掺碳纳米TiO_2光催化降解空气中苯的实验研究

采用火焰化学气相沉积法法制备了掺碳纳米TiO2光催化剂,对催化剂进行了表征。利用自制的连续管式光催化氧化装置研究了掺碳纳米TiO2薄膜对苯气体的光催化降解规律,探讨了相对湿度、初始浓度及苯气体流速等因素对降解率的影响,并与P25粉的光催化性能进行了比较。实验结果表明:在催化剂负载量约为4.7 mg,254 nm和365 nm的8W紫外灯各一盏,相对湿度为80%、苯的初始浓度约为120 mg/m3、苯气体流量为400 mL/min(苯在光催化器中反应时间约为3.5 s)的条件下,苯的降解率可达到15%,高于P25粉的降解效果。     

Application of visible-light photocatalysis with nitrogen-doped or unmodified titanium dioxide for control of indoor-level volatile organic compounds

The present study evaluated visible-light photocatalysis, applying an annular reactor coated with unmodified or nitrogen (N)-doped titanium dioxide (TiO(2)), to cleanse gaseous volatile organic compounds (VOCs) at indoor levels. The surface chemistry investigation of N-doped TiO(2) suggested that there was no significant residual of sulfate ions or urea species on the surface of the N-doped TiO(2). Under visible-light irradiation, the photocatalytic technique using N-doped TiO(2) was much superior to that for unmodified TiO(2) for the degradation of VOCs. Moreover, the degradation efficiency by a reactor coated with N-doped TiO(2) was well above 90% for four target compounds (ethyl benzene, o,m,p-xylenes), suggesting that this photocatalytic system can be effectively employed to cleanse these pollutants at indoor air quality (IAQ) levels. The degradation efficiency of all target compounds increased as the stream flow rate (SFR) decreased. For most target compounds, a reactor with a lower hydraulic diameter (HD) exhibited elevated degradation efficiency. The result on humidity effect suggested that the N-doped photocatalyst could be employed effectively to remove four target compounds (ethyl benzene, o,m,p-xylenes) under conditions of less humidified environments, including a typical indoor comfort range (50-60%). Consequently, it is suggested that with appropriate photocatalytic conditions, a visible-light-assisted N-doped photocatalytic system is clearly an important tool for improving IAQ.     

The photocatalytic degradation of trichloroethane by chemical vapor deposition method prepared titanium dioxide catalyst

The purpose of the investigation was to study the photocatalytic reaction of trichloroethane using a TiO(2) catalyst deposited in an annular reactor by the chemical vapor deposition (CVD) method. The experimental results indicated the highest decomposition rate of the trichloroethane was 2.71 micro mol/(sm(2)) and the conversion ratio reached a maximum of 99.9%. When the humidity was below 154 micro M, the reaction rate slightly increased with increasing humidity. However, the reaction rate decreased as the humidity increased >154 micro M. Oxygen played a role as an electron acceptor in the reaction, and reduced the recombination of the photogenerated electron-hole pairs. Therefore, the reaction rate rose as the oxygen concentration increased. Nevertheless, after the oxygen concentration reached 12%, the reaction rate reached it maximum and was constant in spite of increasing oxygen concentration. As the initial reactant concentration increased, the reaction rate increased, but the conversion ratio dropped. An increase of light intensity resulted in an increase in the number of photons and thus increased the reaction rate. Accordingly the decomposition of trichloroethane could be fitted by the semi-empirical bimolecular Langmuir-Hinshelwood model. Moreover, the reaction rate was proportional to the 0.48-order of the light intensity.     

TiO2 hydrosols with high activity for photocatalytic degradation of formaldehyde in a gaseous phase

Two types of TiO2 hydrosols (TOSO and HTO) were prepared from titanium sulfate (TiOSO4) and metatitanic acid (H2TiO3) by a chemical precipitation-peptization method, respectively. The prepared hydrosols were characterized by means of X-ray diffraction, particle size distribution, scanning electron microscopy, UV-vis spectroscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller and Barret-Joyner-Halender methods. The results showed that the TiO2 hydrosols with an anatase crystal structure had smaller particle sizes, higher surface areas, larger pore volume, and higher transparence than Degussa P-25 suspension. The photocatalytic activity of the TiO2 hydrosols was evaluated for formaldehyde degradation under UVA illumination in a gaseous phase. The results demonstrated that the photocatalytic activity with the catalyst loading of 2mgcm(-2) was ranked as an order of HTO>TOSO>P-25. The photocatalytic activity was further studied using the HTO catalyst under different experimental conditions. The results showed that catalyst loading, relative humidity, and initial concentration could influence the efficiency of HCHO photocatalytic degradation. It was found that a catalyst loading of more than 2mgcm(-2) and a relative humidity of 55% were two essential conditions for achieving the best performance under these experimental conditions. The repeated experiments indicated that the HTO catalyst was reasonably stable and could be repeatedly used for the HCHO oxidation under UVA irradiation. This investigation would be helpful to promote the application of TiO2 photocatalytic technique for indoor air purification.     

