Photocatalytic degradation of methyl orange using a TiO2/Ti mesh electrode with 3D nanotube arrays

To further improve the photocatalytic techniques for water purification and wastewater treatment, we successfully prepared a new type of TiO(2)/Ti mesh photoelectrode, by anodization in ethylene glycol solution. The three-dimensional arrays of nanotubes formed on Ti mesh show a significant improvement in photocatalytic activity, compared to the nanotube arrays formed on foil. This can be demonstrated by about 22 and 38% enhancement in the degradation efficiency per mass and per area, respectively, when TiO(2)/Ti mesh electrode was used to photocatalyze methyl orange (MO). Furthermore, the effects of different parameters on MO photodegradation were investigated, such as different photoelectrode calcination temperature, the initial pH value of MO solution, and the present of hydrogen peroxide. The superior photocatalytic activity could be achieved by the TiO(2)/Ti mesh photoelectrode calcinated at 550 °C, due to the appearance of mixed crystal phases of anatase and rutile. In strong acidic or caustic conditions, such as pH 1 or 13, a high degradation efficiency can be both obtained. The presence of H(2)O(2) in photocatalytic reactions can promote photocatalytic degradation efficiencies. Moreover, the experimental results demonstrated the excellent stability and reliability of the TiO(2)/Ti mesh electrode.     

TiO_2-(线性低密度聚乙烯-g-马来酸酐)/低密度聚乙烯薄膜的制备及其光催化降解性能

以线性低密度聚乙烯(LLDPE)-g-马来酸酐(MA)作为相容剂制备了可光催化降解的TiO_2-(LLDPE-gMA)/LDPE薄膜。采用SEM、XRD、FT-IR对制备的TiO_2-(LLDPE-g-MA)/LDPE薄膜样品进行了表征。由于引入的LLDPE-g-MA改善了纳米TiO_2与LDPE之间的相容性,TiO_2-(LLDPE-g-MA)/LDPE薄膜具有更高的伸长率。SEM结果显示,LLDPE-g-MA显著削弱了纳米TiO_2在LDPE中的团聚,使高分散度的纳米TiO_2具备更高的光催化降解效率,增加了降解过程中的膜质量的损失。     

全降解聚甲基乙撑碳酸酯/埃洛石纳米管复合材料的制备与性能

通过熔融共混的方法制备了聚甲基乙撑碳酸酯/埃洛石纳米管(PPC/HNTs)复合材料,并利用万能试验机、差示扫描量热分析仪(DSC)、热重分析仪(TG)及扫描电子显微镜(SEM)分别研究了复合材料的力学性能、热性能及微观形态。结果表明,HNTs的加入显著提高了材料的拉伸强度和拉伸模量,但是降低了材料的断裂伸长率和热稳定性,HNTs的用量对材料的玻璃化温度影响不大,不同用量的HNTs以纳米尺度均匀分散在PPC基体中。     

Titanium dioxide-mediated heterogeneous photocatalytic degradation of terbufos: parameter study and reaction pathways

The photocatalytic degradation of terbufos in aqueous suspensions was investigated by using titanium dioxide (TiO(2)) as a photocatalyst. About 99% of terbufos was degraded after UV irradiation for 90 min. Factors such as pH of the system, TiO(2) dosage, and presence of anions were found to influence the degradation rate. Photodegradation of terbufos by TiO(2)/UV exhibited pseudo-first-order reaction kinetics, and a reaction quantum yield of 0.289. The electrical energy consumption per order of magnitude for photocatalytic degradation of terbufos was calculated and showed that a moderated efficiency (E(EO)=71 kWh/(m(3)order)) was obtained in TiO(2)/UV process. To obtain a better understanding of the mechanistic details of this TiO(2)-assisted photodegradation of terbufos with UV irradiation, the intermediates of the processes were separated, identified, and characterized by the solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) technique. The probable photodegradation pathways were proposed and discussed.     

Mechanical behaviour and essential work of fracture of halloysite nanotubes filled polyamide 6 nanocomposites

Polyamide 6 (PA 6)/halloysite nanotubes (HNT) nanocomposites were prepared by melt-extrusion compounding via masterbatch dilution process. A homogeneous dispersion of HNTs in PA 6 matrix was achieved. Differential scanning calorimetric measurements showed that addition of HNTs into PA 6 matrix enhanced the crystallization temperature and degree of crystallinity, thus indicating an effective nucleation induced by the addition of HNTs. Upon halloysite addition, glass transition temperature, storage modulus, Young modulus, tensile strength and notched Charpy impact strength increased without loss of ductility. For the first time, the essential work of fracture (EWF) concept was used to analyse the toughening and fracture behaviour of PA 6/HNT systems. Significant increase (+38%) of the essential work of fracture of PA 6/HNT nanocomposites was noticed at HNTs contents as low as 4 wt.%.     

