Simultaneous decontamination of hexavalent chromium and methyl tert-butyl ether by UV/TiO2 process

Hexavalent chromium and methyl tert-butyl ether (MTBE) are two important environmental pollutants. Simultaneous decontamination of Cr(VI) and MTBE was studied by UV/TiO2 process. The influences of pH and the concentrations of pollutants on the kinetics of the photocatalytic reactions were evaluated. Dark adsorption tests showed that the acidic pH favored the adsorption of Cr(VI) while neutral pH favored the adsorption of MTBE. Under UV irradiation, Cr(VI) reduction was observed in Cr(VI)/TiO2 system, and MTBE oxidation was observed in MTBE/TiO2 system. The system containing Cr(VI) and MTBE by UV/TiO2 process demonstrated the synergistic effect between oxidation of MTBE and reduction of Cr(VI). The results demonstrated that two pollutants Cr(VI) and MTBE could be eliminated simultaneously by UV/TiO2 process. tert-Butyl formate, tert-butyl alcohol and acetone were identified as primary degradation products of MTBE by gas chromatography-mass spectrometry in the degradation of MTBE by UV/TiO2 process.     

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.     

Column study of Cr(VI) removal by cationic hydrogel for in-situ remediation of contaminated groundwater and soil

Column experiments were conducted for examining the effectiveness of the cationic hydrogel on Cr(VI) removal from groundwater and soil. For in-situ groundwater remediation, the effects of background anions, humic acid (HA) and pH were studied. Cr(VI) has a higher preference for being adsorbed onto the cationic hydrogel than sulphate, bicarbonate ions and HA. However, the adsorbed HA reduced the Cr(VI) removal capacity of the cationic hydrogel, especially after regeneration of the adsorbents, probably due to the blockage of adsorption sites. The Cr(VI) removal was slightly influenced by the groundwater pH that could be attributed to Cr(VI) speciation. The 6-cycle regeneration and reusability study shows that the effectiveness of the cationic hydrogel remained almost unchanged. On average, 93% of the adsorbed Cr(VI) was recovered in each cycle and concentrated Cr(VI) solution was obtained after regeneration. For in-situ soil remediation, the flushing water pH had an insignificant effect on the release of Cr(VI) from the soils. Multiple-pulse flushing increased the removal of Cr(VI) from the soils. In contrast, more flushing water and longer operation may be required to achieve the same removal level by continuous flushing.     

Photocatalytic degradation of lignin using Pt/TiO2 as the catalyst

Photocatalytic degradation of lignin was studied with the use of catalysts TiO(2) and Pt/TiO(2). The influence of several experimental parameters, i.e. pH, catalyst dosage and illumination on lignin degradation was investigated. The results showed that application of UV irradiation alone has almost no effect on the reduction of dissolved organic carbon (DOC) and American Dye Manufacture Institute value (ADMI). However, the addition of TiO(2) and Pt/TiO(2) reduced the original DOC (251 mg l(-1)) by more than 40% within 30 min of treatment and the reaction can be simulated with pseudo-first order kinetics. Rapid degradation of lignin was observed in acidic solution using either TiO(2) or Pt/TiO(2) as the catalyst compared to high pH cases. The content of Pt in the Pt/TiO(2) catalyst is 1%. In addition, too much catalyst addition has not increased the DOC and ADMI reduction proportionally. The investigation also indicated that the photocatalytic degradation rates could be enhanced 1-6 times faster after doping TiO(2) with Pt in different pH cases. A modified Nernst type model was adopted to simulate the decoloring process using TiO(2) and Pt/TiO(2) based on the profiles of oxidation reduction potential during the photocatalytic reaction. The developed equation can be used to predict the color removal efficiency of lignin wastewater by the photocatalytic process.     

