Photodegradation of bisphenol-A in a batch TiO2 suspension reactor

In this work, the photocatalytic behaviors of bisphenol-A (BPA), which has been listed as one of endocrine disrupting chemicals, were carried out in a batch TiO₂ suspension reactor. The photodegradation efficiency has been investigated under the controlled process parameters including initial BPA concentration (i.e., 1–50 mg L^?1), TiO₂ dosage (i.e., 5–600 mg/200 cm³), initial pH (i.e., 3–11), and temperature (i.e., 10–70 °C). It was found that the optimal conditions in the photoreaction process could be coped with at initial BPA concentration = 20 mg L^?1, TiO₂ dosage = 0.5 g L^?1 (100 mg/200 cm³), initial pH = 7.0, and temperature = 25 °C. According to the Langmuir–Hinshelwood model, the results showed that the photodegradation kinetics for the destruction of BPA in water also followed the first-order model well. The apparent first-order reaction constants (k_obs), thus obtained from the fittings of the model, were in line with the destruction-removal efficiencies of BPA in all the photocatalytic experiments. Based on the intermediate products identified in the study, the possible mechanisms for the photodegradation of BPA in water were also proposed in the present study.     

Photodegradation of methyl tert-butyl ether (MTBE) by UV/H2O2 and UV/TiO2

Two UV-based advanced oxidation processes (AOPs), UV/H2O2 and UV/TiO2, were tested in batch reactor systems to evaluate the removal efficiencies and optimal conditions for the photodegradation of methyl tert-butyl ether (MTBE). The optimal conditions at an initial MTBE concentration of 1 mM ([MTBE]0=1 mM) were acidic and 15 mM H2O2 in UV/H2O2 system, and pH 3.0 and 2.0 g/l TiO2 in UV/TiO2 suspended slurries system under 254-nm UV irradiation. Under the optimal conditions, MTBE photodegradation during the initial period of 60 min in UV/H2O2 and UV/TiO2 systems reached 98 and 80%, respectively. In both systems, MTBE photodegradation decreased with increasing [MTBE]0. While MTBE photodegradation rates increased with increasing dosage of H2O2 (5-15 mM) and TiO2 (0.5-3 g/l), further increase in the dosage of H2O2 (20 mM) or TiO2 (4 g/l) adversely reduced the MTBE photodegradation. Pseudo first-order kinetics with regard to [MTBE] can be used to describe the MTBE photodegradation in both systems. The pseudo first-order rate constants linearly increased with the increase in the molar ratio of [H2O2]0 to [MTBE]0 in UV/H2O2 system and linearly increased with the decrease in [MTBE]0 in UV/TiO2 system.     

Removal of Pb(II) from aqueous solution on chitosan/TiO(2) hybrid film

This paper presents the adsorption of Pb(II) from aqueous solution using chitosan/TiO(2) hybrid film (CTF) adsorbent. Batch experiments were carried out as a function of solution pH, adsorption time, Pb(II) concentration and temperature. The equilibrium data fitted well with the linear Freundlich model. The adsorption process was proved to be the second grade reaction and the theoretically maximum adsorption amount at equilibrium was 36.8 mg-Pb/g. The influence parameters were optimized by response surface method (RSM), such as initial metal concentration, pH and temperature. The extreme points were gained by the Statistical Analysis System software: initial metal concentration is 50-55 mg/l, pH is 3-4 and temperature is 60 degrees C. Very high regression coefficient (R(2)=0.9689) indicates excellent evaluation of experimental data by second-order polynomial regression model. Under this condition the theoretical adsorption efficiency is 90.6%. It illuminates that this model is reliable to optimize the adsorption process and CTF is suitable for adsorbing Pb(II) from aqueous solution.     

Enhanced activity of bismuth-compounded TiO(2) nanoparticles for photocatalytically degrading rhodamine B solution

TiO(2) nanoparticles compounded with different amounts of bismuth were prepared by a sol-gel method, and the effects of compounding bismuth on the phase transformation, photoinduced charge separation and photocatalytic activity for degrading rhodamine B solution were mainly investigated, along with enhancement mechanism of photocatalytic activity of TiO(2) nanoparticles by compounding bismuth species. It can be confirmed that, by means of X-ray diffraction (XRD), surface photovoltage spectroscopy (SPS) and ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), compounding bismuth can extend the optical response, and effectively inhibit the phase transformation process from anatase to rutile, consequently greatly improving the anatase crystallinity so as to promote the photoinduced charge separation. These factors are responsible for the increase in the photocatalytic activity of TiO(2) compounded with an appropriate amount of bismuth species.     