H(2)O(2)-sensitized TiO(2)/SiO(2) composites with high photocatalytic activity under visible irradiation

TiO(2)/SiO(2) composite photocatalysts were prepared by depositing of TiO(2) onto nano-SiO(2) particles. X-ray diffraction (XRD), transmission electron micrograph (TEM), Raman spectrometer, UV-Vis diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy (FT-IR) were employed to characterize the properties of the synthesized TiO(2)/SiO(2) composites. These results indicated that the products without calcination were amorphous, and calcination could enhance the crystallinity of TiO(2). Increases in the amount of TiO(2) would decrease the dispersion in the composites. H(2)O(2)-sensitized TiO(2)/SiO(2) composite photocatalysts could absorb visible light at wavelength below 550 nm. The photocatalytic activity of as-prepared catalysts was characterized by methyl-orange degradation. The results showed the uncalcined composite photocatalysts with amorphous TiO(2) exhibited higher photocatalytic activity under visible light, and the activity of catalysts with TiO(2) content over 30% decreased with increasing of TiO(2) content. Increases in the calcination temperature and TiO(2) content promote the formation of bulk TiO(2) and result in a decrease in activity.     

Incorporation of halloysite nanotubes into PVDF matrix: Nucleation of electroactive phase accompany with significant reinforcement and dimensional stability improvement

Poly(vinylidene fluoride)/halloysite nanotubes (PVDF/HNTs) nanocomposites were prepared via melt compounding. Electroactive β- and γ-phases of PVDF were nucleated by the HNTs due to electrical interaction between negatively charged surface of the HNTs and CH₂ groups of the PVDF. The ends and surface defects of the HNTs were also responsible for the formation of γ-phase, since long trans conformations with gauche defects were induced at the two regions via the formation of hydrogen bonding. In addition to nucleation of the electroactive phase, the HNTs were found to reinforce the PVDF matrix and improve its dimensional stability, as evidenced by the substantially increased tensile strength and Young’s modulus, and the remarkably decreased coefficient of thermal expansion (CTE). The improved tensile property and reduced CTE were attributed to the uniformly dispersed HNTs and good interfacial interaction between HNTs and PVDF matrix via hydrogen bonding.     

Synergy between surface adsorption and photocatalysis during degradation of humic acid on TiO2/activated carbon composites

A photocatalyst comprising nano-sized TiO(2) particles on granular activated carbon (GAC) was prepared by a sol-dipping-gel process. The TiO(2)/GAC composite was characterized by scanning electron microscopy (SEM), X-ray diffractiometry (XRD) and nitrogen sorptometry, and its photocatalytic activity was studied through the degradation of humic acid (HA) in a quartz glass reactor. The factors influencing photocatalysis were investigated and the GAC was found to be an ideal substrate for nano-sized TiO(2) immobilization. A 99.5% removal efficiency for HA from solution was achieved at an initial concentration of 15 mg/L in a period of 3h. It was found that degradation of HA on the TiO(2)/GAC composite was facilitated by the synergistic relationship between surface adsorption characteristics and photocatalytic potential. The fitting of experimental results with the Langmuir-Hinshelwood (L-H) model showed that the reaction rate constant and the adsorption constant values were 0.1124 mg/(L min) and 0.3402 L/mg. The latter is 1.7 times of the calculated value by fitting the adsorption equilibrium data into the Langmuir equation.     

Photocatalytic degradation of p-phenylenediamine with TiO2-coated magnetic PMMA microspheres in an aqueous solution

This study investigates the photocatalytic degradation of p-phenylenediamine (PPD) with titanium dioxide-coated magnetic poly(methyl methacrylate) (TiO2/mPMMA) microspheres. The TiO2/mPMMA microspheres are employed as novel photocatalysts with the advantages of high photocatalytic activity, magnetic separability, and good durability. The scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), and transmission electron microscopy (TEM) images of the TiO2/mPMMA microspheres are used to characterize the morphology, element content, and distribution patterns of magnetite and TiO2 nanoparticles. The BET-specific surface area and saturation magnetization of the TiO2/mPMMA microspheres are observed as 2.21 m(2)/g and 4.81 emu/g, respectively. The photocatalytic degradation of PPD are performed under various experimental conditions to examine the effects of initial PPD concentration, TiO2/mPMMA microsphere dosage, and illumination condition on the eliminations of PPD and chemical oxygen demand (COD) concentrations. Good repeatability of photocatalytic performance with the use of the TiO2/mPMMA microspheres has been demonstrated in the multi-run experiments. The photocatalytic kinetics for the reductions of PPD and COD associated with the initial PPD concentration, UV radiation intensity, and TiO2/mPMMA microsphere dosage are proposed. The relationships between the reduction percentages of COD and PPD are clearly presented.     

