UV/H2O2作用下冰中苯酚的光转化及其与羟基自由基的关系

在UV和H₂O₂作用下考察pH值、 光强、 H₂O₂初始浓度和无机离子等对冰中苯酚光解的影响, 并利用二甲基亚砜（DMSO）捕获体系中生成的
羟基自由基（·OH）研究·OH对冰中苯酚光解的影响. 实验结果表明: H₂O₂可显著促进冰中产生·OH及苯酚光解; 改变光强、 pH值和H₂O₂的初始浓度, 苯酚的光解率随体系中·OH浓度的增加而增大; 加入NO^-₂和NO^-₃可抑制体系中产生·OH及苯酚光解; 加入SO^2-₄不影响体系中·OH的产生及苯酚光解; 加入CO^2-₃和HCO^-₃可抑制体系中产生·OH, 但对苯酚光解影响较小, 这是由于体系中产生了其他自由基所致.     

大枣多糖的提取与抗活性氧研究

为了分析大枣多糖对各类活性氧的清除能力,建立了热水提取-乙醇沉淀-氯仿、正丁醇去蛋白的工艺以提取大枣多糖(JPS),并作了糖的含量测定.用化学发光分析法分别测定提取的JPS对全血化学发光法中的全血白细胞呼吸爆发中产生的活性氧(H2O2、O2(-·)、·OH)、连苯三酚自氧化法产生的O2(-·)(超氧阴离子自由基)、抗坏血酸-Cu2+-H2O2体系产生的·OH(羟氧自由基)以及H2O2-鲁米诺发光体系中的H2O2的清除作用.结果:大枣多糖的得率为0.848%,总糖含量为37.7% .测定JPS清除·OH、O2(-·)、H2O2、白细胞呼吸爆发中产生的氧自由基活性的AOV值分别为109.48、9057.9 、312.01、5.204.结论:JPS具有清除氧自由基的作用,其活性大小与多糖的用量呈正相关.在全血生理环境下,对全血化学发光中活性氧的清除能力最强.     

Preparation of metal oxide doped ACNFs and their adsorption performance for low concentration SO2

Metal oxide （TiO2 or Co304） doped activated carbon nanofibers （ACNFs） were prepared by electrospinning. These nanofibers were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and Brunner- Emmett-Teller method （BET）. The results show that the average diameters of ACNFs were within the range of 200-500 nm, and the lengths were several tens of micrometers. The specific surface areas were 1146.7 m2/g for TiO2-doped ACNFs and 1238.5 m2/g for Co304-doped ACNFs, respectively. The electrospun nanofibers were used for adsorption of low concentration sulfur dioxide （SO2）. The results showed that the adsorption rates of these ACNFs increased with an increase in SO2concentration. When the SO2 concentration was 1.0 μg/mL, the adsorption rates of TiO2-doped ACNFs and Co3Oa-doped ACNFs were 66.2% and 67.1%, respectively. The adsorption rate also increased as the adsorption time increased. When the adsorption time was 40 min, the adsorption rates were 67.6% and 69.0% for TiO2-doped ACNFs and Co304-doped ACNFs, respectively. The adsorption rate decreased as the adsorption temperature increased below 60℃, while it increased as the adsorption temperature increased to more than 60℃.     

Photoluminescence and cathodoluminescence properties of a novel CaLaGa307：Dy3＋ phosphor

A single host white emitting phosphor, CaLaGa3O7:Dy3+, was synthesized by chemical co-precipitation. Field emission scanning electron microscopy, X-ray diffraction, laser particle size analysis, and photoluminescence and cathodoluminescence spectra were used to investigate the structural and optical properties of the phosphor. The phosphor particles were composed of microspheres with a slight tendency to agglomerate, and an average diameter was of about 1.0 μm. The Dy3+ ions acted as luminescent centers, and substituted La3+ ions in the single crystal lattice of CaLaGa3O7 where they were located in Cs sites. Under excitation with ultraviolet light and a low voltage electron beam, the CaLaGa3O7:Dy3+ phosphor exhibited the characteristic emission of Dy3+ (4F9/2-6H15/2 and 4F9/2-6H13/2 transitions) with intense yellow emission at about 573 nm. The chromaticity coordinates for the phosphor were in the white region. The relevant luminescence mechanisms of the phosphor are investigated. This phosphor may be applied in both field emission displays and white light-emitting diodes.     

