Mixed Phase Anatase/rutile Titanium Dioxide Nanotubes for Enhanced Photocatalytic Degradation of Methylene-blue

Titanium dioxide Nanotubes(TNTs) prepared by electroless deposition have been annealed at air ambient and low temperature. As a result, the anatase/rutile phase composition of the TNTs can be tailored to the needs of later applications. Nanotubes with anatase/rutile mixed phase ratio of 4:1 have been produced in this report and further examined for their photocatalytical behavior. The photocatalytical properties of the TNTs have been observed by degradation of methylene-blue in aqueous solution under low power UV-light irradiation. The results shown in this report are based on the synergetic effect between rutile and anatase,which results in the mixed phase TiO 2 nanotubes having enhanced photocatalytical properties.

Fabrication of anatase titanium dioxide nanotubes by electroless deposition using polycarbonate for separate casting method

Titanium dioxide nanotubes(TNTs)were prepared by electroless deposition using ion track etched polycarbonate templates.The ion tracks were prepared to the desired diameter of the TNTs outer diameter.Titanium dioxide nanotubes with a diameter of minimum 80 nm having a wall thickness of minimum 10 nm can be fabricated using this method.To achieve nanotubes with thin walls and small surface roughness the tubes were generated by a several steps procedure under aqueous conditions at nearly room temperature.The presented approach will process open end nanotubes with well defined outer diameter and wall thickness.Using this method TNT arrays up to 109 tubes per cm2having a tube length up to 30μm can be produced,single tubes are also possible.The structural properties of the grown TNTs were investigated by using various analytical techniques,i.e.scanning electron microscopy(SEM),energy dispersive X-ray fluoresence spectrometer(EDX),X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),Raman spectroscopy and Photoluminescence.

Uniform nanoplating of metallic magnesium film on titanium dioxide nanotubes as a skeleton for reversible Na metal anode

To meet the low-cost concept advocated by the sodium metal anode,this paper reports the use of a pulsed electrodeposition technology with ionic liquids as electrolytes to achieve uniform nanoplating of metallic magnesium films at around 20 nm on spaced titanium dioxide(TiO_(2))nanotubes(STNA-Mg).First,the sodiophilic magnesium metal coating can effectively reduce the nucleation overpotential of sodium metal.Moreover,three-dimensional STNA can limit the volume expansion during sodium metal plating and stripping to achieve the ultrastable deposition and stripping of sodium metals with a high Coulombic efficiency of up to 99.5%and a small voltage polarization of 5 mV in symmetric Na||Na batteries.In addition,the comparative study of sodium metal deposition behavior of STNA-Mg and STNA-Cu prepared by the same route further confirmed the advantage of magnesium metal to guide sodium metal growth.Finally,the prepared STNA-Mg-Na metal anode and commercial sodium vanadium phosphate cathode were assembled into a full cell,delivering a discharge capacity of 110.2 mAh·g^(-1)with a retention rate of 95.6%after 110 cycles at 1C rate.

Enhancement of corona discharge induced wind generation with carbon nanotube and titanium dioxide decoration

Dip-coated double-wall carbon nanotubes(DWCNTs) and titanium dioxide(TiO2) sol have been prepared and smeared onto the tip of a conductive iron needle which serves as the corona discharge anode in a needle-cylinder corona system.Compared with the discharge electrode of a CNT-coated needle tip, great advancements have been achieved with the TiO_2/CNT-coated electrode, including higher discharge current, ionic wind velocity, and energy conversion efficiency,together with lower corona onset voltage and power consumption.Several parameters related to the discharge have been phenomenologically and mathematically studied for comparison.Thanks to the morphology reorientation of the CNT layer and the anti-oxidation of TiO_2, better performance of corona discharge induced wind generation of the TiO2/CNT-coated electrode system has been achieved.This novel decoration may provide better thoughts about the corona discharge application and wind generation.

Study of Band Gap of Carbon Nanotube-Titanium Dioxide Heterostructures

The authors present a photoluminescence and UV （ultraviolet）-optical absorbance study on single walled carbon nanotubes CNTs （carbon nanotubes） and TiO2 mixtures. The authors observed variation of△ф = 0.6 eV in optical gap for micrometric anatase and 0.1 eV for nanometric rutile or anatase at a concentration of CNTs of about 1.5 weight %. The large difference in △ф is attributed to differences in dimensions of dioxide grains and in morphology of CNTs/Ti02 composites. Photoluminescence emission is drastically reduced and absorption in the UV range is increased at low CNT concentration for both anatase and rutile phases.