Photocatalytic degradation of gaseous benzene over TiO2/Sr2CeO4: preparation and photocatalytic behavior of TiO2/Sr2CeO4

The paper demonstrates that the photocatalytic activity of TiO(2) towards the decomposition of gaseous benzene in a batch reactor can be greatly improved by loading TiO(2) on the surface of Sr(2)CeO(4). The research investigates the optimum loading amount of TiO(2) on Sr(2)CeO(4) in enhancing the photocatalytic activity of TiO(2). The prepared photocatalyst was characterized by XRD, UV-vis diffuse reflectance and XPS analyses. TiO(2) is loaded on Sr(2)CeO(4) at 773K. TiO(2)/Sr(2)CeO(4) absorbs much more visible light than TiO(2). The XPS spectrum shows that there are Ti, O, C, Sr elements on the surface of the TiO(2)/Sr(2)CeO(4), and that the binding energy value of Ti2p transfers to a lower value. TiO(2)/Sr(2)CeO(4) demonstrates 2.0 times the photocatalytic activity of pure TiO(2). Based upon these observations, the mechanistic role of Sr(2)CeO(4) in the photocatalytic oxidation reaction has been suggested.     

Interactions between halloysite nanotubes and 2,5-bis(2-benzoxazolyl) thiophene and their effects on reinforcement of polypropylene/halloysite nanocomposites

Many types of clay tend to absorb organics via electron transferring interactions between the clay and the organics. This may be utilized to design clay incorporated polymer composites with better interfacial properties. In the present paper, 2,5-bis(2-benzoxazolyl) thiophene (BBT), capable of donating electrons, is selected as the interfacial modifier for polypropylene (PP)/halloysite nanotube (HNTs) composites. The electron transfer between HNTs and BBT are confirmed. The mechanical properties and the unique morphology of the nanocomposites are examined. Formation of fibrils of BBT in the presence of HNTs is found in the nanocomposites. The chemical composition of the fibrils in the nanocomposites is found to be composed of largely BBT and a small amount of HNTs. The formation mechanism of BBT fibrils are elucidated to be the strong interactions between BBT and HNTs under melt shearing. The formation of the BBT fibrils leads to much higher crystallinity compared with previously reported PP nanocomposites. The nanocomposites with BBT show substantially increased tensile and flexural properties, which are attributed to the enhanced crystallinity of the nanocomposites.     

P(MMA-AN)/TiO2复合粒子的制备及光催化性能

采用原位乳液聚合方法制备了基于共价键结合的P(MMA-AN)/TiO2复合粒子,红外光谱和热失重分析结果表明P(MMA-AN)在TiO2表面接枝率为15.9%。以甲基橙溶液为目标污染物,研究了P(MMA-AN)/TiO2复合粒子和TiO2对甲基橙的吸附和光催化降解甲基橙溶液的性能,结果表明:两种粒子对甲基橙的吸附都很少;在相同时间内,P(MMA-AN)/TiO2复合粒子对甲基橙溶液的降解性能优于TiO2,紫外光照180 min后,P(MMA-AN)/TiO2复合粒子对甲基橙溶液的降解率达到了88%,而TiO2仅为74%。     

Mechanical,thermal, and flame-retardant performance of polyamide 11–halloysite nanotube nanocomposites

This study focused on the influence of different filler loadings on the elongation at break and flammability properties of the PA11/FR/HNTs nanocomposites. Polyamide 11 (PA11)/flame-retardant (FR) additives/halloysite nanotubes (HNTs) nanocomposites were melt compounded via twin-screw extrusion for all the compositions. Three FR additive loadings (15, 20, and 25 wt%) and three HNTs loadings (2.5, 5, and 10 wt%) were selected. The formula with 25 % FR and 2.5 % HNT had the lowest additives content and the highest elongation at break of 10.22 % among all UL-94 V-0 rated formulas. A homogeneous dispersion of HNTs in PA11 matrix was observed by transmission electron microscopy. Differential scanning calorimeter measurements indicated that HNTs behaved as nucleating agents by accelerating the rate of crystallization, thus increasing crystallization temperature. The young’s modulus of the PA11 nanocomposites was enhanced with the addition of HNTs. Micro-scale combustion calorimeter results demonstrated that the addition of HNTs also decreased the peak heat release rate of the nanocomposites. These results indicate the effectiveness of HNTs on the mechanical, thermal, and flame-retardant performance of PA11/FR/HNTs nanocomposites.     