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.     

四氧化三铁-石墨烯复合芬顿催化剂用于染料脱色的研究

芬顿催化是污水处理中最常用的技术之一,但是传统芬顿试剂需要对水体进行酸化并造成大量亚铁离子浪费.本文用水合肼还原法制备了四氧化三铁-石墨烯复合芬顿催化剂(Fe3O4-G),测试其催化脱色甲烯蓝的活性.Fe3O4-G样品用透射电镜、X射线光电子能谱和红外光谱等表征.Fe3O4-G能催化双氧水分解氧化脱色甲烯蓝.Fe3O4-G在pH3.5~9.5范围内均能有效催化脱色甲烯蓝,最佳pH为8.5.Fe3O4-G的催化活性几乎不受溶剂的影响,加入自由基淬灭剂叔丁醇对脱色也没有明显抑制.Fe3O4-G在较高的温度下催化能力更强,增大双氧水用量也能促进脱色反应.     

Potential release of hydrogen fluoride from domestic coal in endemic fluorosis area in Guizhou,China

Almost half of the total rural area of Guizhou Province and many regions within the 11 adjacent provinces in southwestern China have a long history(at least 70 years) of endemic fluorosis,including dental fluorosis and osteofluorosis along with its associated deformities and disabilities.Over decades of research,this specific type of endemic fluorosis has been defined as coal-burning fluorosis,which is distinct from drinking-water fluorosis.It is generally acknowledged that indoor burning and combustion of high-fluorine coal leads to food contamination,and fluorine then enters the human body.However,the exact chemical form of fluorine during its release and transfer to the body is still unknown.In the present study,21 domestic coal samples from outcrop and semi-outcrop coal collected in five villages with fluorosis were analyzed by time-of-flight secondary ion mass spectrometry(TOF-SIMS).The total mass fraction of sulfur in the samples ranged from 0.24%-5.58% and total fluorine content ranged 90.2-149.2 mg/kg.H3O+,H2SO4+ and HSO4-were detected in the samples by TOF-SIMS,which indicated that sulfuric acid hydrate(H2SO4.H2O) was present in the samples.F-was detected in all of these,which suggested the samples contain ionic fluorine compounds.Under certain circumstances,such as heating or burning,the prevalence and coexistence of the acid(H2SO4.H2O) and base(F-) would lead to a neutralization reaction producing volatile hydrogen fluoride(HF,bp = 19.5℃).This would be the chemical form of fluorine released from the coal.Further studies using HF and SO2 test tubes on headspace gas over coal samples heated to 200℃ in the laboratory and on headspace gas over stoves or chimney tops at rural residences confirmed the release of HF.     

Soft chemical synthesis and luminescence properties of red long-lasting phosphors Y2O2S:Sm3+

Sm³⁺-activated Y₂O₂S red phosphors were prepared by the combustion method and microemulsion method at the first time. X-ray characterization and electron diffraction show that, Y₂O₂S:Sm³⁺, Ti⁴⁺, Mg²⁺ samples prepared by these two methods are pure hexagonal crystals in structure with a trivial change due to dopants. Scanning electron microscopy (SEM) results show that the product presents an almond-like sheet in uniform size. Under the excitation of 269 nm ultraviolet light, Y₂O₂S:Sm³⁺ samples fabricated by these two methods exhibit three main groups of red emission lines located at 564, 604, and 656 nm, respectively, which are attributed to the transitions of 4G_5/2 →6H_5/2, 4G_5/2 →6H_7/2, 4G_5/2 →6H_9/2, respectively. The samples prepared by microemulsion are seven times higher in fluorescent emission intensity and half time longer in afterglow time than that prepared by combustion.     