Photocatalytic degradation of gaseous benzene over TiO2/Sr2CeO4: kinetic model and degradation mechanisms

Photocatalytic oxidation of benzene in air was carried out over TiO2/Sr2CeO4 catalysts. The prepared photocatalyst was characterized by SBET, UV-vis diffuse reflectance and XPS. TiO2/Sr2CeO4 absorbs much more visible light than TiO2 in the visible light region. The XPS spectrum shows that the binding energy value of Ti 2p3/2 transfers to a lower value. The main purpose was to investigate the kinetic model and degradation mechanisms. The kinetic data matched well with the Langmuir-Hinshelwood (L-H) kinetic model with the limiting rate constant and the adsorption constant in this case were 0.0064 mg l-1 min-1 and 9.2078 l mg-1, respectively. No gas-phase intermediates were detected by direct GC/FID analysis under the conditions despite the high benzene concentration. Ethyl acetate and (3-methyl-oxiran-2-yl)-methanol were two major identified intermediates which were accompanied by butylated hydroxytoluene, 2,6-bis(1,1-dimethylethyl)-4,4-dimethylycyclohe, 2,5-cyclohexadiene-1,4,dione,2,6-bis(1,1-dim). It is plausible that at least one of these less-reactive intermediates caused the deactivation of the photocatalyst. Finally, the photocatalytic oxidation mechanisms were speculated.     

Study on photocatalytic degradation of several volatile organic compounds

The gas-phase photolytic and photocatalytic reactions of several aromatics and chlorohydrocarbons were investigated. The experimental results revealed that chlorohydrocarbons like trichloroethylene, dichloromethane and chloroform could be degraded through either photolysis or photocatalysis under irradiation of germicidal lamp, and the elimination rate of chlorohydrocarbons through photolysis was quicker than that through photocatalysis. UV light from a germicidal lamp could directly lead to degradation of toluene but could hardly act on benzene. The photodegradation rate for these volatile organic compounds (VOCs) through photolysis followed an order: trichloroethylene>chloroform>dichloromethane>toluene>benzene>carbon tetrachloride, and through photocatalysis followed: trichloroethylene>chloroform>toluene>dichloromethane>benzene>carbon tetrachloride. Besides, a series of modified TiO2 photocatalysts were prepared by depositing noble metal, doping with transition metal ion, recombining with metal oxides and modifying with super strong acid. Activity of these catalysts was examined upon photocatalytic degradation of benzene as a typical compound that was hard to be degraded. It indicated that these modification methods could promote the activity of TiO2 catalyst to different extent. The apparent zero-order reaction rate constant for degrading benzene over SnO2/TiO2 catalyst had the highest value, which was nearly three times as that over P25 TiO2. But it simultaneously had the lowest rate for mineralizing the objective compound. In spite that Fe3+/TiO2 catalyst behaved slightly less active than SnO2/TiO2 for degradation of benzene, the mineralization rate over Fe3+/TiO2 was the highest one among the prepared catalysts.     

Benzene oxidation with ozone over supported manganese oxide catalysts: effect of catalyst support and reaction conditions

Catalytic oxidation of gaseous benzene with ozone was carried out over supported manganese oxides to investigate the factors controlling the catalytic activities. The rate for benzene oxidation linearly increased with the surface area of catalyst, regardless of the kinds of catalyst support, whereas the ratio of ozone decomposition rate to benzene oxidation rate was larger for SiO(2)-supported catalyst than Al(2)O(3)-, TiO(2)-, and ZrO(2)-supported catalysts. The rate for benzene oxidation and CO(x) selectivity increased with the reaction temperature (22-100 degrees C) and were improved by the addition of water vapor to reaction gases. Benzene conversion and carbon balance increased with ozone concentration.     