Impact of Annealing Treatment on the Behaviour of Titanium Dioxide Nanotube Layers

In this work, we study the influence of the annealing treatment on the behaviour of titanium dioxide nanotube layers. The heat treatment protocol is actually the key parameter to induce stable oxide layers and needs to be better understood. Nanotube layers were prepared by electrochemical anodization of Ti foil in 0.4 wt% hydrofluoric acid solution during 20 minutes and then annealed in air atmosphere. In-situ X-ray diffraction analysis, coupled with thermogravimetry, gives us an inside on the oxidation behaviour of titanium dioxide nanotube layers compared to bulk reference samples. Structural studies were performed at 700°C for 12 h in order to follow the time consequences on the oxidation of the material, in sufficient stability conditions. In-situ XRD brought to light that the amorphous oxide layer induced by anodization is responsible for the simultaneous growths of anatase and rutile phase during the first 30 minutes of annealing while the bulk sample oxidation leads to the nucleation of a small amount of anatase TiO2. The initial amorphous oxide layer created by anodization is also responsible for the delay in crystallization compared to the bulk sample. Thermogravimetric analysis exhibits parabolic shape of the mass gain for both anodized and bulk sample;this kinetics is caused by the formation of a rutile external protective layer, as depicted by the associated in-situ XRD diffractograms. We recorded that titanium dioxide nanotube layers exhibit a lower mean mass gain than the bulk, because of the presence of an initial amorphous oxide layer on anodized samples. In-situ XRD results also provide accurate information concerning the sub-layers behavior during the annealing treatment for the bulk and nanostructured layer. Anatase crystallites are mainly localized at the interface oxide layer-metal and the rutile is at the external interface. Sample surface topography was characterized using scanning electron microscopy (SEM). As a probe of the photoactivity of the annealed TiO2 nanotube layers, degradation of an acid orange 7 (AO7) dye solution and 4-chlorophenol under UV irradiation (at 365 nm) were performed. Such titanium dioxide nanotube layers show an efficient photocatalytic activity and the analytical results confirm the degradation mechanism of the 4-chlorophenol reported elsewhere.

Study on Photocatalytic Degradation of Organic Dye by Titanium Dioxide Nanotube Array

Titanium based titanium dioxide （TiO2） nanotube arrays were prepared by electrochemical oxidation method, their microstructures were characterized, and the effects of sintering temperature and initial dye concentration and pH value on degradation performance of TiO2 nanotubc arrays wcrc investigated with methyl orange as a degradation object. The results showed that TiO2 nanotube arrays prepared by sintering at 500 ℃ exhibited good morphology and the highest photocata- lyric degradation efficiency; the degradation efficiency of the TiO2 nano material （500 ℃ ） to high concentration dye was higher than that to low concentration dye; the TiO2 nanotube array （500 ℃ ） exhibited higher degradation efficiency on dye solution at the pH of 3 than on that at the pH of 5.77 ; and the degradation efficien- cy of the TiO2 nanotube array （500 ℃） to 10 mg/L methyl orange solution （pH =3） reached 85.2%.

Study of Dye Absorption in Carbon Nanotube-Titanium Dioxide Heterostructures

In this work, the authors present a study of dye absorption in TiO2 doped with CNTs （carbon nanotubes）. Absorption decreases exponentially with the increase of CNTs in the film, while morphological characterization, conducted by SEM （scanning electron microscope） and TEM （transmission electron microscope） microscopes, suggests that this behavior is strongly related to morphological structure of grown films. For CNTs amounts greater than 1%, the authors observe the formation of CNTs clusters randomly distribute on TiO2 bulk, which strongly reduces the film porosity quenching the dye absorption. Comparison with optical properties of CNT/TiO2 filmstudied in the previous work, suggest that the best level of doping is with 0.5% of CNTs. FTIR （Fourier transform infrared spectroscopy） measurements conducted on a series of pristine and doped samples clearly indicate the absence of change in allotropic species of TiO2, while AFM （atomic force microscope） analysis indicates that the sample roughness strongly changes with doping, preventing the dye adsorption. Finally, measurements of cell efficiency indicate an increase of 5% in cells with 0.5% of CNT doping and a decrease for greater values.

