Photocatalytic degradation of mixed gaseous carbonyl compounds at low level on adsorptive TiO2/SiO2 photocatalyst using a fluidized bed reactor

An adsorptive silica-supported titania photocatalyst TiO(2)/SiO(2) was prepared by using nanosized titania (anatase) immobilized on silica gel by the sol-gel technique with the titanium tetra isopropoxide as the main raw material and acetic acid as the acid catalyst. Meanwhile the structure and properties of the TiO(2)/SiO(2) photocatalyst were studied by means of many modern analysis techniques such as TEM, XRD, and BET. Gas-solid heterogeneous photocatalytic decomposition of four carbonyl compounds mixture at low concentration levels over ultraviolet irradiated TiO(2)/SiO(2) photocatalyst were carried out with high degradation efficiencies in a coaxial triple-cylinder-type fluidized bed photocatalytic reactor, which provided efficient continuous contact of ultraviolet photons, silica-supported titania photocatalyst, and gaseous reactants. Experimental results showed that the photocatalyst had a high adsorption performance and a good photocatalytic activity for four carbonyl compounds mixture. Some factors influencing the photocatalytic decomposition of the mixed carbonyl compounds, i.e. the gas flowrate, relative humidity, concentration of oxygen, and illumination time, were discussed in detail. It is found that the photocatalytic reaction rate of four carbonyl compounds decreased in this order: propionaldehyde, acetone, acetaldehyde and formaldehyde.     

Decomposition of benzene and toluene in air streams in fixed-film photoreactors coated with TiO2 catalyst

The decomposition of benzene and toluene in air streams by UV/TiO2 process was studied in different annular photoreactors under various operating conditions. The shells of reactors used in this research are made of stainless steel, Pyrex glass, or titanium. The TiO2 film was coated to the inner surface of the reactors by either rotating coating or sol-gel techniques. The TiO2 films coated by sol-gel technique were found to be smoother and more uniform than those coated by rotating coating. However, experimental results indicated that the photocatalysis of benzene or toluene in a glass reactor with rotating-coated TiO2 film delivered higher decompositions in air streams than that with sol-gel coated reactors. Benzene and toluene were decomposed more effectively in a coated glass reactor than in a coated stainless steel reactor under the same operating conditions. The presence of water vapor in air-stream plays an important role in the decomposition of benzene and toluene, and a relative humidity of approximately 5-6% was found to be adequate. The presence of excessive amounts of humidity retarded the decomposition to certain extents possibly results from the competitive adsorption of water molecules on the active sites of TiO2.     

Titanium dioxide mediated photocatalytic degradation of monochlorobenzene in aqueous phase

The reaction sequence for the photocatalytic degradation of monochlorobenzene (MCB) in UV/TiO2 process, including substrate adsorption, degradation, and mineralization, was studied. The theoretical maximum quantity of MCB that could be adsorbed onto TiO2 surface in aqueous phase was 0.18+/-0.04 micromol m(-2) of TiO2. In accordance with the upper limit of the relative surface coverage of MCB molecules to surface hydroxyls of TiO2 was around 2.2%, the water molecules as the major adjacent species near TiO2 surface would compete with MCB molecules. Increasing the initial substrate concentration to an appropriate value or enhancing the affinity between the MCB and the TiO2 surface by adjusting the solution pH would promote the photocatalytic degradation. Experimental results revealed that the neutral medium was beneficial for the degradation of MCB. In comparison, the mineralization was most improved at acidic condition. Generally, 90% of the total organic carbon (TOC) was mineralized after 240 min illumination time in the examined pH range except solution pH 11. The suppressed mineralization of MCB at solution pH 11 was ascribed to the lack of adsorption. A simplified 2-step consecutive kinetic model was used to simulate the mineralization.     

