TiO2/SiO2纳米粒子光催化降解庚烯/二氧化硫

以TiO₂/SiO₂纳米粒子为催化剂， 研究了催化剂不同焙烧温度对二氧化硫与庚烯光催化反应的影响. 结果表明， 经600 ℃焙烧的催化剂对庚烯的降解最好. 同时研究了庚烯和二氧化硫的初始浓度、 氧气和水蒸气的不同含量及光强等因素对其光催化氧化降解的影响. 庚烯的降解速率随着二氧化硫浓度的增加而增加， 最终趋于稳定. 在二氧化硫浓度一定时， 庚烯的反应速率分别随着氧气和水分子含量的增加而不断增大， 氧含量为20%时速率最大； 水分子含量为444 μmol/L时速率最大. 庚烯的反应速率随着光强的增加而增大， 光强增至8.32 mW/cm²时， 反应速率趋于定值. 通过FT-IR和GC-MS测定初步确定了反应产物.     

Photodegradation of 17α-Ethynylestradiol in Aqueous Solution with Nitzschia hantzschiana or Chlorella vulgaris and Fe^3＋

0　IntroductionTherehasbeenincreasingconcernabouttheenvironmentaleffectsofoestrogensandxenoestrogens[1 ] .17α ethynylestradiol(EE2 ) (Fig .1)isasyntheticestrogenicsteroidthathastherapeuticuses (e.g .Oralcontraception) .Syntheticestrogensaregenerallymorestableinwaterthannaturalestrogensandhavegreaterpotency.Theyaredifficulttobeabsolutelyremovedfromwastewatersbyprimaryandsecondarytreatment.Thedegradationchemistryofthiscom poundhasnotbeenextensivelystudied .Therearefewpublishedarticlesstudying…     

Degradation of the antibiotic sulfamonomethoxine sodium in aqueous solution by photo-Fenton oxidation

In this study, photo-Fenton oxidation was applied to degradation of sulfamonomethoxine sodium (SMMS) in aqueous solution. The operation parameters of pH, temperature, and concentrations of H2O2, Fe2+ and SMMS were investigated. The optimum conditions for the photo-Fenton process were determined as follows: [SMMS]=4.53 mg/L, pH 4.0, [H2O2]=0.49 mmol/L, [Fe2+]= 19.51 μmol/L and T=25°C. Under these conditions 98.5% of the SMMS degraded. The kinetics were also studied, and degradation of SMMS by the photo-Fenton process could be described by first-order kinetics. The apparent activation energy was calculated as 23.95 kJ/mol. Mineralization of the process was investigated by measuring the chemical oxygen demand (COD), and the COD decreased by 99% after 120 min. This process could be used as a pretreatment method for wastewater containing sulfamonomethoxine sodium.     

Preparation of Zn-doped TiO2 nanotubes electrode and its application in pentachlorophenol photoelectrocatalytic degradation

Zn-doped titanium oxide （TiO2） nanotubes electrode was prepared on a titanium plate by direct anodic oxidation and immersing method in sequence. Field emission scanning electron microscopy （FESEM） showed that the Zn-doped TiO2 nanotubes were well aligned and organized into high density uniform arrays with diameter ranging from 50 to 90 nm. The length and the thickness were about 200 and 15 nm respectively. TiO2 anatase phase was identified by X-ray diffraction （XRD）. X-ray photoelectronspectroscopy （XPS） indicated that Zn ions were mainly located on the surface of TiO2 nanotubes in form of ZnO clusters. Compared with TiO2 nanotubes electrode, about 20 nm red shift in the spectrum of UV-vis absorption was observed. The degradation of pentachlorophenol （PCP） in aqueous solution under the same condition （initial concentration of PCP： 20 mg/L; concentration of Na2SO4：0.01 mol/L and pH： 7.03） was carried out using Zn-doped TiO2 nanotubes electrode and TiO2 nanotubes electrode. The degradation rates of PCP using Zn-doped TiO2 nanotubes electrode were found to be twice and 5.8 times as high as that using TiO2 nanotubes electrode by UV radiation （400 μw/cm^2） and visible light radiation （4500 μw/cm^2）, respectively. 73.5% of PCP was removed using Zn-doped TiO2 nanotubes electrode against 45.5% removed using TiO2 nanotubes electrode in 120 min under UV radiation. While under visible light radiation, the degradation efficiency of PCP was 18.4% using Zn-doped TiO2 nanotubes electrode against 3.2% using TiO2 nanotubes electrode in 120 min. The optimum concentration of Zn doping was found to be 0.909%. The PCP degradation efficiencies of the 10 repeated experiments by Zn-doped TiO2 nanotubes electrode were rather stable with the deviation within 3.0%.     