TiO2-UV photocatalytic oxidation of Reactive Yellow 14: effect of operational parameters

The photocatalytic decolourisation and degradation of an azo dye Reactive Yellow (RY14) in aqueous solution with TiO(2) as photocatalyst in slurry form has been carried out using UV-A radiation (365 nm). The effect of various parameters such as catalyst loading, radiation intensity and initial dye concentration on the dye removal was investigated to find optimum conditions. The decolourisation and degradation kinetics have been analysed. Both follow modified Langmuir-Hinshelwood kinetic (L-H) model. A study on the effect of electron acceptors on photooxidation reveals that both decolourisation and degradation increase in the presence of H(2)O(2), (NH(4))(2)S(2)O(8), KBrO(3), to certain dosage beyond which the enhancement effect is negligible. But negative effects are observed in the presence of NaCl or Na(2)CO(3).     

Kinetic study on photocatalytic degradation of C.I. Acid Yellow 23 by ZnO photocatalyst

The potential of a common semiconductor, ZnO, has been explored as an effective catalyst for the photodegradation of C.I. Acid Yellow 23 (AY23). The effects of process parameters such as, catalyst loading, initial dye concentration, light intensity, and pH on the extent of photodegradation have been investigated. Substantial reduction of COD, besides removal of color, was also achieved. A rate equation for the degradation based on Langmuir-Hinshelwood (L-H) model has been proposed. The results show that the adsorption constant (K(ads)) and rate constant (k(L-H)) in L-H model are dependent to the light intensity, and increase with increasing the light intensity. With inserting the light intensity parameter to L-H equation, this model can be used for predicting the removal rate at different light intensities and initial concentrations of AY23. A comparison between experimental and calculated apparent reaction rate constants shows that the results obtained from the L-H modified model are in good agreement with experimental data.     

The catalytic oxidation of aromatic hydrocarbons over supported metal oxide

The catalytic activity of metals (Cu, Mn, Fe, V, Mo, Co, Ni, Zn)/gamma-Al2O3 was investigated to bring about the complete oxidation of benzene, toluene and xylene (BTX). Among them, Cu/gamma-Al2O3 was found to be the most promising catalyst based on activity. X-ray diffraction (XRD), Brunauer Emmett Teller method (BET), electron probe X-ray micro analysis (EPMA) and temperature programmed reduction (TPR) by H2 were used to characterize a series of supported copper catalysts. Increasing the calcination temperature resulted in decreasing the specific surface areas of catalysts and, subsequently, the catalytic activity. Copper loadings on gamma-Al2O3 had a great effect on catalytic activity, and 5 wt.% Cu/gamma-Al2O3 catalyst was observed to be the most active, which might be contributed to the well-dispersed copper surface phase. Using TiO2 (anatase), TiO2 (rutile), SiO2 (I) and SiO2 (II) as support instead of gamma-Al2O3, the activity sequence of 5 wt.% Cu with respect to the support was gamma-Al2O3 > TiO2 (rutile) > TiO2 (anatase)>SiO2 (I) > SiO2 (II), and this appeared to be correlated with the distribution of copper on support rather than with the specific surface area of the catalyst. The smaller particle size of copper, due to its high dispersion on support, had a positive effect on catalytic activity. The activity of 5 wt.% Cu/gamma-Al2O3 with respect to the VOC molecule was observed to follow this sequence: toluene > xylene > benzene. Increasing the reactant concentration exerted an inhibiting effect on the catalytic activity.     

Adsorption and photocatalytic decolorization of a synthetic dye erythrosine on anatase TiO2 and ZnO surfaces

The UV radiation assisted photocatalytic decolorization/degradation kinetics of an anionic dye erythrosine (ER), has been studied over TiO2 and ZnO surfaces. Since adsorption is the prerequisite condition for decolorization/degradation of dye molecules in presence of heterogeneous catalysis, the Langmuir and Freundlich isotherms were examined to verify the adsorption intensity. Standard adsorption free energy measurement implies that the adsorption of ER on both TiO2 and ZnO surfaces is spontaneous endothermic process. The effect of catalyst loading (TiO2/ZnO) revealed the fact that the maximum decolorization rate is obtained under an optimized catalyst loading condition. The decolorization efficiency was also investigated over the pH range of 5.0-10.0 indicating that increasing pH enhances decolorization efficiency. The influence of H2O2 on decolorization efficiency was found noticeable since it is a hydroxyl radical provider. The kinetic study of this degradation indicates that under the experimental condition, the decolorization mechanism follows zero order kinetics on the basis of Langmuir-Hinshelwood (L-H) heterogeneous reaction mechanism.     