RTV silicone rubber composites reinforced with carbon nanotubes,titanium-di-oxide and their hybrid:Mechanical and piezoelectric actuation performance

The use of nanofillers with high surface area and extreme purity in polymer composite is an effective strategy to obtain high performance polymeric nanocomposites.Therefore,the effect of nanofillers such as carbon nanotubes(CNT),titanium dioxide(TiO_(2)),and their hybrid on rubber-based composites was studied.In this study,rubber nanocomposites were fabricated by using room temperature vulcanized(RTV)silicone rubber matrix and nanofillers(i.e.CNT,TiO_(2),and CNT-TiO_(2))through solution casting method.Here,the purity and surface area of CNT(purity:>96%and BET surface area:300 m2/g)and TiO_(2)(purity:>98%and BET surface area:165 m2/g)were estimated by field emission scanning electron microscopy/energy dispersive X-ray(FESEM-EDX)and adsorption isotherms.The mechanical properties of the rubber nanocomposites were enhanced by incorporating nanofillers.The compressive modulus was 2.18 MPa for unfilled composites and increased to 6.8 MPa(CNT),3.95 MPa(CNT-TiO_(2)),and 2.44 MPa(TiO_(2))at 5 phr,respectively.Similarly,the tensile strength was 0.54 MPa for unfilled composites and increased to 1.37 MPa(CNT),1.33 MPa(CNT-TiO_(2))and 0.61 MPa(TiO_(2))at 5 phr,respectively.Further,the actuation displacement was improved with increasing input voltage and it was 2 mm for CNT,1.6 mm for CNT-TiO_(2) hybrid and 0.5 mm for TiO_(2) at 10 kV.Moreover,a series of experiments show the potential application in piezoelectric actuation.

Preparation of N-Doped TiO_2-Loaded Halloysite Nanotubes and Its Photocatalytic Activity under Solar-Light Irradiation

The N-doped TiO2-loaded halloysite nanotubes(N-Ti O2/HNTs) nanocomposites were prepared by using chemical vapor deposition method which was realized in autoclave. The photocatalytic activity of nanocomposites was evaluated by virtue of the decomposition of formaldehyde gas under solar-light irradiation. The XRD patterns verified that the anatase structured TiO2 was deposited on HNTs. The TEM images showed that the surface of HNTs was covered with nanosized TiO2 with a particle size of ca. 20 nm. The UV-vis spectra indicated that the N-Ti O2/HNTs presented a significant absorption band in the visible region between 400 nm and 600 nm. Under solar-light irradiation, the highest degradation rate of formaldehyde gas attained 90% after 100 min of solar-light irradiation. The combination of the photocatalytic property of TiO2 and the unique structure of halloysite would assert a promising perspective in degradation of organic pollutants.

EFFECTS OF INHALED TiO_2 NANOTUBES ON LUNG TISSUE AND SERUM BIOCHEMICAL INDEXES OF MICE

To evaluate the acute lung toxicity and the effect on serum biochemical indexes of inhaled TiO2 nanotubes , healthy and adult Kunming mice are exposed to aerosols of TiO2nanotubes in a sealed chamber , the concentration of which is 250mg / m 3 while another group of mice are exposed to room air only served as control.The blood , alveolar lavaged fluid and lungs of the mice are collected and examined after exposed for 7 , 14and 28d , respectively.The serum analysis shows that glucose ( Glu ) values with 7dexposure , alanine aminotransferase ( ALT ) and aspartate aminotransferase ( AST ) activities with 28dinhalation , and total bile acid ( TBA ) values with 7 , 28d as well as the creatine kinase ( CK ) levels with 28dexposure are significantly different from those of controls ( P< 0.05 ) .The pathological findings exhibit that more TiO 2 nanotubes are found in the interstitium of pulmonary alveoli with the experimental time prolonged.The results suggest that TiO 2 nanotubes do produce adverse responses to the lung and serum biochemical indexes of mice.Moreover , the responses become severer with the exposed-time prolonged.

Preparation and characterization of new photocatalyst combined MWCNTs with TiO_2 nanotubes

A new type of photocatalysts MWCNTs/TiO2-NTs nanocomposites prepared by combining multi-walled carbon nanotube(MWCNTs) with TiO2-derived nanotubes were synthesized by a modified hydrothermal method. The SEM,XRD,UV-Vis and TG-DTG were used to characterize its property. The produced MWCNTs/TiO2-NTs nanocomposites were used as the catalysts for photo-degradation of aquatic humic substances,Their photocatalytic efficiency was evaluated by the photodegradation of humic acid in an aqueous solution under ultraviolet light irradiation. The results show MWCNTs could enhance the activity of the photocatalysts;the best degradation efficiency was obtained by using MWCNTs/TiO2-NTs nanocomposites containing 20% MWCNTs as the photo-catalyst.