Photocatalytic production of hydrogen in single component and mixture systems of electron donors and monitoring adsorption of donors by in situ infrared spectroscopy

The photocatalytic production of hydrogen using aqueous Pt/TiO2 suspension has been investigated in single component and mixture systems of electron donors (pollutants). The reaction systems consisted of oxalic acid, formic acid and formaldehyde, respectively. The adsorption of these donors on TiO2 was also monitored by in situ attenuated total reflection infrared spectroscopy (ATRIR). In the single component systems, the efficiency order of electron donors is as follows: H2C2O4 > HCOOH > HCHO. The order is consistent with the order of adsorption affinity of the electron donors on TiO2 determined by ATRIR, which suggests a link between the strength of surface interaction and the efficiency of photocatalytic hydrogen evolution. In the binary mixture systems, competitive inhibition kinetics is observed. When a donor adsorbed strongly on TiO2 in a state of saturated adsorption in a binary system, the overall rate of the hydrogen evolution is consistent with that of decomposition of the donor, and the system can be treated as a single component system.     

CdS-TiO2/MWCNTs结构表征及其光催化性能

采用溶胶-凝胶法,制备了多壁碳纳米管（MWCNTs）负载的双组分复合半导体光催化剂CdS-TiO2/MWCNTs。通过透射电镜（TEM）、比表面分析（BET）、X射线衍射（XRD）和紫外-可见吸收光谱（UV-vis）等分析方法对光催化剂进行了结构表征,并考察了CdS-TiO2/MWCNTs对甲苯降解的光催化性能。结果表明：纳米活性粒子CdS-TiO2均匀负载于MWCNTs上,比表面积、光吸收阈值和强度增大,活性粒子间以及活性粒子与载体之间具有协同作用,有利于光催化性能的提高,CdS-TiO2/MWCNTs在主波长为254 nm紫外光照射下对甲苯的降解效果较好,去除率可达55.3%。     

纳米TiO2光催化氧化去除水中痕量双氯芬酸的研究

以TiCl4为前驱体,采用水解法经不同温度煅烧制备了具有不同理化性能的纳米TiO2光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、物理吸附仪、紫外—可见光漫反射吸收光谱(UV-Vis DRS)等手段对纳米TiO2的晶相结构、粒径、孔径分布以及禁带宽度等进行了表征。以蒸馏水配制的双氯芬酸溶液为目标物,进行了纳米TiO2光催化氧化去除双氯芬酸的活性测试,研究了纳米TiO2的理化性能与光催化氧化活性之间的关系。结果表明,经400℃煅烧制得的纳米TiO2样品具有最高的光催化氧化活性,其在紫外光照射60min下对双氯芬酸的去除率为98%左右,比单独紫外光照射高出85百分点。纳米TiO2光催化氧化去除双氯芬酸的反应近似一级反应动力学模型,其中经400℃煅烧制得的纳米TiO2光催化氧化去除双氯芬酸的表观反应速率常数为0.054 54min-1,是普通商用TiO2的2倍左右,与德国Degussa P-25TiO2的光催化氧化活性最相近。     

Fine route for an efficient removal of 2,4-dichlorophenoxyacetic acid (2,4-D) by zeolite-supported TiO2

Zeolites HY, Hbeta and HZSM-5 with different physico-chemical properties were chosen as support for TiO2 to illustrate their adsorption, dispersion and electronic structure in photocatalysis. The extent of TiO2 loading was monitored by XRD and BET surface area measurements. The adsorption capacity of HY zeolite was found to be high and hence chosen for further modification to continue the investigation. Photodegradation kinetics were carried out with 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution. The extent of 2,4-D degradation on TiO2/HY loading revealed the importance of adsorption in photocatalysis. Mineralisation studies on all three zeolites with 1 wt.% TiO2 loading demonstrated the good dispersion properties of TiO2/HY. Its photocatalytic activity was found to be excellent with formulated 2,4-D. Comparison of relative photonic efficiencies demonstrated that supported photocatalysts exhibited higher activity than some of the commercial photocatalysts. The high activity of supported TiO2 is due to synergistic effects of improved adsorption of 2,4-D and efficient delocalisation of photogenerated electrons by zeolite support.     