Photodecomposition of volatile organic compounds using TiO2 nanoparticles

This study examined the photodecomposition of volatile organic compounds (VOCs) using TiO2 catalyst fabricated by the Submerged Arc Nanoparticle Synthesis System (SANSS). TiO2 catalyst was employed to decompose volatile organic compounds and compare with Degussa-P25 TiO2 in terms of decomposition efficiency. In the electric discharge manufacturing process, a Ti bar, applied as the electrode, was melted and vaporized under high temperature. The vaporized Ti powders were then rapidly quenched under low-temperature and low-pressure conditions in deionized water, thus nucleating and forming nanocrystalline powders uniformly dispersed in the base solvent. The average diameter of the TiO2 nanoparticles was 20 nm. X-ray diffraction analysis confirmed that the nanoparticles in the deionized water were Anatase type TiO2. It was found that gaseous toluene exposed to UV irradiation produced intermediates that were even harder to decompose. After 60-min photocomposition, Degussa-P25 TiO2 reduced the concentration of gaseous toluene to 8.18% while the concentration after decomposition by SANSS TiO2 catalyst dropped to 0.35%. Under UV irradiation at 253.7 +/- 184.9 nm, TiO2 prepared by SANSS can produce strong chemical debonding energy, thus showing great efficiency, superior to that of Degussa-P25 TiO2, in decomposing gaseous toluene and its intermediates.     

活性炭负载纳米TiO2光催化降解气相丙酮

以钛酸四丁酯为前驱体,采用溶胶-凝胶法制得Fe、N离子共掺杂的以活性炭(AC)为载体的光催化剂(TiO2/AC),在紫外光照射下进行了气相丙酮的光催化降解研究。探讨了丙酮初始质量浓度、紫外光光强、催化剂用量、反应器内湿度等因素对其降解率的影响。结果表明,活性炭与TiO2的协同作用大大提高了对丙酮的降解效果;紫外光光强的增加对丙酮降解率有一定提高;使用3g光催化剂,丙酮的初始质量浓度为39.40mg/L;反应器内相对湿度为63%时,丙酮的降解效果最好,降解反应155min后丙酮的降解率达92.63%;催化剂循环使用6次后丙酮的降解率为83.91%。     

Comparison of the treatment methods efficiency for decolorization and mineralization of Reactive Black 5 azo dye

Degradation of Reactive Black 5 (RB5), a well-known non-biodegradable disazo dye, has been studied using UV/TiO2, wet-air oxidation (WAO), electro-Fenton (EF) and UV/electro-Fenton (UV/EF) advanced oxidation processes (AOPs). The efficiency of substrate decolorization and mineralization in each process has been comparatively discussed by decreases in concentration and total organic carbon content of RB5 solutions. The most efficient method on decolorization and mineralization was observed to be WAO process. Mineralization efficiency was observed in the order of WAO>UV/TiO2>UV/EF>EF. Final solutions of AOPs applications after 90 min treatment can be disposed safely to environment. Photocatalytic degradation kinetics of RB5 successfully fitted to Langmuir-Hinshelwood (L-H) kinetics model. The values of second order degradation rate constant (k') and adsorption constant (K) were determined as 5.085 mg L(-1)min(-1) and 0.112 L mg(-1), respectively.     

ACF负载TiO2光催化清除低浓度气态苯的实验研究

为有效清除密闭环境中低浓度气态苯,以钛酸丁酯为前驱物,采用sol -gel法和浸渍-提拉法制备了TiO2/ACF复合材料.采用正交试验研究了溶胶凝胶工艺参数中去离子水、无水乙醇、冰醋酸的加入量以及TiO2/ACF煅烧温度对ACF/TiO2光催化性能的影响,在动态试验装置中,考察了TiO2/ACF对低浓度气态苯清除效果,...     

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.     

炭包覆TiO2复合物对低浓度苯的光催化降解

通过将TiO2粉末和聚乙二醇混合,随后在氮气气氛下热处理合成了炭包覆TiO2.利用粉末X射线衍射、紫外-可见漫反射光谱、透射电子显微镜和氮吸附对炭包覆TiO2复合物样品进行了表征,并研究了其对浓度为～1.2×10-5苯的光催化活性.结果表明:炭包覆量受热处理温度和聚乙二醇用量的影响,随着温度的升高和聚乙二醇量的减少而减少;TiO2的结晶度随着温度的升高而提高,但是炭包覆对TiO2晶体的生长有抑制作用.炭包覆锐钛矿样品比纯TiO2表现出对苯更高的光催化活性,这是由于炭吸附作用导致锐钛矿颗粒周围的苯浓度增加以及包覆炭可导致电荷的有效分离;另一个原因是锐钛矿相结晶度的提高.因此,要获得对苯具有高光催化活性的炭包覆TiO2需要综合考虑碳含量和锐钛矿晶体结构.