Preparation of titanium dioxide-double-walled carbon nanotubes and its application in flexible dye-sensitized solar cells

Titanium dioxide-double-walled carbon nano- tubes （TiO2-DWCNTs） with DWCNTs/TiO2 of 20 wt.% is prepared by a conventional sol-gel method. Doping the TiO2-DWCNTs in TiO2 photoanode, a flexible dye- sensitized solar cell （DSSC） is fabricated. The sample is characterized by scanning electron microscopy, X-ray diffraction （XRD）, Fourier transform infrared spectroscopy （FTIR） absorption, ultraviolet-visible spectroscopy （UV- vis） absorption spectra , electrochemical impedance spec- troscopy （EIS） technique and photovoltaic measurement. It is found that adding a certain amount of TiO2-DWCNTs can efficiently decrease the resistance of charge transport, improve dye adsorption. Under an optimal condition, a flexible DSSC contained with 0.50 wt.% TiOz-DWCNTs achieves a light-to-electric energy conversion efficiency of 3.89% under a simulate solar light irradiation of 100 mW. cm^2.

rGO/TNTs复合光催化剂的制备及其降解苯酚的性能研究

为提高光催化降解苯酚废水的性能,以P25为钛源,采用浓碱水热法制备二氧化钛纳米管(TNTs),水热法合成还原氧化石墨烯二氧化钛纳米管(rGO/TNTs)复合光催化剂。通过SEM,FTIR和EDS对材料进行了表征,并研究了不同的苯酚初始质量浓度、rGO/TNTs投加量、溶液pH值及H 2O 2添加量下rGO/TNTs对苯酚降解的反应动力学规律,测试了rGO/TNTs在紫外光和可见光下对水中苯酚的降解性能。结果表明,rGO和TNTs通过Ti—O—C化学键紧密结合在一起。不同影响因素下rGO/TNTs对苯酚的降解均符合一级反应动力学方程。在最佳光催化反应条件下,10 W紫外光和500 W可见光下rGO/TNTs对10 mg/L苯酚的降解率可分别达97%和98%。rGO/TNTs在较大程度上拓宽了TNTs的光响应范围,并具有较高的稳定性和循环利用率。

Absorption mechanism of carbon-nanotube paper- titanium dioxide as a multifunctional barrier material for lithium-sulfur batteries

Lithium-sulfur batteries attract much interest as energy storage devices for their low cost, high specific capacity, and energy density. However, the insulating properties of sulfur and high solubility of lithium polysulfides decrease the utilization of active materials by the battery resulting in poor cycling performance. Herein, we design a multifunctional carbon-nanotube paper/titanium-dioxide barrier which effectively reduces active material loss and suppresses the diffusion of lithium polysulfides to the anode, thereby improving the cycling stability of lithium-sulfur batteries. Using this barrier, an activated carbon/sulfur cathode with 70% sulfur content delivers stable cycling performance and high Coulombic efficiency （-99%） over 250 cycles at a current rate of 0.5 C. The improved electrochemical performance is attributed to the synergistic effects of the carbon nanotube paper and titanium dioxide, involving the physical barrier, chemical adsorption from the binding formation of Ti-S and S-O, and other interactions unique to the titanium dioxide and sulfur species.

Heterostructured ZnFe_2O_4/Fe_2TiO_5/TiO_2 Composite Nanotube Arrays with an Improved Photocatalysis Degradation Efficiency Under Simulated Sunlight Irradiation

To improve the visible light absorption and photocatalytic activity of titanium dioxide nanotube arrays(TONTAs), ZnFe_2O_4(ZFO) nanocrystals were perfused into pristine TONTA pipelines using a novel bias voltageassisted perfusion method. ZFO nanocrystals were well anchored on the inner walls of the pristine TONTAs when the ZFO suspensions(0.025 mg m L^(-1)) were kept under a60 V bias voltage for 1 h. After annealing at 750 °C for2 h, the heterostructured ZFO/Fe_2 TiO_5(FTO)/TiO_2 composite nanotube arrays were successfully obtained. Furthermore, Fe^(3+)was reduced to Fe^(2+)when solid solution reactions occurred at the interface of ZFO and the pristine TONTAs. Introducing ZFO significantly enhanced thevisible light absorption of the ZFO/FTO/TONTAs relative to that of the annealed TONTAs. The coexistence of type I and staggered type II band alignment in the ZFO/FTO/TONTAs facilitated the separation of photogenerated electrons and holes, thereby improving the efficiency of the ZFO/FTO/TONTAs for photocatalytic degradation of methylene blue when irradiated with simulated sunlight.