Mineralogical and sink-float studies of Jajarm low-grade bauxite

Jajarm’s bauxite deposits are mainly diasporic, and they have a low mass ratio of Al₂O₃/SiO₂. It is necessary to increase the run-of-mine mass ratio before feeding the material to the Bayer process. Chemical analysis indicated that the low-grade bauxite sample from Jajarm contained 43.9wt% Al₂O₃ and 13.35wt% SiO₂, resulting in a mass ratio of 3.29. According to mineralogical studies, the presence of aluminosilicate minerals such as kaolinite, illite, and quartz was the main reason for the decrease of the mass ratio. Microscopic observations revealed that, with the size reduction from -1000+710 to -38 μm, the liberation degree of diaspore increased from 10% to 60%, and that of aluminosilicates increased from 20% to 85%. Heavy liquids with the densities of 2.8, 3.0, 3.2, and 3.4 g/cm3 were used to evaluate the heavy media separation in three sizes, i.e., -3350+710, -710+212, and -212+125 μm. Laboratory studies confirm that the density of 3.2 g/cm3 can produce the concentrates (in sunk fractions) with recoveries of 89.09%, 91.24%, and 84.68% with the Al₂O₃/SiO₂ mass ratios of 5.03, 5.16, and 5.15 for the -3350+710, -710+212, and -212+125 μm sizes, respectively.     

Dissociation of methanol in intense femtosecond laser field

Methanol was irradiated by 80 fs laser pulse, intensity range of 10¹³–10¹⁴ W/cm². A TOF-mass spectrometer was coupled to the laser system and used to detect the ions produced. The parent ions CH₃OH⁺ appeared firstly at the laser intensity of 1.4×10¹³ W/cm². While the laser intensity was gradually increased, the parent ions were dissociated and the primary ions CH₂OH⁺ were given as verified from the irradiation of deuterated methanol (CH₃OD) showing the C—H bond cracking firstly. While the laser intensity was further increased to 2.0 × 10¹³ W/cm², the C—O bonds of the parent ions also broke to give CH₃ ⁺. When the laser intensity was higher, smaller fragment ions like CH⁺, C⁺, OH⁺ and O⁺ also appeared. Among the fragment ions, only H⁺ ion yield had anisotropic angular distribution dependence on the laser polarization vector in the dissociation of methanol. All the experimental observations show that the dissociation of methanol proceeds through stepwise mechanism but not Coulomb explosion.     

Preparation and photocatalytic properties of ilmenite NiTiO<Subscript>3</Subscript> powders for degradation of humic acid in water

The powders of ilmenite structure NiTiO₃ were prepared by a modified Pechini process using tetrabutyl titanate and nickel acetate as raw materials, and using citric acid and ethanol as a chelating agent and a solvent respectively. The powder samples were characterized by thermogravimetric and differential thermal analysis (TG-DTA) and X-ray diffraction (XRD). The photocatalytic activity of NiTiO₃ under the irradiation of ultraviolet rays (UV) light was evaluated by degrading humic acid (HA) in water as a probe reaction. The possible photodegradation mechanism was studied by the examination of active species ·OH, ·O₂⁻, and holes (h⁺) through adding scavengers. The TG-DTA and XRD results indicated that the good crystal structure of ilmenite phase NiTiO₃ could be obtained when the Ni-Ti citrate complex was calcined at 600°C. The photocatalytic activity experiments indicated that NiTiO₃ had favourable photocatalytic activity under the irradiation of UV light, and the photocatalytic degradation rate of HA reached 95.3% after a 2.5 h reaction with the photocatalyst calcined at 600°C and a photocatalyst dosage of 0.4 g/L. The possible photocatalytic mechanism was deduced that holes (h⁺) and ·OH radicals are the major reactive active species in the photocatalytic reaction, and dissolved oxygen plays a weak role in the degradation of HA.     