Photocatalytic degradation of polycyclic aromatic hydrocarbons on soil surfaces using TiO(2) under UV light

The photocatalytic degradation of phenanthrene (PHE), pyrene (PYRE) and benzo[a]pyrene (BaP) on soil surfaces in the presence of TiO(2) using ultraviolet (UV) light source was investigated in a photo chamber, in which the temperature was maintained 30 degrees C. The effects of various factors, namely TiO(2), soil pH, humic acid, and UV wavelength, on the degradation performance of polycyclic aromatic hydrocarbons (PAHs) were studied. The results show that photocatalytic degradation of PAHs follows the pseudo-first-order kinetics. Catalyst TiO(2) accelerated the photodegradation of PHE, PYRE and BaP significantly, with their half-lives being reduced from 533.15 to 130.77h, 630.09 to 192.53h and 363.22 to 103.26h, respectively, when the TiO(2) content was 0.5%. In acidic or alkaline conditions, the photocatalytic degradation rates of the PAHs were greater than those in neutral conditions. Humic acid significantly enhanced the PAH photocatalytic degradation by sensitizing radicals capable of oxidizing PAHs. Photocatalytic degradation rates of PYRE and BaP on soil surfaces with 2% TiO(2) were different at UV irradiation wavelengths of 254, 310 and 365nm, respectively. The synergistic effect of UV irradiation and TiO(2) catalysis was efficient for degradation of PAHs in contaminated soil.     

Preparation and properties of natural nanocomposites based on natural rubber and naturally occurring halloysite nanotubes

A ‘green’ composite based on natural halloysite nanotubes (HNTs) and natural rubber (NR) was prepared by mechanical mixing. A silane coupling agent, bis (triethoxysilylpropyl)-tetrasulphide, was utilized to enhance the properties of these composites. It was observed that the reinforcing activity of HNTs was superior to commercial silica coupled with the same amount of silane coupling agent. Moreover the on-set thermal degradation decomposition temperature was improved by ∼64 °C with the addition of 10 parts HNTs per hundred of rubber. Transmission electron microscopic images confirmed the good dispersion of the HNTs in the rubber matrix, whereas X-ray diffraction studies showed a little change in interlayer spacing between the two silicate layers of HNTs.     

Synthesis and performance of novel magnetically separable nanospheres of titanium dioxide photocatalyst with egg-like structure

A magnetically separable photocatalyst TiO(2)/SiO(2)/NiFe(2)O(4) (TSN) nanosphere with egg-like structure was prepared by a unique process that combined a liquid catalytic phase transformation method, reverse micelle technique and chemical precipitation means. The prepared photocatalyst shows high photocatalytic activity for the degradation of methyl orange in water. The magnetic property measurements indicate that the photocatalyst possesses a superparamagnetic nature. It can be separated from water when an external magnetic field is added and redispersed into water solution after the external magnetic field is eliminated. It is one of the promising photocatalysts for wastewater treatment. A transmission electron microscope (TEM) and an x-ray diffractometer (XRD) were used to characterize the structure of the TSN photocatalyst. The results indicate that nickel ferrite core nanoparticles were completely encapsulated into monodisperse silica nanospheres as carrier, and titania nanoparticle aggregates were coated onto the surface of SN nanospheres, forming an imperfect TiO(2) shell for photocatalysis. The SiO(2) layer between the NiFe(2)O(4) core and the TiO(2) shell effectively prevents the injection of charges from TiO(2) particles to NiFe(2)O(4), which gives rise to an increase in photocatalytic activity. Moreover, the recycled TSN exhibits good repeatability of the photocatalytic activity.     

Photocatalytic ozonation of dimethyl phthalate with TiO2 prepared by a hydrothermal method

TiO(2) was prepared by a hydrothermal method at a low temperature and used to degrade and mineralize dimethyl phthalate (DMP). TiO(2) was characterized by XRD, TEM, BET and UV-vis techniques. The characteristics of TiO(2) prepared by a hydrothermal method (h-t TiO(2)) included a good crystalline anatase phase, greater surface area, stronger absorption to UV light wavelength and lower agglomeration than TiO(2) prepared by a classic sol-gel method (s-g TiO(2)). The photocatalytic activity of h-t TiO(2) prepared under optimal hydrothermal condition (180°C for 10h) was 2.5 times higher than that of s-g TiO(2) in degrading DMP. The process of photocatalysis combined with UV irradiation and ozonation (TiO(2)/UV/O(3)) considerably improved the mineralization and degradation of DMP compared to photocatalysis combined with UV irradiation (TiO(2)/UV), ozonation combined with UV irradiation (UV/O(3)), and ozonation alone (O(3)). A kinetic study showed the mineralization in TiO(2)/UV/O(3) followed the Langmuir-Hinshelwood model.     