Photodegradation of rhodamine B under visible light by bimetal codoped TiO2 nanocrystals

In the search for efficient photocatalysts working under visible light, we have investigated the effect of metal ions (Bi/Co, Fe/Co) codoping on the photocatalytic activity of TiO(2) prepared by stearic acid gel method. UV-vis spectra revealed that doped Co enhanced the absorbency of TiO(2) under visible light, and Bi/Co codoped TiO(2) showed higher absorbance than Fe/Co codoped TiO(2). The photoreaction based on the prepared samples for photodegradation of 20mg/l rhodamine B solution was examined. The results showed that Fe(0.1%)/Co(0.4%) codoped TiO(2) had the highest photoactivity among all as-prepared samples under visible light, though less absorbency of visible light, indicating that the photoactivity not only benefits from absorbency but also relates to the cooperative effect of the two dopants.     

Synthesis of Fe(2)O(3)/TiO(2) nanorod-nanotube arrays by filling TiO(2) nanotubes with Fe

Synthesis of hematite (α-Fe(2)O(3)) nanostructures on a titania (TiO(2)) nanotubular template is carried out using a pulsed electrodeposition technique. The TiO(2) nanotubes are prepared by the sonoelectrochemical anodization method and are filled with iron (Fe) by pulsed electrodeposition. The Fe/TiO(2) composite is then annealed in an O(2) atmosphere to convert it to Fe(2)O(3)/TiO(2) nanorod-nanotube arrays. The length of the Fe(2)O(3) inside the TiO(2) nanotubes can be tuned from 50 to 550?nm by changing the deposition time. The composite material is characterized by scanning electron microscopy, transmission electron microscopy and diffuse reflectance ultraviolet-visible studies to confirm the formation of one-dimensional Fe(2)O(3)/TiO(2) nanorod-nanotube arrays. The present approach can be used for designing variable one-dimensional metal oxide heterostructures.     

Granularity in ion-beam-sputtered TiO(2) films

TiO(2)-SiO(2) multilayer dielectric stacks that were deposited by ion-beam sputtering were found to have a granular structure. The grains were in the TiO(2) layers rather than in the SiO(2) layers. Their formation was due to the heating of the film during deposition. When the apparatus was modified to reduce the substrate temperature, the granularity was eliminated.     

Enhanced TiO2 photocatalytic degradation of bisphenol E by beta-cyclodextrin in suspended solutions

Enhancement of beta-cyclodextrin (beta-CD) on TiO(2) photocatalytic degradation of bisphenol E (BPE, bis(4-hydroxyphenyl)ethane) was investigated under a 250 W metal halide lamp (lambda> or =365 nm) in this work. In the system of photocatalytic degradation of BPE, the photodegradation rate of BPE in aqueous solutions containing beta-CD and TiO(2) was obviously faster than that in aqueous solutions containing only TiO(2). After 40 min of irradiation, beta-CD could increase the photodegradation efficiency by about 26% for 10 mg l(-1) BPE in the UV-vis/TiO(2) system and the photodegradation of 2.5-20.0 mg l(-1) BPE in aqueous solutions was found to follow pseudo-first-order law and the adsorption constant and the reaction rate constant of BPE in the system containing beta-CD and TiO(2) are obviously higher than those in the system containing only TiO(2), the influence factors on photodegradation of BPE were studied and described in details, such as beta-CD concentration, pH, BPE initial concentration and gas medium. The formation of CO(2) as a result of mineralization of BPE was observed during the photodegradation process. After 120 min of irradiation, the mineralization efficiency of BPE reached 61% in the presence of beta-CD, whereas mineralization efficiency was only 23% in the absence of beta-CD. The enhancement of photodegradation of BPE could be dependent on the enhancement of adsorption of BPE on TiO(2) surface and moderate inclusion-depth of BPE in the beta-CD cavity.     

Photodegradation of crystal violet in TiO(2) suspensions using UV-vis irradiation from two microwave-powered electrodeless discharge lamps (EDL(-2)): products, mechanism and feasibility

Aqueous crystal violet (CV) solutions containing P25-TiO(2) photocatalyst were irradiated with ultraviolet-visible (UV-vis) light from two microwave-powered electrodeless discharge lamps (EDL(-2)). The results demonstrated that approximately 94.4% of CV was effectively removed after 3 min of irradiation, with a pseudo-first order kinetic constant of 0.838 min(-1). According to 32 kinds of products, a five-step degradation pathway of CV was proposed. Further investigations showed that (1) three kinds of N-demethylated products and 4-dimethylaminobenzophenone (DLBP) were the main intermediates; (2) malachite green (MG) and leuco-crystal violet could not be generated by N-demethylation and phototransformation reactions, respectively; (3) bis(4-(dimethylamino)phenyl)methanone preferentially generated via decomposition of the conjugated structure of CV could be further N-demethylated into DLBP. Moreover, the unique degradation pathways of CV and MG were ascribed to the different substituents on the conjugated structures. Additionally, the cost and kinetic constant of different processes was also evaluated, and the results indicated the feasibility of this method for treatment of CV in field situations.     