Photoelectrochemical synergetic degradation of Acid Orange II with TiO2 modified β-PbO2 electrode

Electrochemically assisted photocatalysis is an effective approach to improve photocatalytic efficiency. In this paper, modified β-PbO2 electrode was prepared by TiO2 co-deposition and characterized by SEM and XRD. Then 2.0g TiO2 modified β-PbO2 electrode (2.0 g TiO2 involved in the 200 mL co-deposition solution) was used in electrochemically assisted photocatalytic degradation of Acid Orange II and the influence of initial pH values was investigated when the potential applied across the electrodes was 1.5 V. When the potential applied was 2.5 V, the difference of the degradation process and the final products were studied. The results indicated that 2.0 g TiO2 modified β-PbO2 electrode was different from the unmodified one in that the β-PbO2 crystals became finer and the electrode became more compact and more uniform. The synergetic effect in electrochemically assisted photocatalytic degradation of Acid Orange Ⅱ was observed and degradation efficiency and TOC removal were the highest at initial solution pH 2.0. By UV-visible spectral analysis, it was proved that photoelectrochemical synergetic degradation of Acid Orange Ⅱ went through the step of producing main product maleic acid for the solution at the initial pH 2.0 within 2 h, but the degradation was slow for the solution at the initial pH 12.0.     

Preparation,crystal structure and quantum chemical investigation of [Li(NTO) (H2O)]

[Li(NTO)(H₂O)₂] was prepared by mixing the aqueous solution of 3-nitro-1,2,4-triazol-5-one (NTO) and lithium hydroxide. The crystal structure of [Li(NTO)(H₂O)₂] was determined by single crystal diffraction analysis. The crystal is monoclinic, space group P2₁/n with crystal parameters of a = 0.742 0(2) nm, b = 0.344 9(1) nm,c = 2.490 6(3) nm, β= 94.89(1)°, Z = 4,D _c , = 1.799 g cm⁻³,V = 0.635 nm³, μ = 1.591 cm⁻¹, F(000) = 392. The finalR is 0.051. The MNDO MO calculation shows that the coordinate bonds of title compound possess certain extent of covalent character. O₂ atom of NTO anion is bonded to Li atom; the nitro group will be lost first when NTO is decomposed.     

Hydroxyl in continental deep subduction zone: Evidence from UHP eclogites of the Dabie Mountains

Infrared spectra in the region of 3 000 to 4 000 cm⁻¹ have been measured by an FTIR spectrometer on minerals in UHP eclogites from the Bixiling and Shuanghe areas, the Dabie Mountains. It is shown that omphacite is the most important hydrous mineral (100–200 μg/g) in UHP eclogites. Garnet and quartz contain virtually no H₂O or OH. Accessory mineral rutile contains a significant amount of OH (>1 000 μg/g). Coesite gives no indication of the presence of OH but apparent H₂O bands. The results have considerable implications for existing forms and contents of hydroxyl in the continental deep subduction zone, the eastern Dabie Mountains.     

Effect of Nano red elemental selenium on GPx activity of broiler chick kidney cells<Emphasis Type="Italic">in vitro</Emphasis>

A new selenium source, Nano red elemental selenium (Nano-Se) was used to study the effect on the GPx activity of broiler chick kidney cells (BCKC)in vitro, Sodium selenite (Na₂SeO₃) and seleno-1-methionine (Se-Met) were used as the controls. The results showed that the effects of three kinds of Se forms on the GPx activity of BCKC were accordant (p>0.05) compared with each other at 0.01. 0.05 and 0.10 μmol/L Se concentrations treatments. In the range of 0.00–0.10 μmol/L Se concentrations, the GPx activity increased with elevation of Se concentrations in medium. For the three kinds of Se forms, the GPx activity reached the climax at 0.10 μmol/L Se concentration. At 0.20 and 0.30 μmol/L Se concentrations, the influnces of three kinds of Se forms were not accordant with one another. For Nano-Se, the GPx activity at 0.20 and 0.30 μmoi/L Se concentrations remained the same as that at 0.10 μmol/L Se concentration treatment. For Se-Met, the GPx activity at 0.20 μmol/L Se concentration treatment remained the same with 0.10 μmol/L treatment; the GPx activity at 0.30 μmol/L Se concentration treatment was declined significantly (p<0.05) compared with 0.10 or 0.20 μmol/L treatment. For Na₂SeO₃, the GPx activity falled gradually with Se concentration increasing from 0.10 μmol/L to 0.30 μmol/L, and at 0.30 μmol/L Se concentration treatment, the GPx activity was less than the original of BCKC. The results implicated, on the GPx activity of BCKCin vitro, the ranking of width range of the most suitable Se concentration for nutrition curve of the three Se formes is Nano-Se>Se-Met>Na₂SeO₃. Foundation item: Supported by the Key Item of the Science and Technology Bureau of Zhejiang Province (021122680) Biography: Xu Bao-hua (1966-), male, Associate professor, Ph. D. research direction: nanobiology and animal nutrition.     