PBTCA稳定零价纳米铁的制备及其去除水中Cr(Ⅵ)

以2-膦酸丁烷-1,2,4三羧酸(PBTCA)为稳定剂,通过FeCl3.6H2O与NaBH4反应,利用液相还原法制备稳定纳米级零价铁颗粒(P-NZVI),并用透射电子显微镜(TEM)、扫描电子显微镜(SEM)及X射线衍射(XRD)进行表征,颗粒平均粒径为73 nm。考察了Cr(Ⅵ)溶液初始浓度、pH、NZVI投加量、温度等条件对Cr(Ⅵ)去除效果的影响,并与同等条件下不加稳定剂制备的纳米铁(N-NZVI)进行对比。结果表明:Cr(Ⅵ)的去除率随温度和纳米铁投加量增加而升高,随pH和Cr(Ⅵ)溶液初始浓度升高而降低。在相同实验条件下,P-NZVI对Cr(Ⅵ)的去除效果明显优于N-NZVI,表明改性后纳米铁在地表水原位修复领域具有较好的应用前景。     

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.     

光催化降解水体异味物质2-MIB的机理

以水体异味物质2-甲基异莰醇(2-methylisoborneol,2-MIB)为研究对象,在紫外光(λ<380 nm)照射下,探讨TiO2(P25)对2-MIB的光催化降解特性及光化学作用机理。结果表明,UV/TiO2光催化体系可以有效去除水体异味物质2-MIB,紫外光照射60 min,对2-MIB的降解率达95%。同时研究了光催化降解体系介质pH,共存腐殖酸(HA)和过硫酸钾(K2S2O8)对UV/TiO2光催化体系降解2-MIB的影响,发现低浓度HA([HA]≤0.5 mg/L)可以提高2-MIB降解速率,当HA浓度高于0.5 mg/L,2-MIB降解反应受到抑制;同时当加入电子受体K2S2O8后,降解体系中活性物种羟基自由基(.OH)明显增加,提高了TiO2对2-MIB的降解能力。利用苯甲酸荧光光度法和POD-DPD显色法跟踪测定降解过程中羟基自由基(·OH)和过氧化氢(H2O2)的变化,表明光催化反应涉及·OH机理。     

TiO2胶体光催化降解罗丹明B染料

TiO2胶体从钛氧有机物水解制备,表征的方法有:X射线衍射光谱(XRD)、激光散射粒径分布、傅立叶变换红外光谱(FT-IR)、X射线光电子谱(XPS)和透射电子显微镜(TEM)。利用罗丹明B染料分子作为探针分子研究TiO2胶体的光催化活性,分析了pH、催化剂用量、外加氧化剂(H2O2)用量及罗丹明B初始浓度对TiO2胶体光催化活性的影响。结果表明:制备的TiO2胶体粒子平均粒径为13.8 nm(激光散法测定),光催化降解罗丹明B染料的反应属于一级动力学反应,可以用Langmuir-Hinshewood模型加以描述,反应速率常数k1为0.08413 mg/(L.min),平衡吸附常数k2为1.5305 L/mg;在pH为6,TiO2胶体用量为0.04%,H2O2(含量30%)用量为0.2%(V/V),光照度为69.6μW/cm2时,5 h后罗丹明B染料的降解率可达到99%以上;相似的条件,0.2%的P25 TiO2粉体光催化处理染料水时,罗丹明B的降解率为90%。纳米TiO2胶体不仅可以提高罗丹明B的光催化降解率,还具有用量少,可有效降低水处理成本的特点。     

TiO2光催化降解水中土霉素的动力学研究

环境中抗生素的出现及其引起的危害正受到越来越多的关注。以高压汞灯为光源，选用较为广泛的抗生素土霉素（OTC）为处理对象。考察了初始质量浓度、反应过程中光照、催化剂投加量、溶液起始pH、溶液中DOM和NO^-₃对光催化降解的影响，研究了其光降解动力学。结果表明，TiO₂光催化氧化法能够有效去除水中半微量的OTC，OTC的光降解过程符合一级反应动力学模型；UV/TiO₂联用工艺对TOC也有很好的去除效果，反应90 min，TOC去除率可达74%；OTC的初始浓度从30 mg/L增大到90 mg/L，反应速率从0.0619 min^-1降低到0.0130 min^-1；随着光催化剂投加量的增大，光降解速率常数先增大后减小；增加溶液的pH值，速率常数逐渐减小；溶液中的DOM和NO^-₃也可以影响光降解效率。     