The combination of rotating disk photocatalytic reactor and TiO2 nanotube arrays for environmental pollutants removal

A combined photocatalytic system on one single TiO(2)-nanotube (TNT)/Ti photocatalyst, which was indeed the functional combination of photon-efficient thin-film and conventional bulk-phase photocatalysis processes, was effectively developed in rotating disk photocatalytic reactor for environmental purification applications. The TNT/Ti rotating disk, of uniform size and well-aligned, was successfully prepared by direct anodic oxidation on a dominantly large surface area of 38 cm(2), compared to the typical 1 cm(2) in available literature. To estimate the potentials of combined photocatalytic system for environmental applications, the degradation of rhodamine B was carried out under the optimized conditions, a substrate removal efficiency of nearly 90% and a mineralization efficiency of 56% were observed for initial 20 mg/L solution after 3 h treatment. Compared with the combined photocatalytic system on TiO(2) nanoparticle disk, a significant improvement in substrate removal efficiency of about 25-40% was observed on TNT/Ti disk. It was confirmed that the main degradation of rhodamine B occurred on the upper half of TNT/Ti disk above the heavily colorized sample solution, which was attributed to the superior UV utilization efficiency and the resultant high interfacial photoactivity.     

Photocatalytic degradation of azo dyes using Au:TiO2, gamma-Fe2O3:TiO2 functional nanosystems

We report photocatalytic degradation studies on Navy Blue HE2R (NB) dye on significant details as a representative from the class of azo dyes using functional nanosystems specifically designed to allow a strong photocatalytic activity. A modified sol-gel route was employed to synthesize Au and gamma-Fe2O3 modified TiO2 nanoparticles (NPs) at low temperature. The attachment strategy is better because it allows clear surface of TiO2 to remain open for photo-catalysis. X-ray diffraction, Raman and UV-VIS spectroscopy studies showed the presence of gold and iron oxide phases along-with the anatase TiO2 phase. TEM studies showed TiO2 nanocomposite particles of size approximately 10-12 nm. A detailed investigation on heterogeneous photocatalytic performance for Navy Blue HE2R dye was done using the as-synthesized catalysts Au:TiO2 and gamma-Fe2O3:TiO2 in aqueous suspension under 8 W low-pressure mercury vapour lamp irradiation. Also, the photocatalytic degradation of Amranth and Orange G azo dyes were studied. The surface modified TiO2 NPs showed significantly improved photocatalytic activity as compared to pure TiO2. Exposure of the dye to the UV light in the presence of pure and gold NPs attached TiO2 catalysts caused dye degradation of about approximately 20% and approximately 80%, respectively, in the first couple of hours. In the presence of gamma-Fe2O3 NPs attached TiO2, a remarkable approximately 95% degradation of the azo dye was observed only in the first 15 min of UV exposure. The process parameters for the optimum catalytic activity are established which lead to a complete decoloration and substantial dye degradation, supported by the values of the Chemical Oxygen Demand (COD) approximately 93% and Total Organic Carbon (TOC) approximately 65% of the treated dye solution after 5 hours on the employment of the UV/Au:TiO2/H2O2 photocatalytic process.     

泡沫镍负载TiO2和TiO2/Al2O3薄膜的光催化性能研究

以泡沫镍为载体，Al2O3作为过渡中间层，用溶胶-凝胶法在泡沫镍上负载锐钛矿相的TiO2薄膜，制成泡沫金属基的TiO2和TiO2／Al2O3光催化剂，利用XRD和FE-SEM等测试手段对其性质进行表征，用乙醛气体的光催化降解测试其活性．研究表明：泡沫镍负载的TiO2和TiO2／Al2O3薄膜具有良好的光催化活性，特别是TiO2／Al2O3薄膜具有更高的催化活性．这是由于负载的Al2O3过渡中间层增大了载体的比表面积，具有吸附浓缩作用，同时也增加了负载光催化剂的活性位数量．实验表明：TiO2／Al2O3薄膜的光催化活性和稳定性较单一的TiO2薄膜有非常显著的提高．