Fabrication of double-walled carbon nanotube film/TiO_2 nanotube array heterojunctions with length-dependent photoresponse for broad band photodetectors

A novel photodetector based on double-walled carbon nanotube （DWCNT） film/TiO2 nanotube array （TNA） heterojunctions was fabricated, which exhibited high photoresponse in a broad spectral range. The photoresponse of the detector was dramatically dependent on the length of the TNAs. High photocurrent-to-dark current ratio with a value of 3360 was observed in the visible range by optimizing the lengths of the TNAs. The photosensitive regions could be extended into the near-infrared range. These results reveal that DWCNT film/TNA heterojunctions show potential applications for broad band photodetectors.

One-pot Synthesis of TiO2 Nanoparticles in Suspensions for Quantification of Titanium Debris Release in Biological Liquids

In this work we have developed an analytical method to measure potential titanium debris released from TiO2 nanotube layers devices immersed in biological fluids. This quantitative study is highly required to ensure both the security and non toxicity of the nanostructured surfaces used as future implantable medical devices in the living. A one-pot synthesis process is developed to produce high quality standard solutions of titanium dioxide nanoparticles in aqueous medium. The elaborated dispersion is then used to fabricate standard solutions in both aqueous and human blood plasma media. The synthesized nanoparticles dispersion was characterized by granulometry. The nanoparticles structure and morphology were then observed using Transmission Electron Microscopy (TEM). Thermogravimetric Analysis (TGA) was used to evaluate the concentration of TiO2 in the suspension. A quantitative routine by the use of Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) is developed. The quantification threshold of titanium species is found to be in the 30 - 40 ppb range. None interference is detected between the particles and the human blood plasma. Using the established quantitative routine, the titanium species release from titania nanotube layers in human blood plasma is evaluated.

Feasibility of a Chronic Foreign Body Infection Model Studying the Influence of TiO2 Nanotube Layers on Bacterial Contamination

Bacterial infections on the surface of medical devices are a significant problem in therapeutic approach, especially when implants are used in the living. In cardiology, pacemaker generator pocket surfaces, made in titanium alloy can be colonized by pathogen microorganism. This contamination represents a major risk of sepsis, endocarditis and localized infections for patients. A way to limit this bacterial contamination is to modify the surface topography using nano-structuration process of the titanium alloy surface of the implanted devices. The aim of this study is to evaluate the influence of TiO2 nanotube layers on bacterial infection in the living, considering the feasibility of an animal model of chronic foreign body infection. TiO2 nanotube layers prepared by electrochemical anodization of Ti foil in 0.4 wt% hydrofluoric acid solution were implanted subcutaneously in Wistar rats. Three weeks after implantation, TiO2 implants were contaminated by a Staphylococcus epidermilis strain using two different concentrations at 106 and 108 colony forming unit (CFU) in order to induce a sufficient infection level and to avoid unwanted over infection consequences on rats health during the experiments. After 28 days in the living, 75% of nanotube layers initially submitted to the 108 CFU inoculum were contaminated while only 25% nanotube layers initially submitted to the 106 CFU inoculum remained infected. This significant result underlines the influence of TiO2 nanotube layers in decreasing the infection level. Our in vitro experiments showed that the synthesized TiO2 nanotubes indeed decreased the Staphylococcus epidermilis adhesion compared to unanodized Ti foil.

BaTiO_(3)热释电薄膜制备及性能研究

四方相BaTiO_(3)作为一种热释电材料,具有表面浸润性随温度而变化的性质,有望用在两相换热系统表面改善沸腾、提高换热效率。采用阳极氧化法制备了TiO_(2)纳米管,在此基础上利用水热合成法实现了BaTiO_(3)纳米管阵列薄膜的可控制备。通过调整氧化电压、NH4F浓度和氧化时间等参数,研究了纳米管的表面形貌和物相结构变化。结果表明:由于高电压导致电子电流增大,产生的氧气泡尺寸增大,纳米管的管径随氧化电压的增加而增加,管径分布在60~140nm,管壁厚度为10nm。增加NH4F浓度和氧化时间有助于TiO_(2)纳米管的形成。对钛片进行抛光处理可以显著提高氧化生成的纳米管阵列的平坦度。通过延长水热时间和增加高温退火处理,成功地将BaTiO_(3)立方相转换为具有热释电效应的四方相,且同较长水热时间的样品相比,经退火处理的样品具有更好的热释电性能。本研究结果为进一步研究阳极氧化TiO_(2)纳米管的生长机制,以及利用热释电材料自发极化强度变化来改善沸腾传热提供了参考价值。