Photodegradation and toxicity changes of antibiotics in UV and UV/H(2)O(2) process

The photodegradation of three antibiotics, oxytetracycline (OTC), doxycycline (DTC), and ciprofloxacin (CIP) in UV and UV/H(2)O(2) process was investigated with a low-pressure UV lamp system. Experiments were performed in buffered ultrapure water (UW), local surface water (SW), and treated water from local municipal drinking water treatment plant (DW) and wastewater treatment plant (WW). The efficiency of UV/H(2)O(2) process was affected by water quality. For all of the three selected antibiotics, the fastest degradation was observed in DW, and the slowest degradation occurred in WW. This phenomenon can be explained by R(OH,UV), defined as the experimentally determined OH radical exposure per UV fluence. The R(OH,UV) values represent the background OH radical scavenging in water matrix, obtained by the degradation of para-chlorobenzoic acid (pCBA), a probe compound. In natural water, the indirect degradation of CIP did not significantly increase with the addition of H(2)O(2) due to its effective degradation by UV direct photolysis. Moreover, the formation of several photoproducts and oxidation products of antibiotics in UV/H(2)O(2) process was identified using GC-MS. Toxicity assessed by Vibrio fischer (V. fischer), was increased in UV photolysis, for the photoproducts still preserving the characteristic structure of the parent compounds. While in UV/H(2)O(2) process, toxicity increased first, and then decreased; nontoxic products were formed by the oxidation of OH radical. In this process, detoxification was much easier than mineralization for the tested antibiotics, and the optimal time for the degradation of pollutants in UV/H(2)O(2) process would be determined by parent compound degradation and toxicity changes.     

Photocatalytic degradation of aqueous propoxur solution using TiO2 and Hbeta zeolite-supported TiO2

Photocatalytic activity of TiO2 and zeolites supported TiO2 were investigated using propoxur as a model pollutant. Hbeta, HY and H-ZSM-5 zeolites were examined as supports for TiO2. Hbeta was chosen as the TiO2 support based on the adsorption capacity of propoxur on these zeolites (Hbeta>HY=H-ZSM-5). TiO2/Hbeta photocatalysts with different wt.% were prepared and characterized by XRD, FT-IR and BET surface area. The progress of photocatalytic degradation of aqueous propoxur solution using TiO2 (Degussa P-25) and TiO2 supported on Hbeta zeolite was monitored using TOC analyzer, HPLC and UV-vis spectrophotometer. The degradation of propoxur was systematically studied by varying the experimental parameters in order to achieve maximum degradation efficiency. The initial rate of degradation with TiO2/Hbeta was higher than with bare TiO2. TOC results revealed that TiO2 requires 600min for complete mineralization of propoxur whereas TiO2/Hbeta requires only 480min. TiO2/Hbeta showed enhanced photodegradation due to its high adsorption capacity on which the pollutant molecules are pooled closely and hence degraded effectively.     

Mesoporous TiO2/Carbon Beads: One-Pot Preparation and Their Application in Visible-Light-Induced Photodegradation

Nano-Micro Letters - Mesoporous TiO2/Carbon beads have been prepared via a facile impregnation-carbonization approach, in which a porous anion-exchange resin and K2TiO(C2O4)2 were used as hard...     

Aqueous Cr(VI) photo-reduction catalyzed by TiO2 and sulfated TiO2

TiO(2) and sulfated TiO(2) (SO(4)(2-)/TiO(2)) catalysts with different textural properties were prepared under different calcination temperatures and the photo-reduction of Cr(VI) to Cr(III) catalyzed by these catalysts was investigated. For the photocatalytic reduction of Cr(VI), the photocatalytic activities of the TiO(2) samples were found to be strongly dependent of the calcination temperature and TiO(2) calcined at 400 degrees C showed a higher catalytic activity compared to other TiO(2) catalysts. In contrast, sulfation of TiO(2) stabilized the catalytic activities of SO(4)(2-)/TiO(2) catalysts. At low calcination temperature, SO(4)(2-)/TiO(2) catalysts exhibited catalytic activities almost comparable with that of TiO(2) and the catalytic activities of SO(4)(2-)/TiO(2) catalysts were markedly higher than TiO(2) under high calcination temperature. In addition, the removal of surface SO(4)(2-) of SO(4)(2-)/TiO(2) catalyst led to a marked decrease of the catalytic activity for Cr(VI) photo-reduction, suggesting that the presence of surface SO(4)(2-) provided an acid environment over the catalyst surface and favored the photo-reduction of Cr(VI).     