NO adsorption study on the distribution of Ni2 + ions on the various micro-environments of carriers

The decrease of the electron density in the d orbits of Ni2+ ions, resulting from the disturbance of micro-environments in which Ni2+ ions are located, makes the frequency of adsorbed NO shift higher. The shift degree is determined mainly by the property of the microenvi-ronments. When Ni2+ ions are located on SII , SII · (SI ·) sites of Y zeolite or on the surface of γ-alumina, their NO adsorption gives rise to IR bands at 1 905, 1 900 and 1 855-1 875 cm-1, respectively. The distribution of Ni2 + ions on the various micro-environments of USY zeolite, AI2O3 and MS mixed carrier has also been discussed according to the different frequencies of adsorbed NO, as well as the influence of NiO loading.     

Structure and photocatalytic properties of TiO<Subscript>2</Subscript>-Graphene Oxide intercalated composite

TiO2-Graphene Oxide intercalated composite (TiO2-Graphene Oxide) has been successfully prepared at low temperature (80°C) with graphite oxide (GO) and titanium sulfate (Ti(SO4)2) as initial reactants.GO was firstly exfoliated by NaOH and formed single and multi-layered graphite oxide mixture which can be defined as graphene oxide,[TiO]2+ induced by the hydrolysis of Ti(SO4)2 diffused into graphene oxide interlayer by electrostatic attraction.The nucleation and growth of TiO2 crystallites took place at low temperature and TiO2-Graphene Oxide composite was successfully synthesized.Furthermore,the photocatalytic properties of TiO2-Graphene Oxide under the irradiation of UV light were also studied.The results show that the degradation rate of methyl orange is 1.16 mg min-1 g-1(refer to the efficiency of the initial 15 min).Compared with P25 powder,this kind of intercalation composite owns much better efficiency.On the other hand,the reusable properties and stable properties of TiO2-Graphene Oxide intercalated composite are also discussed in this paper.At last,crystalline structure,interface status,thermal properties and microscopic structure of TiO2-Graphene Oxide were characterized by X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS),thermogravimetric analysis (TGA),field emission scanning electron microscopy (FESEM) and high-resolution Transmission Electron Microscopy (HRTEM).Also,we have analyzed major influencing factors and mechanism of the composite structures which evidently improve the photocatalytic properties.     

高磷赤铁矿制备碳化铁的产物分离试验研究

利用高磷鲕状赤铁矿制备碳化铁,产物中含磷组分是影响碳化铁质量的关键因素。为了探究分离方式和添加剂对产物中含磷组分分离的影响,在1023K下分别用无添加、添加2%V2O5和添加5%Na2SO4的高磷鲕状赤铁矿制备碳化铁,将制得的产物球磨不同时间后采用磁选或离心+磁选的方式进行产物分离,最后分析产物中含磷组分的变化。结果表明,延长球磨时间可以提高产物的脱磷率,但球磨时间过长会降低产物的铁收得率,以球磨2h为宜;无添加剂时制备所得碳化铁试样球磨时间从1h延长至2h后,脱磷率从18.17%升至18.48%,再增加离心分离操作后,会进一步提升产物的脱磷率至23.04%;添加5%Na_2SO_4和2%V_2O_5均可破坏铁矿石的鲕状结构,有利于含Fe组分与脉石的分离,但添加Na_2SO_4会降低产物的碳化铁含量,而V_2O_5的添加则可同时促进碳化铁的生成以及提高产物的脱磷率,是一种较好的添加剂。     

One-pot synthesis of Sb-Fe-carbon-fiber composites with in situ catalytic growth of carbon fibers

