Preparation and shape memory properties of TiO_2/PLCL biodegradable polymer nanocomposites

The preparation of TiO2/poly（L-lactide-co-ε-caprolactone）（PLCL） nanocomposites and their properties were reported.TiO2nanoparticles were surface modified by ring-opening polymerization of ε-caprolactone（ε-CL）.The resulting poly（ε-caprolactone）-grafted TiO2（g-TiO2） was characterized by Fourier transform infrared spectroscopy（FTIR）,thermogravimetric analysis（TGA） and transmission electron microscopy（TEM）.The g-TiO2can be uniformly dispersed in chloroform and the g-TiO2/PLCL nanocomposites were successfully fabricated through solvent-casting method.The effects of the content of g-TiO2nanoparticles on tensile properties and shape memory properties were investigated.A significant improvement in the tensile properties of the 5% g-TiO2/PLCL mass fraction nanocomposite is obtained：an increase of 113% in the tensile strength and an increase of 11% in the elongation at break over pure PLCL polymer.The g-TiO2/PLCL nanocomposites with a certain amount of g-TiO2content have better shape memory properties than pure PLCL polymer.The g-TiO2nanoparticles play an additional physical crosslinks which are contributed to improvement of the shape memory properties.

Distance-Dependent Long-Range Electron Transfer in Protein:a Case Study of Photosynthetic Bacterial Light-Harvesting Antenna Complex LH2 Assembled on TiO 2 Nanoparticle by Femto-Second Time-Resolved Spectroscopy

The function of protein in long-range biological electron transfer is a question of debate. We report some preliminary results in femtosecond spectroscopic study of photosynthetic bacterial light-harvesting antenna complex assembled onto TiO2 nanoparticle with an average size of 8 nm in diameter. Crystal structure shows that photosynthetic bacterial antenna complex LH2 has a ring-like structure composed by alpha- and beta-apoprotein helices. The alpha- and beta-transmembrance helices construct two concentric cylinders with pigments bacteriochlorophyll a (Bchl a) and carotenoid (Car) buried inside the protein. We attempt to insert TiO2 nanoparticle into the cavity of the inner cylindrical hollow of LH2 to investigate the nature of the electron transfer between the excited-state Bchl a and the TiO2 nanoparticle. A significant decrease in the ground state bleaching recovery time constant for Bchl a at 850 run (B850) in respect to that of the Bchl a in free LH2 has been observed. By using the relation of distance-dependent long-range electron transfer rate in protein, the distance between the donor B850 and the acceptor TiO2 nanoparticle has been estimated, which is about 0.6 nm. The proposed method of assembling proteins onto wide-gap semiconductor nanoparticle can be a promising way to determine the role of the protein playing in biological electron transfer processes.

Effect of sub-acute exposure to TiO_2 nanoparticles on oxidative stress and histopathological changes in Juvenile Carp (Cyprinus carpio)

Increasing application of nanotechnology highlights the need to clarify and understand nanotoxicity. Mammalian and in vitro studies have raised concerns about the toxicity of titanium dioxide nanoparticles （TiO2-NPs）, but there are limited data on ecotoxicity to aquatic organisms. In this work, the sub-acute toxicity of TiO2-NPs to carp （Cyprinus carpio） was assessed. Superoxide dismutase （SOD）, catalase （CAT） and peroxidase （POD） activities and lipid peroxidation （LPO） levels in liver, gill and brain tissues of carps varied with concentration of TiO2-NPs suspensions and exposure time （up to 8 d）. As a result, 100 and 200 mg/L TiO2-NPs caused statistically significant decrease in SOD, CAT and POD activities and significant increase in LPO levels in tissues （P 〈 0.05）, suggesting that the fish exposed to these two concentrations of TiO2-NPs suffered from the oxidative stress. The extent of depletion of antioxidant enzymes activities and the elevation of LPO in the liver was the greatest, indicating that the liver might be the most susceptible organ to TiO2-NPs exposure. In addition, carps had gill pathologies including edema and thickening of gill lamellae as well as gill filaments, and liver pathologies including necrotic and apoptosis hepatocytes after exposed to 100 and 200 mg/L TiO2-NPs for 20 d. These results indicated a potential risk from TiO2-NPs released into the aqueous environment.