超临界干燥法制备的锐钛矿TiO_2纳米晶光催化降解亚甲基蓝的研究

以自制的锐钛矿TiO2纳米晶为光催化剂,高压汞灯为光源,考察了亚甲基蓝溶液初始浓度、催化剂用量、pH值、O2和Fe^3＋等因素对其光催化降解的影响．结果表明,适宜的pH值为5．6,最佳的催化剂用量为1．5g／L,通入一定量氧或加入少量的Fe^3＋离子能有效的促进TiO2光催化亚甲基蓝降解．     

二氧化钛光催化降解地下水中的六六六

通过实验证实了利用二氧化钛作为催化剂光降解地下水中六六六的可行性. 讨论了光照时间、 光照强度、 地下水pH值、 温度等因素对降解效果的影响. 由正交实验确定出最佳降解条件： 8 W紫外光灯管照射、 光照时间为30 min、 地下水pH=5、 温度为14 ℃， 降解率为47.96%, 考察了Fe₃₊,Mn₂₊对光降解效果的影响.     

银掺杂多孔氧化钛光催化甲基橙降解反应条件的探究

利用溶胶-凝胶法结合光还原法制备Ag掺杂多孔TiO_2光催化剂,以甲基橙的降解效果为评价标准,考查了光照降解时间、光催化剂用量、甲基橙溶液初始浓度、溶液pH值对光催化剂催化降解甲基橙的影响。结果表明,本方法制备的光催化剂无论是在紫外光还是可见光下均具有优良的光催化性能:在浓度为10 mg/L的甲基橙溶液中,4 g/L光催化剂,紫外光照射80 min,甲基橙可实现100%完全降解;相同催化条件下,可见光照100 min,甲基橙完全降解;当反应溶液pH=2时,紫外光和可见光都可在20 min内实现甲基橙的完全降解。     

Modification of TiO2 nanotubes arrays by CdS and their photoelectrocatalytic hydrogen generation properties

In order to realize hydrogen generation under visible light, novel CdS/TiO2 nanotubes arrays are developed by electrochemical anodizaUon of Ti in 0.15 mol/L NHTF ＋ 0.08 mol/L H2C2O4 electrolyte. The diameter of the nanotube is 80-100 nm and the length is approximately 550 nm. The CdS nano-particles are deposited on the TiO2 nanotubes arrays by chemical bath deposition （CBD） in the ammonia-thiourea system. A 300 W Xe lamp is used as the light source, CdS/TiO2 nanotube arrays are used as the photoanode with the application of 1.0 V bath voltage, and 0.1 mol/L Na2S ＋ 0.04 mol/L Na2SO3 solution is used as the electrolyte, then the rate of photoelectrocatalytic hydrogen generation is 245.4 μL/（h·cm^2）. This opens new perspectives for photoelectrocatalytic hydrogen generation by using CdS/TiO2 nanotubes arrays.     

The presence of phosphorylation form of D1 protein in its cross-linked aggregates in high light treated spinach leaves in vivo

Photosystem Ⅱ (PS Ⅱ ) is a pigment-protein com-plex that catalyses the primary photochemistry leading to oxygen evolution and electron flow in oxygenic phototrophs. The reaction center of PSⅡ is composed of the D1 and D2 proteins to which all the redox…     

Catalytic oxidation of phenol in wastewater-A new application of the amorphous Fe78Si9B13 alloy

The amorphous Fe78Si9B13 alloy was used as a heterogeneous Fenton catalyst in the process of phenol degradation.The influences of main operating parameters such as reaction temperature,catalyst amount,hydrogen peroxide dosage and initial pH of solution on phenol degradation rate were investigated.The maximum mineralization of phenol was achieved at 60°C,6 g/L Fe78Si9B13, 0.31 mol/L hydrogen peroxide,with an initial pH of 2.5.More than 99%of phenol was completely removed under the optimum conditions within 10 min for a solution containing 1000 mg/L of phenol.Batch experiments for solutions containing phenol con- centrations ranging from 50 to 2000 mg/L were investigated under the above conditions and the same excellent degradation rate was obtained.The Fe78Si9B13 showed better catalytic activity than iron powder and Fe 2+ .Addition of n-butannol(hydroxyl radical scavenger)decreased the degradation rate of phenol,which demonstrates that hydroxyl radicals were mainly responsible for the removal of phenol.We demonstrated that phenol may be degraded by hydroxyl radicals decomposed by hydrogen peroxide on the surface of Fe78Si9B13 and illustrated the reaction mechanism for this process.This amorphous alloy exhibited high stability in recycling experiments and showed excellent reuse performance even after continuous operations of 8 cycles.     