超声波-TiO_2光催化联合处理垃圾渗滤液

采用超声波强化TiO2光催化技术处理垃圾渗滤液。研究了TiO2催化剂用量、光照作用、超声波作用、pH值、曝气作用等因素对垃圾渗滤液中COD和氨氮去除率的影响。结果表明,在TiO2粉末的投加量为2 g/L、pH值为11时,先采用功率为292.5 W的超声波辐射3 min,再以高压汞灯(250 W)照射3 min,垃圾渗滤液中的COD和NH3-N去除率分别达到50.1%和75%。若在同一条件下进行饱和曝气可以使NH3-N去除率进一步达到85.3%,但会降低COD的去除率。     

Degradation of azo dye Procion Red MX-5B by photocatalytic oxidation

The photocatalytic oxidation (PCO) of a monoazo dye Procion Red MX-5B under various physico-chemical conditions was investigated. Degradation of the dye by PCO was enhanced by augmentation in UV intensity, titanium dioxide and hydrogen peroxide concentrations but was inhibited by increase in initial dye concentration. The PCO process was affected by pH in a peculiar way. In the presence of 100 mg/l of TiO2 and the absence of H2O2, the highest reaction rate was observed when the initial pH was 10. With 500 mg/l of TiO2 and 10 mM of H2O2, the reaction was the fastest at initial pH of 3-5. The optimal conditions for the degradation of the dye, at an UV intensity of 17 mW/cm2, were determined to be: TiO2 concentration, 500 mg/l; initial H2O2 concentration, 10 mM; initial pH, 5.0. Monitoring of TOC loss showed that the dye was mineralized by 90% within 80 min under these conditions. Nevertheless, the persistence of a low level of TOC indicated that mineralization was not complete and dead-end product(s) which was (were) resistant to PCO might have accumulated.     

Mechanisms of chromium and arsenite adsorption by amino-functionalized SBA-15

The adsorption of Cr(VI) and As(III) by amino-functionalized SBA-15 (NH₂-SBA-15) from single and binary systems were investigated in this work. The effects of pH and temperature on the adsorption of NH₂-SBA-15 were studied. Adsorption kinetics, isotherm model, and thermodynamics were studied to analyze the experimental data. pH 2 was the optimum condition for the adsorption of Cr(VI) and pH 4 for As(III) adsorption. Increasing temperature had a positive effect on the removal of both Cr(VI) and As(III). The Freundlich isotherm model can depict the adsorption process best. The pseudo-second-order kinetic model fitted well with the kinetic data of Cr(VI) and As(III) in the single-component system. In the binary system, the adsorption of As(III) by NH₂-SBA-15 was slightly enhanced with the presence of Cr(VI); however, As(III) had no obvious effect on the removal of Cr(VI). Regeneration experiments indicated that 0.1 mol/L NaHCO₃ was an efficient desorbent for the recovery of Cr(VI) and As(III) from NH₂-SBA-15; the desorption rates for Cr(VI) and As(III) were 91.6 and 33.59 %, respectively. After five recycling cycles, the removal rates were 88 and 7 % for Cr(VI) and As(III) adsorption by NH₂-SBA-15, respectively.     

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.     