Analysis of trace mercury in water by solid phase extraction using dithizone modified nanometer titanium dioxide and cold vapor atomic absorption spectrometry

A new method for analysis of trace mercury in water samples was developed, based on the combination of preconcentration/separation using dithizone-modified nanometer titanium dioxide （TiO2） as a solid phase extractant and determination by cold vapor atomic adsorption spectrometry （CVAAS）. Dithizone was dissolved with alcohol and loaded on the surface of nano-sized TiO2 powders by stirring. The static adsorption behavior of Hg^2＋on the dithizone-modified nanoparficles was investigated in detail. It was found that excellent adsorption ratio for Hg^2＋ could be obtained in the pH range of 7-8 with an oscillation time of 15 rain, and a 5 mL of 3.5 mol·L^-1 HCI solution could quantitatively elute Hg^2＋ from nanometer TiO2 powder. Common coexisting ions caused no obvious influence on the determination of mercury. The mechanisms for the adsorption and desorption were discussed. The detection limit （30） for Hg^2＋ was calculated to be 5 ng·L^-1. The proposed method was applied to the determination of Hg^2＋ in a mineral water sample and a Zhujiang River water sample. By the standard addition method, the average recoveries were found to be 94.4%-108.3% with RSD （n = 5） of 2.9%-3.5%.

STM and STS investigations of Ce-doped TiO_2 nanoparticles

Ce-doped titanium oxide nanoparticles were investigated in the paper. The surface structures of undoped and Ce-doped TiO2 nanoparticles were observed by scanning tunneling microscopy （STM）. The experimental results of scanning tunneling spectroscopy （STS） show that the surface electronic structures of TiO2 nanoparticles are modified by introducing new electronic states in the surface band gap through cerium ion doping. The results are discussed in terms of the influence of doping concentration on the surface band gap of TiO2.

Fabrication of SPES/Nano-TiO_2 Composite Ultrafiltration Membrane and Its Anti-fouling Mechanism

Membrane fouling is one of the major obstacles for reaching a high flux over a prolonged period of ultrafiltration（UF）process.In this study,a sulfonated-polyethersulfone（SPES）/nano-TiO2 composite UF membrane with good anti-fouling performance was fabricated by phase inversion and self-assembly methods.The TiO2 nanoparticle self-assembly on the SPES membrane surface was confirmed by X-ray photoelectron spectroscopy （XPS）and FT-IR spectrometer.The morphology and hydrophilicity were characterized by scanning electron microscopy（SEM）,atomic force microscopy（AFM）and contact angle goniometer,respectively.The anti-fouling mechanism of composite UF membrane was discussed through the analysis of the micro-structure and component of UF membrane surface.The results showed that the TiO2 content and the micro-structure of the composite UF membrane surface had great influence on the separation and anti-fouling performance.

Electrochemical determination of vitamin C in the presence of uric acid by a novel TiO_2 nanoparticles modified carbon paste electrode

The electrochemical behavior of vitamin C（ascorbic acid or AA） is investigated on the surface of a carbon-paste electrode modified with TiO2 nanoparticles and 2,2＇-（1,2 butanediylbis（nitriloethylidyne））-bis-hydroquinone（BBNBH）.The prepared modified electrode showed an efficient catalytic role in the electrochemical oxidation of AA,leading to remarkable decrease in oxidation overpotential and enhancement of the kinetics of the electrode reaction.This modified electrode exhibits well-separated oxidation peaks for AA and uric acid（UA）.The modified electrode is successfully applied for the accurate determination of AA in pharmaceutical preparations.

Effect of TiO_2 Nanoparticles on Photochromism of WO_3 Colloids

WO2 and TiO2 colMds were synthesized by the hydrolysis technique and part of the TiO2 colloid was treated by means of the hydrothermal method. The photochromic performances of the resulting materials obtained via combining the WO3 colloid with the treated TiO2 colloid and the non-treated TiO2 colloid, respectively, are very different. The TiO2 colloid without hydrothermal treatment can effectively improve the photochromic performance of the WO3colloid. The TiO2 nanoparticles were investigated in detail by XRD, TEM, surface photovohage spectra（SPS） and field-induced surface photovoltage spectrometry（FISPS）. The photochromism mechanism of WO3 colloid is discussed.