Steps on anatase TiO2(101)

Surface defects strongly influence the surface chemistry of metal oxides, and a detailed picture of defect structures may help to understand reactivity and overall materials performance in many applications. We report first-principles calculations of step edges, the most common intrinsic defects on surfaces (and probably the predominant ones on nanoparticles). We have determined the structure, energetics, and chemistry of step edges on the (101) surface of TiO(2) anatase, an important photocatalytic material. Scanning tunnelling microscopy measurements of step-edge configurations and the contrast in atomically resolved images agree remarkably well with the theoretical predictions. Step-edge formation energies as well as the adsorption energies of water scale with the surface energy of the step facet, a trend that is expected to generally hold for metal oxide surfaces. Depending on the terrace/step configuration, this can lead to a situation where a step is less reactive than the flat terrace.     

Highly active nanocrystalline TiO(2) photoelectrodes

A simple method for the fabrication of highly photoactive nanocrystalline two-layer TiO(2) electrodes for solar cell applications is presented. Diluted titanium acetylacetonate has been used as a precursor for covering SnO(2):F (FTO) films with dense packed TiO(2) nanocrystallites. The nanoporous thick TiO(2) film follows the dense packed thin TiO(2) film as a second layer. For the latter, amorphous TiO(2) nanoparticles have been successfully synthesized by a sol-gel technique in an acidic environment with pH<1 and hydrothermal growth at a temperature of 200?°C. The acidic nanoparticle gel was neutralized by basic ammonia and a TiO(2) gel of pH?5 was obtained; this pH value is higher than the recently reported value of 3.1 (Park et al 2005 Adv. Mater. 17 2349-53). Highly interconnected, nanoporous, transparent and active TiO(2) films have been fabricated from the pH?5 gel. SEM, AFM and XRD analyses have been carried out for investigation of the crystal structure and the size of nanoparticles as well as the surface morphology of the films. Investigation of the photocurrent-voltage characteristics has shown improvement in cell performance along with the modification of the surface morphology, depending on pH of the TiO(2) gel. Increasing the pH of the gel from 2.1 to 5 enhanced the overall conversion efficiency of the dye-sensitized solar cells by approximately 30%. An energy conversion efficiency of 8.83% has been achieved for the cell (AM1.5, 100 mWcm(-2) simulated sunlight) compared to 6.61% efficiency in the absence of ammonia in the TiO(2) gel.     

纳米TiO2对不饱和聚酯树脂(TiO2/UPR)的改性

将纳米TiO2粉加入到不饱和聚酯中进行同时增韧增强改性，在用简支梁冲击强度表征纳米TiO2／UPR的韧性时，发现树脂有明显的脆韧转变现象，在脆－韧转变点TiO2含量为6％（质量分数），纳米TiO2/UPR弯曲强度和冲击强度分别比UPR提高了55％和46％。在扫描电子显微镜下观测纳米TiO2／UPR的冲击断口形貌时发现，在脆－韧转变点附近纳米TiO2／UPR的微观形态发生了从脆性断裂到韧性断裂的形貌特征。     

Photodegradation of 2-mercaptobenzothiazole in the gamma-Fe(2)O(3)/oxalate suspension under UVA light irradiation

The aim of this study is to investigate the effect of various factors on the photodegradation of organic pollutants in natural environment with co-existence of iron oxides and oxalic acid. 2-Mercaptobenzothiazole (MBT) was selected as a model pollutant, while gamma-Fe(2)O(3) was selected as iron oxide. The crystal structure and morphology of the prepared gamma-Fe(2)O(3) was determined by X-ray diffractograms (XRD) and scanning electron microscopy (SEM), respectively. The specific surface area was 14.36 m(2)/g by Brunauer-Emmett-Teller (BET) method. The adsorption behavior of gamma-Fe(2)O(3) was evaluated by Langmuir model. The effect of the dosage of iron oxide, initial concentration of oxalic acid (C(ox)(0)), initial pH value, the light intensity and additional transition metal cations on MBT photodegradation was investigated in the gamma-Fe(2)O(3)/oxalate suspension under UVA light irradiation. The optimal gamma-Fe(2)O(3) dosage was 0.4 g/L and the optimal C(ox)(0) was 0.8 mM with the UVA light intensity of 1800 mW/cm(2). And the optimal dosage of gamma-Fe(2)O(3) and C(ox)(0) for MBT degradation also depended strongly on the light intensity. The optimal gamma-Fe(2)O(3) dosage was 0.1, 0.25 and 0.4 g/L, and the optimal C(ox)(0) was 1.0, 0.8, and 0.8 mM with the light intensity of 600, 1200 and 1800 mW/cm(2), respectively. The optimal initial pH value was at 3.0. The additional transition metal cations including Cu(2+), Ni(2+) or Mn(2+) could significantly accelerate MBT degradation. This investigation will give a new insight to understanding the MBT photodegradation in natural environment.