Photocatalytic oxidation of toxic organohalides with TiO2/UV: the effects of humic substances and organic mixtures

TiO2/UV photocatalytic oxidation of DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane), 1,2,3-trichlorobenzene and 4-chlorophenol were examined in aqueous solution in the presence of humic substances and organic mixtures to study if the degradation rates were affected. Both commercial and natural humic substances were observed to retard the photodegradation rates, with a greater effect from the natural humic substances. Acetonitrile and isopropanol also caused significant retardation of 4-chlorophenol photodegradation. The overall retardation can be attributed to the combination of light attenuation, inhibition and competition effects. Moreover, the TiO2/UV system favors the decomposition of compounds that have stronger adsorption onto the TiO2 surface. To engineer effective treatment facilities that use the TiO2/UV system for the treatment of toxic substances in wastewater, the methodology must allow for concerns about adventitious species which are present.     

Photocatalytic degradation of the herbicide erioglaucine in the presence of nanosized titanium dioxide: comparison and modeling of reaction kinetics

The present work mainly deals with photocatalytic degradation of a herbicide, erioglaucine, in water in the presence of TiO2 nanoparticles (Degussa P-25) under ultraviolet (UV) light illumination (30 W). The degradation rate of erioglaucine was not so high when the photolysis was carried out in the absence of TiO2 and it was negligible in the absence of UV light. We have studied the influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO2, irradiation time and initial concentration of erioglaucine on the photodegradation efficiency of erioglaucine. A kinetic model is applied for the photocatalytic oxidation by the UV/TiO2 system. Experimental results indicated that the photocatalytic degradation process could be explained in terms of the Langmuir-Hinshelwood kinetic model. The values of the adsorption equilibrium constant, K, and the second order kinetic rate constant, k, were 0.116 ppm-1 and 0.984 ppm min-1, respectively. In this work, we also compared the reactivity between the commercial TiO2 Degussa P-25 and a rutile TiO2. The photocatalytic activities of both photocatalysts were tested using the herbicide solution. We have noticed that photodegradation efficiency was different between both of them. The higher photoactivity of Degussa P-25 compared to that of rutile TiO2 for the photodegradation of erioglaucine may be due to higher hydroxyl content, higher surface area, nano-size and crystallinity of the Degussa P-25. Our results also showed that the UV/TiO2 process with Degussa P-25 as photocatalyst was appropriate as the effective treatment method for removal of erioglaucine from a real wastewater. The electrical energy consumption per order of magnitude for photocatalytic degradation of erioglaucine was lower with Degussa P-25 than in the presence of rutile TiO2.     

Superior photodecomposition of pyrene by metal ion-loaded TiO₂ catalyst under UV light irradiation

BACKGROUND: The photocatalytic degradation of pyrene under UV (125 W Hg-Arc, 10.4 mW/cm2) irradiation of TiO2 aqueous suspension has been found to be highly improved with the dissolved transition metal ions like Cu2+, Fe3+, Ag+, and Au3+, etc. As the reduction potential of these metals lies below the conduction band (CB) position (?0.1 eV) of TiO2, the photoexcited electron transfer occurs more readily and reduces electron–hole recombination rate. Therefore, it has a beneficial influence on the photocatalytic ability of TiO2 because of rapid Fermi energy equilibrium between the CB of TiO2 and its surface adsorbed metal ions. RESULTS AND DISCUSSION: The Fermi level is referred to as the electrochemical potential and plays an important role in the band theory of solids. When metal and semiconductor are in contact, electron migration from photoirradiated semiconductor to the deposited metal occurs at the interface until two Fermi levels equilibrate and enhanced the photocatalytic activity of semiconductor photocatalyst. Ni2+ having more negative reduction potential (?0.25 eV) than the CB of TiO2 imparts negligible co-catalytic activity to TiO2 photoreaction. It also revealed that loading of Au3+ ions displayed higher degradation rate of pyrene than Au photodeposition. Furthermore, when the amount of dissolved Fe+3 and Au3+ ions gradually increases from 0.1 to 2 wt.%, the pyrene photodecomposition rate also become faster.     