Surface Texturing of TiO_2 Film by Mist Deposition of TiO_2 Nanoparticles

Unique and various microstructures of titanium oxide(TiO_2 ) film including macroporous structure, chromatic veins and rings, have been easily fabricated by mist deposition method on silicon substrate with mild preparation conditions. Rutile phase TiO_2 nanoparticles were directly used as starting material to prepare film and led to a simple preparation process. It was found that several different microstructures existed in the sample and changed with the varied positions from the center to the edge of the film when the concentration of the TiO_2 suspension is 0.06 mol/l, the deposition time is 30 min, the flow rate is 1 l/min and the temperature is150. The surface texturing shows apparent distinction as the concentration of the TiO_2 suspension decreased to 0.03 mol/l and 0.01 mol/l.

The Gas Nucleation Process Study of Anatase TiO_2 in Atmospheric Non-Thermal Plasma Enhanced Chemical Vapor Deposition

Abstract The gas phase nucleation process of anatase TiO2 in atmospheric non-thermal plasma enhanced chemical vapor deposition is studied. The particles synthesized in the plasma gas phase at different power density were collected outside of the reactor. The structure of the collected particles has been investigated by field scanning electron microscope （FESEM）, X-ray diffraction （XRD）, high resolution transmission electron microscopy （HRTEM） and selected area electron diffraction （SAED）. The analysis shows that uniform crystalline nuclei with average size of several nanometers have been formed in the scale of micro second through this reactive atmo- spheric plasma gas process. The crystallinity of the nanoparticles increases with power density. The high density of crystalline nanonuclei in the plasma gas phase and the low gas temperature are beneficial to the fast deposition of the 3D porous anatase TiO2 film.

Functionalization of Nylon Fabrics with Dopamine Deposition and TiO2 Nanoparticles Immobilization

Ultraviolet(UV)radiation can cause degradation or aging of many polymers and shorten the working-life of their products.Thus,UV protective covers are required in various occasions.Textiles with the UV-shielding function possess unique properties compared with those covers in board or film shapes.TiO_2 nanoparticles(NPs),which were reported to have superior UV blocking function,can be used to produce UV protective covers in combination with fabric.However,efficient and environmentally friendly immobilization of TiO_2 Nps onto the fabrics is challenging.Polydopamine(PDA),a biomimetic synthetic polymer,has attracted great attentions recently due to its superior affinity to various materials and facile application procedure.Hence,in this research,the surface of nylon fabrics was modified by PDA to immobilizeTiO_2 NPs.Themodificationconditionswere systematically optimized.The immobilization of the NPs was confirmed by Fourier transform infrared spectrometer(FTIR)and scanning electron microscope(SEM).The functionalized nylon fabrics were proved to exhibit improved UV protection properties even after washing.This work provides a new and versatile surface modification technique for textiles.

Ag-Cu Nanoparticles Supported on N-Doped TiO2 Nanowire Arrays for Efficient Photocatalytic CO2 Reduction

Photocatalytic reduction of CO2 into various types of fuels has attracted great interest,and serves as a potential solution to addressing current global warming and energy challenges.In this work,Ag-Cu nanoparticles are densely supported on N-doped TiO2 nanowire through a straightforward nanofabrication approach.The range of light absorption by N-doped TiO2 can be tuned to match the plasmonic band of Ag nanoparticles,which allows synergizing a resonant energy transfer process with the Schottky junction.Meanwhile,Cu nanoparticles can provide active sites for the reduction of CO2 molecules.Remarkably,the performance of photocatalytic CO2 reduction is improved to produce CH4 at a rate of 720μmol·g-1·h-1 under full-spectrum irradiation.

Fulvic acid degradation using nanoparticle TiO_2 in a submerged membrane photocatalysis reactor

The degradation of fulvic acid（FA） by nanoparticle TiO2 in a submerged membrane photocatalysis（SMPC） reactor was studied. In this reactor, photocatalytic oxidation and membrane separation co-occured. The continuous air supplier provided O2 for the photocatalytical reaction and mixed the solution through an airflow controller. The particle TiO2 could automatically settle due to gravity without particle agglomeration so it could be easily separated by microfiltration（MF） membrane. It was efficient to maintain high flux of membranes. The effects of operational parameters on the photocatalytic oxidation rate of FA were investigated. Results indicated that photocatalyst at 0.5 g/L and airflow at 0.06 m^3/h were the optimum condition for the removal of fulvic acid, the removal efficiency was higher in acid media than that in alkaline media. The effects of different filtration duration on permeate flux rate of MF with P25 powder and with nanoparticle TiO2 were compared. Experimental results indicated that the permeate flux rate of MF was improved and the membrane fouling phenomenon was reduced with the addition of nanoparticle TiO2 catalyst compared with conventional P25 powder. Therefore, this submerged membrane photocatalysis reactor can faciliate potential application of photocatalytic oxidation process in drinking water treatment.