A Sb-Fe-carbon-fiber (CF) composite was prepared by a chemical vapor deposition (CVD) method with in situ growth of CFs using Sb₂O₃/Fe₂O₃ as the precursor and acetylene (C₂H₂) as the carbon source. The Sb-Fe-CF composite was characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM), and its electrochemical performance was investigated by galvanostatic charge-discharge cycling and electrochemical impedance spectroscopy. The Sb-Fe-CF composite shows a better cycling stability than the Sb-amorphous-carbon composite prepared by the same CVD method but using Sb₂O₃ as the precursor. Improvements in cycling stability of the Sb-Fe-CF composite can be attributed to the formation of three-dimensional network structure by CFs, which can connect Sb particles firmly. In addition, the CF layer can buffer the volume change effectively.     

Preparation and magnetic properties of CoFe2O4/TiO2 composite films

Using （Ti（OC4H9）4） and metal chlorates as starting materials, CoFe2O4/TiO2 composite films were prepared by sol-gel method. The effects of heat treatment temperature and pH of the precursor on microstructure and magnetic properties were studied. The phase structure of the samples was examined by X-ray diffraction. The microstructure was examined by scanning electron microscope, atomic force microscope and polarized microscope. The magnetic property was measured by vibrating sample magnetometer. The results show that the crystals of different phases grow up independently. CoFe2O4 is uniformly embedded into the TiO2 matrix in the prepared composite films, and the growth of composite films is dependent on the heat treatment temperatures and PH of the precursor. The average size of CoFe2O4 crystal is 19 nm in Nanocomposite film prepared when the heat treatment temperature is 800℃ and the pH of the precursor is between 2 and 3. The magnetism of the composite films is enhanced as the heat treatment temperature increases.     

不同离子对氧化锌晶体形貌的影响

以不同Zn盐Zn(CH3COO)2.2H2O,ZnCl2,ZnSO4.7H2O,Zn(NO3)2.6H2O与不同碱NaOH,KOH为原料,制得Zn(OH)42-前驱溶液,使之在水热环境下分解,生成ZnO晶体.产物通过全自动X射线衍射仪(XRD)进行物相分析,扫描电子显微镜(SEM)观测ZnO晶体的形貌和大小.170℃,溶液中的阴离子CH3COO-,SO42-,NO3-,Cl-分别与Na+构成干扰离子对,伴随着晶体生长12 h,晶体成长为片球集状、极性生长明显的花状、极性生长不明显的花状、小尺寸花状ZnO晶体;140℃,溶液中阳离子Na+,K+分别与CH3COO-作为离子对,干扰晶体生长,12 ...     

Reaction between sulfur dioxide and iron oxide cationic clusters

The reactivity of sulfur dioxide （SO2） molecules toward iron oxide cationic clusters （FemOn^＋） is studied by a homemade time-of-flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source and a fast flow reactor. The association products FemOnSO2^＋ can be observed for most of the clusters. The interesting result is that the cooperation effect of SO2 and water is in favor of the adsorption of gas phase water on specific scale iron oxide clusters （Fe2O2^＋ and Fe3O3^＋ ）. The reactivity information obtained may be useful to investigate atmospheric heterogeneous chemistry of related systems.     

Electroless copper-phosphorus coatings with the addition of silicon carbide (SiC) particles

Cu-P-silicon carbide (SiC) composite coatings were deposited by means of electroless plating. The effects of pH values, temperature, and different concentrations of sodium hypophosphite (NaH₂PO₂·H₂O), nickel sulfate (NiSO₄·6H₂O), sodium citrate (C₆H₅Na₃O₇·2H₂O) and SiC on the deposition rate and coating compositions were evaluated, and the bath formulation for Cu-P-SiC composite coatings was optimised. The coating compositions were determined using energy-dispersive X-ray analysis (EDX). The corresponding optimal operating parameters for depositing Cu-P-SiC are as follows: pH 9; temperature, 90℃; NaH₂PO₂·H₂O concentration, 125 g/L; NiSO₄·6H₂O concentration, 3.125 g/L; SiC concentration, 5 g/L; and C₆H₅Na₃O₇·2H₂O concentration, 50 g/L. The surface morphology of the coatings analysed by scanning electron microscopy (SEM) shows that Cu particles are uniformly distributed. The hardness and wear resistance of Cu-P composite coatings are improved with the addition of SiC particles and increase with the increase of SiC content.     