Photocatalytic oxidation of nitrogen oxides using TiO2 loading on woven glass fabric

TiO2 loading on woven glass fabric is applied to treat nitrogen oxides (NOx) by photocatalytic oxidation (PCO). In this paper, the PCO behavior of NO at high concentrations was studied by PCO of NOx at source levels (20-168 ppm). The PCO efficiency reached 27% in this experiment, while the inlet NOx concentration was 168 ppm (147 ppm NO). The dependency of the reaction rate on several key influencing factors (relative humidity, space time, inlet concentration, oxygen percentage) was also studied. The results illustrate that the resulting hydroxyl radical and active oxide play an important role in the oxidation of NOx. The reactions are limited by the thermodynamic equilibrium after ca. 15s space time. A possible explanation for the catalyst deactivation is the accumulation of nitric acid and nitrous acid on the TiO2 surface during the PCO of NOx. However, the photocatalytic activity can be recovered with a simple heat treatment. The results from the study of the effect of the inlet concentration were described with the Langmuir-Hinshelwood model.     

Non-degradable triazine substrates of atrazine and cyanuric acid hydrothermally and in supercritical water under the UV-illuminated photocatalytic cooperation

Strong oxidation by titanium dioxide photocatalysis can occur by photodegradation of organic contaminants in air and water. Some endocrine disruptors such as 2,4-dichlorophenoxy acetic acid (;;; ), 2,4-dichlorophenol (;;; ), nonylphenol (; ), bisphenol A (), diethyl phthalate (; ), etc. which can be neither biodegraded by bacteria nor degraded thermally can be degraded by TiO(2) photocatalytic treatment. However, incomplete photomineralization partly occurred, when TiO(2) photocatalytic degradation is employed for the treatment of certain endocrine disruptors. For example, no atrazine pesticide having triazine skeleton can be completely mineralized even by a photocatalytic procedure; the photodegradation of atrazine ultimately stops at the intermediate step of cyanuric acid, which cannot be photodegraded even after long illumination times ().In this study, the decomposition of atrazine and cyanuric acid was carried out with a device combining photocatalytic degradation in supercritical water (scH(2)O) or hydrothermal water (hyH(2)O). Atrazine and cyanuric acid can be degraded by the cooperation of either scH(2)O or hyH(2)O and UV illuminated TiO(2)-photocatalytic dispersed system under the fixed pressure of 23 MPa at 623 K or 683 K in a 120-ml Hastelloy batch reactor. The photocatalytic degradation method under high temperature and pressure has found appropriate for the photocatalytic oxidation of acetic acid and 2-chlorobiphenyl under continuous flow conditions at 160 degrees C and 20 atm (). In addition, the wet peroxide oxidation of PCBs by high temperature and pressure has been reported (). The main aims of this research are following. (i): the degradation of atrazine and cyanuric acid within the scH(2)O or hyH(2)O, (ii) the decomposition of atrazine and cyanuric acid catalyzed by TiO(2) particles under scH(2)O or hyH(2)O, and the synergistic effect for several reactions with TiO(2) and scH(2)O or hyH(2)O, and (iii) the mineralization yield of nitrogen and chlorine atoms concerning the chemical structures of atrazine or cyanuric acid (only nitrogen).     

亚甲基蓝表面修饰纳米TiO2降解造纸废水动力学

以亚甲基蓝(MB)作为表面修饰剂,采用简单的化学吸附法制备亚甲基蓝表面修饰的纳米TiO2光催化剂(TiO2-MB)。经表面修饰后,TiO2-MB光催化剂波长响应范围红移至可见光区575 nm处。探讨了光催化剂量、光照时间和溶液pH值对TiO2-MB光催化降解造纸废水的影响;研究了纳米TiO2-MB对造纸废水的暗吸附规律和光降解性能。结果表明:纳米TiO2-MB对造纸废水的吸附规律都较好地符合Langmuir和Freundlich吸附等温模型,属于吸热反应;光催化降解动力学符合Langmuir-Hinshelwood动力学模型。在160 W高压汞灯光照80 min,3.0 g/L纳米TiO2-MB光催化降解pH=2.0的造纸废水(COD:2 069.8 mg/L),COD去除率可达94.7%,处理效果远高于避光条件下。光催化剂经8次使用仍具有较高的催化活性。     

