the representative bacteria. Perhaps, this research may provide a new way for PVDF blending modification.     

Fabrication and characterization of a novel TiO2 nanoparticle self-assembly membrane with improved fouling resistance

A novel TiO₂ nanoparticle self-assembly membrane was prepared based on ultrahigh molecular weight poly(styrene-alt-maleic anhydride)/poly(vinylidene fluoride) (SMA/PVDF) blend membrane. TiO₂ nanoparticle solution was beforehand prepared via the controlled hydrolysis of titanium tetraisopropoxide. The diameter (10 nm or less) and anatase crystal structure were analyzed using transmission electron microscopy (TEM) and X-ray diffraction (XRD). The SMA/PVDF blend membranes prepared by the phase inversion method were immersed into the TiO₂ nanoparticle solution for a week to produce TiO₂ self-assembly membranes. The chemical compositions in membrane surface were analyzed by X-ray photoelectron spectroscopy (XPS). The membrane morphologies were measured by scanning electron microscopy (SEM). Finally, the membrane hydrophilicity, protein anti-fouling property and the molecular weight cutoff (MWCO) were characterized by water contact angle measurement, static protein absorption and filtration experiments, respectively. It is demonstrated that, in comparison to PVDF/SMA blend membrane, the permeability and anti-fouling ability of TiO₂ self-assembly membranes were significantly improved.     

Preparation,photocatalytic activity and mechanism of nano-Titania/Nafion hybrid membrane

Nano-Titania/Nafion (TiO₂/Nafion) hybrid membranes were prepared by recasting, using Nafion solution and TiO₂ anatase hydrosol as the raw materials. The microstructure of the hybrid membrane was characterized by X-ray diffraction, high-resolution transmission electron microscopy (HR-TEM), X-ray Photoelectron Spectroscopy and Fourier Transform Infrared Spectroscopy (FT-IR). The photocatalytic properties of TiO₂/Nafion hybrid membranes were evaluated. Furthermore, endurance of photocatalytic activity of the hybrid membrane was investigated. The results indicate that the TiO₂ Nanoparticles are bounded to Nafion molecule via Ti-O-S bonds and the formed flocculates are distributed homogeneously throughout the recasting Nafion membrane, while the initial pure anatase TiO₂ nanoparticles remain intact in re-crystallized membrane. The hybrid membranes possessed excellent photocatalytic activities with and without H₂O₂. Moreover, the degradation of photocatalytic activities has been better controlled with the presence of H₂O₂.     

Enhancement of proton mobility and mitigation of methanol crossover in sPEEK fuel cells by an organically modified titania nanofiller

An organically functionalized titania, TiO₂-RSO₃H, was evaluated as filler in sulfonated polyetheretherketone (sPEEK)-based composite membranes for application in high temperature direct methanol fuel cells. The presence of propylsulfonic acid groups covalently bound onto the TiO₂ surface and the nanometric nature of the additive were analyzed by Raman spectroscopy and transmission electron microscopy, respectively. The properties of the sPEEK/TiO₂-RSO₃H composite membranes were compared with those of the pure sPEEK membranes and those of the sPEEK/TiO₂ composite membranes containing pristine titania nanoparticles at same filler content. Water and methanol transport properties were investigated by NMR methods, including relaxation times and self-diffusion coefficients as function of temperature (up to 130 °C), and pressure (from 0 up to 2 kbar). The incorporation of the nanoadditivies in the sPEEK polymer demonstrates considerable effects on the morphology and stiffness of the membranes, as well as on the transport properties and barrier effect to the methanol crossover. In particular, the functionalization by propylsulfonic acid groups promotes a higher reticulation between the polymeric chains, increasing the tortuosity of the methanol diffusional paths, so reducing the molecular diffusion, while the proton mobility increases being favored by the Grotthus-type mechanism. Conductivity measurements point out that the filler surface functionalization avoids the reduction of the overall proton conduction of the electrolyte due to the embedding of the low-conducting TiO₂. Finally, remarkable improvements were found when using the sPEEK/TiO₂-RSO₃H composite membrane as electrolyte in a DMFC, in terms of reduced methanol crossover and higher current and power density delivered.     