Novel water-based nanolubricant with superior tribological performance in hot steel rolling

Novel water-based nanolubricants using TiO2 nanoparticles(NPs)were synthesised by adding sodium dodecyl benzene sulfonate(SDBS)and glycerol,which exhibited excellent dispersion stability and wettability.The tribological performance of the synthesised nanolubricants was investigated using an Rtec ball-on-disk tribometer,and their application in hot steel rolling was evaluated on a 2-high Hille 100 experimental rolling mill,in comparison to those without SDBS.The water-based nanolubricant containing 4 wt%TiO2 and 0.4 wt%SDBS demonstrated superior tribological performance by decreasing coefficient of friction and ball wear up to 70.5%and 84.3%,respectively,compared to those of pure water.In addition to the lubrication effect,the suspensions also had significant effect on polishing of the work roll surface.The resultant surface improvement thus enabled the decrease in rolling force up to 8.3%under a workpiece reduction of 30%at a rolling temperature of 850◦C.The lubrication mechanisms were primarily ascribed to the formation of lubricating film and ball-bearing effect of the TiO2 NPs.

Apparent 1^st order rate constant of photodegradation of formaldehyde by carbon containing TiO2 nanoparticles

The apparent 1^st order rate constant of photodegradation of formaldehyde by carbon containing TiO2 nanoparticles has been investigated by numerical integration of mass transfer equation with measured degradation degree using a tubular photoreactor. The carbon containing TiO2 nanoparticles are synthesized by the oxidation of TiCl4 in propane/air flame CVD process with futile fraction up to 0.3 and carbon mass fractions up to 0.22, respectively. Thin TiO2 film is coated on the wall of the tubular reactor by sedimentation method. Effects of rutile mass fraction and carbon content have been examined on the apparent 1 ^st order rate constant and results show that, at 570ppm of formaldehyde loaded air stream, 80% relative humidity and about 100nm thin TiOa film, the 1^st order rate constant increases with increasing rutile mass fraction up to 0.3, occurs a maximum at the carbon content of about 5% by weight and is about 2.5 times of that at carbon content about zero or above 10%.

TiO2 nanoparticles in aquatic environments:impact on heavy metals distribution in sediments and overlying water

The extensive application of TiO_(2)nanoparticles(NPs)highlights the importance of investigating their influence on aquatic systems.In this work,the effect of TiO_(2)NPs on heavy metals speciation was studied on a lab scale.For this goal,a series of aquaria containing water,sediment,and TiO_(2)NPs with various concentrations were set up.The study results revealed that TiO_(2)NPs caused(copper)Cu,(mercury)Hg,(titanium)Ti,and(zinc)Zn to be adsorbed by sediments in the forms of exchangeable and Fe-Mn species.According to measurements,30μg/L of TiO_(2)NPs made Cu,Hg,Ti and Zn concentration in the water column decreased from 33,1.14,20,and 32 to 4,0.58,3,and 22.3μg/L,respectively.Manganese(Mn)was also adsorbed by sediment,and in all experiments,its concentration in the water column reduced from 44 to about 20μg/L.Due to the photocatalytic capacity of TiO_(2)NPs,arsenic(As)concentration in the water column increased from 0 to 8.7μg/L with the introduction of30μg/L of TiO_(2)NPs.The sequential extraction results showed that in all experiments,concentrations of lead(Pb),nickel(Ni),and cobalt(Co)remained constant in different chemical species of sediment,which meant conservative behavior of them in presence of TiO_(2)NPs.In addition,a remarkable change was observed in water quality parameters such as ORP,TDS,TOC,BOD,NO3’and PO_(4)after the introduction of TiO_(2)NPs to aquaria.The reason behind these changes could be related to the decomposition of sediment organic content by TiO_(2)NPs.