Abstract：

Carbon-coated TiO2 was synthesized by mixing TiO2 powders and polyethylene glycol,followed by heat treatment in nitrogen atmosphere. All samples were characterized by powder X-ray diffraction,UV diffuse reflectance spectroscopy,high-resolution transmission electron microscopy,and nitrogen adsorption. The photocatalytic activity of carbon-coated TiO2 for benzene degradation was investigated with a benzene concentration of ～ 1.2 × 10-5. Results showed that the residual carbon content was influenced greatly by heat treatment temperature (HTT)and the amount of PEG,which decreased and increased with increasing the temperature and the amount of PEG,respectively. The crystallinity of TiO2 was improved when the HTT increased. However,the carbon residue had an inhibition effect on the crystal growth of TiO2. The carbon-coated anatase samples were shown to exhibit higher photocatalytic activities than the pristine TiO2 because of the adsorption enrichment of benzene by carbon around the anatase particles and of the effective charge separation due to the electronic conduction of carbon. Another important factor affecting photocatalytic activity was the crystallinity of the anatase phase. High photocatalytic activity for benzene requires a balance between the carbon content and the anatase crystalline structure.     

Photocatalytic degradation of monocrotophos pesticide--an endocrine disruptor by magnesium doped titania

Mg-doped TiO(2) with different Mg concentrations were prepared using sol-gel method and characterized by XRD, UV-visible, XPS, SEM and FT-IR. The XRD results revealed that Mg(2+) goes into the TiO(2) lattice. SEM images of the doped and pure TiO(2) indicated that there is a smaller particle size for the doped catalyst compared to that of the pure TiO(2). UV-visible absorption spectra indicated that upon doping with Mg(2+) ion, the catalyst exhibits absorption in visible region. FT-IR and XPS spectra demonstrated that the presence of Mg(2+) ion in the TiO(2) lattice as substitutional dopant. Photocatalytic activity of doped TiO(2) has been evaluated by degradation of the monocrotophos (MCP) pesticide. The effect of solution pH, catalyst dosage and initial concentration of MCP on the photocatalytic activity of Mg-doped TiO(2) with different loadings was studied. It was observed that the rate of degradation of MCP over Mg-doped TiO(2) is better than Pure TiO(2) and Degussa P-25.     

高效光催化降解气相苯纳米TiO2微球的制备EI北大核心CSCD

以四氯化钛为钛源,尿素为沉淀剂前驱物,硫酸钠为分散剂,利用水热法在水-醇体系中制备出纳米TiO2微球。运用X射线衍射、电子显微镜、N2吸附-脱附和紫外-可见光谱等手段表征样品的结构和性质,并考察了水热温度对纳米TiO2微球结构及光催化降解气相苯活性的影响。结果表明,此类微球由纳米颗粒组成,且比表面积大,介孔结构明显,光吸收出现明显的“蓝移”。光催化结果显示,微球具有很高的光催化活性,尤其是180℃下制备的微球仅用20min将苯完全去除,但生成CO2的量仍随时间有所增加,表明微球的强吸附性能促进其光催化降解过程,且矿化率高达5.5,是P25(2.7)的2倍。     

聚苯乙烯蜂窝状多孔膜的制备及应用

以线性聚苯乙烯(PS)为膜材料,采用Breath Figures法制备了高度规整的蜂窝状结构多孔膜.研究了溶液浓度、环境湿度、气体吹扫速度及不同溶剂对多孔膜结构的影响.结果表明,相比于苯和二氯甲烷,氯仿作为溶剂因其挥发度适宜,PS浓度在20～80mg/mL的铸膜溶液可形成规整的蜂窝状结构多孔膜,且膜孔分布均匀、大小均一;制膜的湿度需高于环境湿度,但随着湿度的增加孔径增大;气体吹扫速度可在400～1000mL/min范围,但吹扫速度较大时孔径略有降低.该膜可作为固定诸如辣根过氧化酶等活性酶的载体,用于酶催化反应.