Molecular source of biomarkers by genetic engineering techniques

The mutant lacking ORF469 fragment inSynechocystis sp. PCC 6803 (cyanobacterium) was created by means of DNA recombination. In its genome,ORF ₄₆₉, the key DNA fragment controlling the light-independent pathway of chlorophyll biosynthesis was deleted and replaced by erythromycin resistance cassette. The operation resulted in the fact that the content of chlorophyll in mutant cells was fully controlled by illumination and two kinds of cells were harvested, one is high chlorophyll with concentration of 9.427 μg· mg⁻¹ and the other is low chlorophyll with concentration of 0.695 μg · mg¹. They were subjected to thermal simulation respectively at 300°C for 100 h. The alkanes biomarkers from pyrolysates were analyzed by GC-MS and main difference between high and low chlorophyll cells was found at their contents of isoprenoid hydrocarbons. Pr/nC₁₇ and Ph/nC₁₈ from pyrolysate of low chlorophyll cells were 0.192 and 0.216 respectively, which were about 1/3 and 1/7 of that from high chlorophyll cells. The results provide direct evidence that isoprenoid hydrocarbons such as phytane(Ph) and pristane (Pr) could be derived from chlorophyll. The lipids in algal cells would be the most important contributors to hydrocarbon production in their thermal degradation. The results also indicated that the combination of molecular biology and organic geochemistry would provide a new path to investigate the molecular sources of biomarkers.     

Hybrid plant regeneration from interfamilial somatic hybridization between grapevine (vitia vinifera L.) and Red Thorowax (Bupleurum scorzonerifolium willd)

The protoplasts of Red Thorowax ( Bupleurum scorzonerifolium) irradiated by ultraviolet light (UV) at an intensity of 260μW/cm2 for 0, 1,2 and 3 min respectively were fused with that of grapevine ( Vitia vinifera). The regenerated 19 clones, every one derived from a single fused cell, were identified as hybrids by phenotype, isozyme, chromosome and 5S rDNA spacer region analysis. The results reveal that all of them are somatic hybrids. 11 hybrid calli including asymmetric and symmetric products regenerated somatic embryos and young leaves after 5 months of culture, of which 4 hybrid cell lines derived from asymmetric fusion regenerated plants with roots after 8-10 months of culture. Inspection of chromosome showed that regeneration of whole plant was related to the decrease of chromosome number. Identification of 5S rDNA spacer region of the plants confirmed that they were interfamilial hybrid plants.     

Molecule modification and mass deposition induced by the implantation of low energy Fe+ ion beams into amino acids

Fe⁺ ion beams with the energy of 110 keV were implanted into films of L(+)-cysteine (HSCH₂CH(NH₂)COOH). One of the single crystals grown in hydrochloric acid solution with the implanted samples through slow evaporation was structurally characterized by the X-ray crystallography. The crystal is monoclinic, space group C2, with a = 1.8534(4) nm, b = 0.5234(1) nm, c = 0.7212(1) nm, β= 103.72°, V = 0.67965(3) nm³, Z = 4, F(000) = 144.0, D{clac} = 1.763 g · cm⁻³, μ(MoK _a = 1.06 mm⁻¹, T = 293(2) K. R = 0.0379, wR = 0.0835 for 660 observed reflections (I > 2σ(I)). The structural formula of the crystal compound is (CH₂CH(NH₂)NO₂)ClFe (M _r = 180.38 u). Products of heavy ion beam irradiation were purified and it was directly confirmed that the implanted Fe⁺ ions had been deposited in the novel molecules. The same doses of Fe⁺ ion beams of the same energy were implanted into films of L(+)-cysteine hydrochloride monohydrate. FTIR spectroscopy of the implanted samples proved that some of the original molecules were seriously damaged and significant modifications were induced.