Preparation of TiO_2 Nanoparticles Coated Cotton Fibers at Low Temperature and Their Photocatalytic Activity

TiO_2 nanoparticles coated cotton fiber composite was successfully prepared by using a sol-gel method at low temperature(about 100℃) using tetrabutyl-titanate [Ti(OBu)_4] as raw material.The preparation of the TiO_2 colloid and the composite were described.The properties of resulting materials were characterized by SEM and XRD,the photocatalytic degradation performance was tested using methylene blue(MB) as the target pollutant in aqueous solution.The results showed that the amorphous TiO_2 nanoparticles were distributed evenly on the outer surfaces of cotton fibers,which shows efficient photocatalytic properties when exposed to UV light,the degradation rate of MB reached 95.35% under the conditions of catalyst dosage 2.5 g/L,MB concentration 50 mg/L,irradiation time 120 min,and pH 10,and the photocatalytic activity of TiO_2/cotton fibers remained above 90% of its activity as-prepared after being used four times,the degradation rate of MB could reach 88.78% when irradiation time was 120 min.The photocatalytic degradation of MB could be properly described by the first-order kinetic law.By comparison of the removal rates of MB with and without UV light,it could be affirmed that the disappearance of MB was due to photodegradation rather than adsorption on cotton fibers.

Effects of Metal Oxide Modifications on Photoelectrochemical Properties of Mesoporous TiO2 Nanoparticles Electrodes for Dye-Sensitized Solar Cells

Mesoporous TiO2 （m-TiO2） nanoparticles were used to prepare the porous film electrodes for dye-sensitized solar cells, and a second metal oxide （MgO, ZnO, A1203, or NiO） modifi- cation was carried out by dipping the m-TiO2 electrode into their respective nitrate solution followed by annealing at 500 ℃. Experimental results indicated that the above second metal oxide modifications on m-TiO2 electrode are shown in all cases to act as barrier layer for the interracial charge transfer processes, but film electron transport and interfacial charge recombination characteristics under applied bias voltage were dependent significantly on the existing states and kinds of these second metal oxides. Those changes based on sec- ond metal oxide modifications showed good correlation with the current-voltage analyses of dye-sensitized solar cell, and all modifications were found to increase the open-circuit photo- voltage in various degrees, while the MgO, ZnO, and NiO modifications result in 23%, 13%, and 6% improvement in cell conversion efficiency, respectively. The above observations indi- cate that controlling the charge transport and recombination is very important to improve the photovoltaic performance of TiO2-based solar cell.

Decomposition of formaldehyde based on gold-coated TiO2 nanoparticles

The synthesis of gold nanoparticles caped with visible light-responsible TiO2 nanoparticles. was prepared by using electrochemical Oxidation-Reduction Cycles （ORC） in 0.1 M HCI aqueous solution containing 60 mM visible light-responsible TiO2 nanoparticles. Firstly, an Au substrate was cycled in a deoxygenated aqueous solution containing 0.1 M HCI and 60 mM anatase TiO2 nanoparticles from -0.28 to ＋1.22 V vs Ag/AgCI at 500 mV/s with 25 scans. The durations at the cathodic and anodic vertexes are 10 and 5 s, respectively. After this process, Au-and TiO2-containing complexes were left in the solution. Then a Pt electrode immediately replaced the Au working electrode, and a cathodic overpotential of 0.6 V from the Open Circuit Potential （OCP） was applied under sonification to synthesize Au nanoparticles. Encouragingly, the prepared Au nanoparticles caped with visible light-responsible TiO2 nanoparticles are more active for the decomposition of formaldehyde than pure visible light-responsible TiO2 nanoparticles are in the same condition. After 5 days testing, the formaldehyde was decomposed ca. 35% in containing Au nanoparticles caped with visible light-responsible TiO2 nanoparticles, but the formaldehyde was decomposed only ca. 25% in containing pure visible light-responsible TiO2 nanoparticles.

TiO_2 nanoparticle-based electron transport layer with improved wettability for efficient planar-heterojunction perovskite solar cell

The electron transport layer （ETL） plays an important role in planar heterojunction perovskite solar cell （PSCs）, by affecting the light-harvesting, electron injection and transportation processes, and especially the crystal- lization of perovskite absorber. In this work, we utilized a commercial TKD-TiO2 nanoparticle with a small diameter of 6 nm for the first time to prepare a compact ETL by spin coating. The packing of small-size particles endowed TKD-TiO2 ETL an appropriate surface-wettability, which is beneficial to the crystallization of perovskite deposited via solution-processed method. The uniform and high-transmittance TKD-TiO2 films were successfully incorporated into PSCs as ETLs. Further careful optimization of ETL thickness gave birth to a highest power conversion efficiency of 11.0%, which was much higher than that of PSC using an ETL with the same thickness made by spray pyrolysis. This TKD-TiO2 provided a universal solar material suitable for the further large-scale production of PSCs. The excellent morphology and the convenient preparation method of TKD-TiO2 film gave it an extensive application in photovoltaic devices.