Photocatalytic degradation of p-nitrophenol on nanometer size titanium dioxide surface modified with 5-sulfosalicylic acid

The surface of nanometer size TiO(2) was simply and fast modified by chemical adsorption in saturated solution of 5-sulfosalicylic acid. After surface modification, a stable, yellow surface complex was formed quickly, the wavelength response range of TiO(2) was expanded, it has obvious absorption in the region from 320 to 450 nm; the adsorption efficiency of p-nitrophenol (PNP) by TiO(2) was enhanced from 42% to 84%. The photocatalytic activity was tested on the degradation of PNP. The influences of catalyst and its dosage, pH value, and PNP concentration on the degradation were investigated. On optimal photodegradation conditions, including initial pH 4.0, PNP 5 mg l(-1), catalyst 100 mg, irradiation time 120 min with 160 W high-pressure mercury lamp, the degradation efficiency of PNP was increased from 40% to 88% after surface modification. Surface modification led not only to an increase in the light utilization, but also improved the surface coverage of PNP in comparison with the pure TiO(2). Both of these factors are crucial for the photocatalytic activity of heterogeneous photocatalysis, especially for photodegradation of benzenoid pollutants.     

Modification of carbon-coated TiO2 by iron to increase adsorptivity and photoactivity for phenol

Carbon-coated TiO(2) modified by iron, were prepared from TiO(2) of anatase structure and PET modified by FeC(2)O(4). Catalysts were prepared by mixing powders of TiO(2) and modified PET and heating at different temperatures, from 400 to 800 degrees C under flow of Ar gas. High adsorption of phenol was observed on the catalyst heated at 400 degrees C, confirmed by FT-IR analysis. On this catalyst, fast rate of phenol decomposition was achieved by addition of small amount of H(2)O(2) to the reaction mixture. Phenol decomposition proceeded mainly through the direct oxidation of phenol species adsorbed on the catalyst surface due to the photo-Fenton reaction. Iron-modified carbon-coated TiO(2) catalysts heated at 500-800 degrees C showed almost no phenol adsorption or oxidation.     

Enhanced photocatalytic degradation of VOCs using Ln3+-TiO2 catalysts for indoor air purification

Two types of lanthanide ion-doped titanium dioxide (Ln3+-TiO2) catalysts including La3+-TiO2 and Nd3+-TiO2 were prepared by a sol-gel method. The effects of the lanthanide ion doping on the crystal structure, surface area, adsorption properties, pore size distribution, and surface chemical state of the catalysts were investigated by means of XRD, BET, and XPS. As results, the crystal size decreased significantly, while the specific surface area, t-plot total surface area, micropore volume, and the total pore volume increased owing to the lanthanide ion doping. The nitrogen adsorption-desorption isotherms of the catalysts showed that the N2 adsorption ability of the Ln3+-TiO2 catalysts was better than the TiO2 catalyst. Among them, the 0.7% Ln3+-TiO2 catalysts demonstrated the highest adsorption ability. The photocatalytic activity of the catalysts was investigated in the experiments of the photocatalytic degradation of benzene, toluene, ethylbenzene and o-xylene (BTEX) in a gaseous phase. The photocatalytic efficiency of the TiO2 catalysts with the lanthanide ion doping was remarkably enhanced by BTEX removal. The 1.2% Ln3+-TiO2 catalysts achieved the highest photocatalytic activity. The enhanced photodegradation of BTEX is possibly due to the improved adsorption ability and the enhanced electron-hole pairs separation due to the presence of Ti3+ on the surface of Ln3+-TiO2 catalysts and the electron transfer between the conduction band/defect level and lanthanide crystal field state.     