TiO_2胶体光催化降解罗丹明B染料

TiO2胶体从钛氧有机物水解制备,表征的方法有：X射线衍射光谱（XRD）、激光散射粒径分布、傅立叶变换红外光谱（FT-IR）、X射线光电子谱（XPS）和透射电子显微镜（TEM）。利用罗丹明B染料分子作为探针分子研究TiO2胶体的光催化活性,分析了pH、催化剂用量、外加氧化剂（H2O2）用量及罗丹明B初始浓度对TiO2胶体光催化活性的影响。结果表明：制备的TiO2胶体粒子平均粒径为13.8 nm（激光散法测定）,光催化降解罗丹明B染料的反应属于一级动力学反应,可以用Langmuir-Hinshewood模型加以描述,反应速率常数k1为0.08413 mg/（L.min）,平衡吸附常数k2为1.5305 L/mg;在pH为6,TiO2胶体用量为0.04%,H2O2（含量30%）用量为0.2%（V/V）,光照度为69.6μW/cm2时,5 h后罗丹明B染料的降解率可达到99%以上;相似的条件,0.2%的P25 TiO2粉体光催化处理染料水时,罗丹明B的降解率为90%。纳米TiO2胶体不仅可以提高罗丹明B的光催化降解率,还具有用量少,可有效降低水处理成本的特点。     

Kinetics and mechanism of TNT degradation in TiO2 photocatalysis

The photocatalytic degradation of TNT in a circular photocatalytic reactor, using a UV lamp as a light source and TiO(2) as a photocatalyst, was investigated. The effects of various parameters such as the initial TNT concentration, and the initial pH on the TNT degradation rate of TiO(2) photocatalysis were examined. In the presence of both UV light illumination and TiO(2) catalyst, TNT was more effectively degraded than with either UV or TiO(2) alone. The reaction rate was found to obey pseudo first-order kinetics represented by the Langmuir-Hinshelwood model. In the mineralization study, TNT (30 mg/l) photocatalytic degradation resulted in an approximately 80% TOC decrease after 150 min, and 10% of acetate and 57% of formate were produced as the organic intermediates, and were further degraded. NO(-)(3) NO(-)(2), and NH(+)(4) were detected as the nitrogen byproducts from photocatalysis and photolysis, and more than 50% of the total nitrogen was converted mainly to NO(-)(3)in the photocatalysis. However, NO(-)(3) did not adsorbed on the TiO(2) surface. TNT showed higher photocatalytic degradation efficiency at neutral and basic pH.     

Chromate reduction on humic acid derived from a peat soil--exploration of the activated sites on HAs for chromate removal

Humic substances are a major component of soil organic matter that influence the behavior and fate of heavy metals such as Cr(VI), a toxic and carcinogenic element. In the study, a repetitive extraction technique was used to fractionate humic acids (HAs) from a peat soil into three fractions (denoted as F1, F2, and F3), and the relative importance of O-containing aromatic and aliphatic domains in humic substances for scavenging Cr(VI) was addressed at pH 1. Spectroscopic analyses indicated that the concentrations of aromatic C and O-containing functional groups decreased with a progressive extraction as follows: F1>F2>F3. Cr(VI) removal by HA proceeded slowly, but it was enhanced when light was applied due to the production of efficient reductants, such as superoxide radical and H(2)O(2), for Cr(VI). Higher aromatic- and O-containing F1 fraction exhibited a greater efficiency for Cr(VI) reduction (with a removal rate of ca. 2.89 mmol g(-1) HA under illumination for 3 h). (13)C NMR and FTIR spectra further demonstrated that the carboxyl groups were primarily responsible for Cr(VI) reduction. This study implied the mobility and fate of Cr(VI) would be greatly inhibited in the environments containing such organic groups.     

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.     

Enhanced photocatalytic reduction reaction over Bi(3+)-TiO(2) nanoparticles in presence of formic acid as a hole scavenger