Nafion/PTFE and zirconium phosphate modified Nafion/PTFE composite membranes for direct methanol fuel cells

We prepared Nafion/PTFE (NF) and zirconium phosphate (ZrP) hybridized Nafion/PTFE composite membranes (NF–ZrP). NF–ZrP composite membranes were prepared via two processes. One is impregnating sub-μm porous PTFE membrane directly in a Nafion/ZrOCl₂ solution (NF–Zr–d). The other is impregnating sub-μm porous PTFE membrane in a Nafion solution to prepare NF composite membrane, and then the NF membrane was impregnated in a ZrOCl₂ aqueous solution via in situ precipitation method (NF–Zr–I). The ZrOCl₂ inserted in NF composite membranes was then reacted with phosphoric acid to form ZrP and thus NF–ZrP–d and NF–ZrP–I composite membranes were obtained. The direct methanol fuel cell (DMFC) performances of membrane electrode assemblies prepared from Nafion-117, NF, NF–ZrP–d, and NF–ZrP–I composite membranes were investigated. The effects of introducing sub-μm porous PTFE film and ZrP particles into Nafion membranes on the DMFC performance were investigated. The influence of ZrP hybridizing process into NF membranes (the process of preparing NF–ZrP–I is inserting ZrOCl₂ into NF membranes after Nafion is annealed and the process of preparing NF–ZrP–d is mixing ZrOCl₂ into a Nafion solution before Nafion is annealed) on the morphology of NF–ZrP composite membranes and thus on the DMFC performance was also discussed.     

Preparation and Characterization of TiO2 Thin Films by Sol-Gel Method

Titanium dioxide (TiO₂) thin films have been deposited on silicon and glass substrates by the sol-gel process using titanium iso-propoxide [Ti(O-i-C₃H₇)₄]. The bond configuration of the TiO₂ thin films was analyzed by using FTIR in the wavenumber range from 400 to 4000 cm^–1. The spectral transmittance of as-deposited TiO₂ films deposited on fused silica glass was measured in the wavelength range from 200 to 900 nm. X-ray diffraction measurements were performed to determine the crystallinity of the TiO₂ films. As-deposited films were amorphous. As the film was annealed at higher temperature, the structure was transformed from amorphous to the anatase crystalline state. The chemical composition of the deposited film was investigated using X-ray photoelectron spectroscopy (XPS). The films are essentially stoichiometric with carbon as the dominant impurity on the surface. Raman spectra show the characteristic of TiO₂ anatase phase. The electrical properties of the TiO₂ films were measured using capacitance-voltage (C-V) and current-voltage techniques. From C-V measurements, the dielectric constants were calculated to be approximately 26 for the as-deposited films and 75–82 for films annealed at 700°C in different atmosphere. For the as-deposited samples, the breakdown voltage was 2.7 MV/cm, and for an electric field of 1 MV/cm, the leakage current was 5 × 10^–5 A/cm² and the resistivity was 2.2 × 10¹⁰ -cm.     

Effect of crystallization and annealing on polyacrylonitrile membranes for ultrafiltration

Polyacrylonitrile (PAN) membrane is known as one of the hydrophilic membranes for ultrafiltration. However, the membrane has been preventing from the versatile applications, because the semi-crystalline PAN membranes are so brittle that cannot reuse once the membrane has been dried. The effect of crystalline domains in asymmetric polyacrylonitrile membranes is investigated, when the membranes are annealed in hot water and when the membranes are dried. Asymmetric polyacrylonitrile membranes were prepared via phase inversion process in a water bath and the effect of additive, PVP to the casting solution on the morphology and the water flux and the rejection were investigated. When the membranes were annealed in hot water (80 °C), the size of pores have been reduced and the water flux also decreased. Using wide angle X-ray scattering (WAXS), the effect of absorbed water on PAN membranes was studied. The absorption of water in PAN membranes mainly occurred through amorphous phase like a plasticizer, and induced the change of crystalline structure. The size of crystallite and the degree of crystallinity have changed when the membrane were annealed in the hot water. When the asymmetric PAN membranes were dried, the moisture also plays a crucial role in transforming the crystalline structures. The kinetics of drying strongly influences the size of crystallite as well as the crystallinity.     

溶胶-凝胶法制备聚砜/二氧化钛有机-无机杂化超滤膜

采用溶胶-凝胶法制备了不同TiO₂含量的PSF/TiO₂杂化超滤膜, 并通过SEM, XRD TG/DTA, 超滤实验, 机械性能测试, 水接触角测试等手段对膜的结构和性能进行了表征. 结果表明: 当TiO₂的质量分数为9.3%时, 膜亚层的指状孔消失, 形成了以纳米TiO₂颗粒为交联点的网络状孔, 同时膜的亲水性、机械性能和热稳定性都有明显的改善, 并在截留滤基本保持不变的情况下, 水通量明显提高. 但过高的TiO₂含量(w≥11.9%)会产生严重的纳米颗粒团聚现象而造成膜的各项性能指标下降.