大尺寸大孔径TiO_2/SiO_2光催化剂的制备及甲醛去除研究

以大孔径SiO2为载体,通过钛酸丁酯溶液的浸渍、原位水解以及高温煅烧制备出大尺寸、大孔径的TiO2/SiO2光催化剂。利用自制空气净化装置对室内甲醛的清除进行研究,分别考察了TiO2的百分含量、紫外光光强、温度、湿度和空气流量等不同条件下TiO2/SiO2光催化剂对除去甲醛效率的影响。结果表明,反应温度从10～50℃依次升高,去除率逐渐下降。在相对湿度为50%,TiO2负载率为55.6%,流量为8 m3/h时,甲醛的最佳除去率达96.5%;经过7周时间的考察,发现TiO2/SiO2光催化剂的催化活性没有明显的下降。     

Adsorption and photocatalytic decomposition of roxarsone by TiO2 and its mechanism

Roxarsone (3-nitro-4-hydroxyphenylarsonic acid) has been widely used as organic arsenic additive in animal industry. In this study, the adsorption of roxarsone on TiO₂ under dark conditions, the photocatalytic decomposition of roxarsone under UV/TiO₂, and the possible photocatalytic pathway were investigated. At the initial concentration of 5–35 mg/L, the adsorption of roxarsone fitted well with the pseudo-second-order kinetics. The isotherms analysis showed that the Langmuir model was better than the Freundlich and Dubinin–Radushkevich models for describing the adsorption process. After 7 h of photocatalytic decomposition, a complete disappearance of roxarsone was achieved. The pH value has a significant effect on both adsorption and photocatalytic decomposition of roxarsone. The results of high-performance liquid chromatography-hydride generation-atomic fluorescence spectrometry (HPLC-HG-AFS) and gas chromatography-mass spectrometry (GC/MS) analyses proved the cleavage of the As-C bond during the photocatalytic decomposition process by TiO₂ and the intermediates of the decomposition. Based on the results, a possible photocatalytic decomposition pathway was proposed.     

Enhancement of photocatalytic oxidation of humic acid in TiO2 suspensions by increasing cation strength

This study aimed at improving the photocatalytic (PC) oxidation of humic acids (HA) in TiO2 suspensions by adding cationic ion such as calcium or magnesium. A set of tests was first conducted in the dark to study the adsorption of HA onto TiO2 in suspensions at different pH and calcium concentrations. The experiment demonstrated that the adsorption of HA onto the TiO2 particles was either pH-dependent or calcium strength-dependent due to electrostatic interaction and calcium ion bridging. The photodegradation of HA in the presence of UV irradiation was investigated as a function of pH and the concentration of calcium and magnesium ions. The results showed that the adsorption behavior between HA and TiO2 played a very important role during the PC oxidation process. The PC oxidation could be enhanced at neutral pH by increasing the cation strength. The kinetics of HA PC degradation in TiO2 suspensions with different initial concentrations was also studied using the Langmuir-Hinshelwood model.     

Photocatalytic degradation of dyes on a magnetically separated photocatalyst under visible and UV irradiation

A novel kind of magnetically separable photocatalyst of TiO2/SiO2/gamma-Fe2O3 (TSF) is prepared. Scanning tunnel microscope (STM) and X-ray diffractometer (XRD) were used to characterize the structure of the photocatalyst. In the TSF photocatalyst, a TiO2 shell is for photocatalysis, a gamma-Fe2O3 core as a carrier is for separation by the magnetic field and a SiO2 membrane between the TiO2 shell and the gamma-Fe2O3 core is used to weaken the adverse influence of gamma-Fe2O3 on the photocatalysis of TiO2. Three kinds of dyes, Fluoresein, Orange II and Red acid G, were used to examine the photocatalytic activity of TSF. Due to strong UV adsorption of the gamma-Fe2O3, the photocatalytic activity of TSF was lower than that of the pure TiO2. Deducting the light absorption of the gamma-Fe2O3 particles, the photocatalytic activity of TSF was found to be higher than that of the P25 under UV irradiation. On the other hand, the photocatalytic activity of TSF under visible irradiation was much lower than that of the P25 TiO2 even deducting the visible light absorption of the gamma-Fe2O3 particles. Differences in the photocatalytic mechanisms under UV and visible irradiation lead to the differences in the photodegradation characteristics of dyes on TSF. The recycled TSF exhibited a good repeatability of photocatalytic activity.