A series of Bi(3+)-doped TiO(2) (Bi(3+)-TiO(2)) catalysts with a doping concentration up to 2wt% were prepared by a sol-gel method. The prepared photocatalysts were characterized by different means to determine their chemical composition, surface structure and light absorption properties. The photocatalytic activity of different Bi(3+)-TiO(2) catalysts was evaluated in the photocatalytic reduction of nitrate in aqueous solution under UV illumination. In the experiments, formic acid was used as a hole scavenger to enhance the photocatalytic reduction reaction. The experiments demonstrated that nitrate was effectively degraded in aqueous Bi(3+)-TiO(2) suspension by more than 83% within 150min, while the pH of the solution increased from 3.19 to 5.83 due to the consumption of formic acid. The experimental results indicate that the presence of Bi(3+) in TiO(2) catalysts substantially enhances the photocatalytic reaction of nitrate reduction. It was found that the optimal dosage of 1.5wt% Bi(3+) in TiO(2) achieved the fastest reaction of nitrate reduction under the experimental condition. Bismuth ions deposit on the TiO(2) surface behaves as sites where electrons accumulate. Better separation of electrons and holes on the modified TiO(2) surface allows more efficient channeling of the charge carriers into useful reduction and oxidation reactions rather than recombination reactions. Two intermediate products of nitrite and ammonia during the reaction were also monitored to explore the possible mechanisms of photoluminescence quenching and photocatalytic reduction in the context of donor-acceptor interaction with electron trapping centers.     

Selective removal of Cr(VI) from aqueous solution by adsorption on mangosteen peel

Mangosteen peel, rich in polyphenolic compounds, was used to prepare the adsorbent exhibiting highly selective adsorption for Cr(VI) over other metal ions such as Pb²⁺, Fe³⁺, Zn²⁺, Cd²⁺, and Cr³⁺ at the pH values of 1～4. The chemical modification method proposed by using calcium hydroxide is quite cost-effective and ecofriendly without using any toxic reagents or causing any secondary pollution. The adsorption isotherm results revealed that the adsorption of Cr(VI) on the gel fit well the Langmuir adsorption model, and the maximum adsorption capacity for Cr(VI) at pH levels 1, 2, 3, and 4 was evaluated to be 2.46, 2.44, 1.99, and 2.14 mol/kg, respectively. The adsorption mechanism for Cr(VI) on the saponified gel was verified to follow an esterifiaction reaction coupled with the reduction of Cr(VI) to Cr(III) in which H⁺ plays a role of promoter. Thus, modified mangosteen peel gel has the prominent selectivity and low cost for Cr(VI) removal.     

Comparison of azo dye degradation efficiency using UV/single semiconductor and UV/coupled semiconductor systems

This study examined degradation of azo dyes using photocatalytic oxidation (UV/semiconductor). The model substrates employed in this work were Procion Red MX-5B and Amaranth, while the photocatalysts were TiO2, ZnO, and SnO2. UV-Vis spectrum analysis demonstrated that the band gap energies of TiO2, ZnO, and SnO2 were 3.17, 2.92, and 4.13 eV, respectively. The band gap energy of SnO2 is insufficient to initiate photocatalytic reaction after UV irradiation (365 nm). The reaction rate constants fit a first-order reaction model and the reaction rate constant of Procion Red MX-5B for TiO2+SnO2 (0.31 h-1) is larger than that of TiO2 (0.24 h-1) and SnO2 at pH 10. The difference between the conduction bands of SnO2 and TiO2 enables the former to act as a sink for the photogenerated electrons. Most of the reaction rate constants had higher values at pH 10 than pH 7, and thus the OH attack could be assumed to represent the main reaction in this investigation. The quantities of sulfate and chloride ions released are below stoichiometry during the degradation. Owing to the sulfonate groups of Amaranth exceeding Procion Red MX-5B, Amaranth had larger electrostatic attraction than Procion Red MX-5B with the surface of ZnO, and also had higher adsorption percentage than Procion Red MX-5B on the surface of ZnO. The trend of adsorption is consistent with the reaction rate constant at pH 7, namely Amaranth>Procion Red MX-5B. The sulfate dissociation rate constant of Amaranth in UV/ZnO at pH 7 (0.49 h-1) approaches the overall rate constant (0.53 h-1); therefore, the first step involved in Amaranth can be suggested to the cleavage of the bonds of the C-S in Amaranth, causing sulfate ion formation.