Preparation of narrow band gap V2O5/TiO2 composite films by micro-arc oxidation

V₂O₅/TiO₂ composite films were prepared on pure titanium substrates via micro-arc oxidation (MAO) in electrolytes consisting of NaVO₃. Their morphology and elements were characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis. Phase composition and valence states of species in the films were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS) were also employed to evaluate the photophysical property of the films. The V₂O₅/TiO₂ composite films show a sheet-like morphology. Not only V₂O₅ phase appears in the films when the NaVO₃ concentration of the electrolyte is higher than 6.10 g/L and is loaded at the surface of anatase, but also V⁴⁺ is incorporated into the crystal lattice of anatase. In comparison with pure TiO₂ films the V₂O₅/TiO₂ composite films exhibit significantly narrow band gap energy. The film prepared in an electrolyte consisting of NaVO₃ with a concentration of 8.54 g/L exhibits the narrowest band gap energy, which is approximately 1.89 eV. The V₂O₅/TiO₂ composite films also have the significantly enhanced visible light photocatalytic activity. The film prepared in an electrolyte consisting of NaVO₃ with a concentration of 8.54 g/L exhibits the best photocatalytic activity and about 93% of rhodamine is degraded after 14 h visible light radiation.     

Mechanism and kinetics for scavenging superoxide anion by progesterone

The chemical reaction of progesterone with superoxide anion O^.-₂ in 0.1 mol/L NaHCO₃ medium is studied by polarography. Differing from the indirect inhibition of O^.-₂ generation by synthesized glucocorticoids in mechanism, the function that progesterone scavenges O^.-₂ is ascribed to that O^.-₂ directly oxidizes the C == C double bond conjugated with the carbonyl moiety of progesterone molecule to a free radical, and then is reduced to H₂O₂. The result obtained in this work gives new evidence for biomedical research. The equation of rate constant of the oxidization reaction is deduced, and the apparent rate constant obtained is 308 L·mol^-1·s^-1.     

Experimental studies on silicate structures of basaltic glasses quenched at 1 65093 and 1–3.5 GPa

A series of melting experiments was carried cut at 1 650°C and 1.00–3.00 GPa using alkaline basalt as starting material. The cornpitions of quenched basaltic glasses in the products were detected by electron micro probe. Their CIPW norms were calculated and their refractive indices were determined by the oil-infused method. The Raman spectrum of the quenched basaltic glasses indicates that their main structural species are monomer [Si₂O₄]1⁴⁻, chain [Si₂O₆]1^4- and sheet [Si₂O₅]1^2-. The relationship at the same temperature between the proportions of integrated areas of structural species, and compositions and pressures was discussed.     

Temperature effect on the corrosion and passivation characterization of Ni<Subscript>82.3</Subscript>Cr<Subscript>7</Subscript>Fe<Subscript>3</Subscript>Si<Subscript>4.5</Subscript>B<Subscript>3.2</Subscript> alloy in acidic media

The effects of temperature on corrosion and the electrochemical behavior of Ni_82.3Cr₇Fe₃Si_4.5B_3.2 glassy alloy in HCl, H₂SO₄, and H₃PO₄ acids were studied using AC and DC techniques. Impedance data reveal that the susceptibility to localized corrosion increases with increasing temperature. Potentiodynamic polarization curves reveal that the bulk glassy alloy is spontaneously passivated at all the investigated temperature in H₂SO₄ and H₃PO₄ solutions. A localized corrosion effect in HCl solution is clearly observed. The apparent activation energies in the regions of Tafel, active, and passive, as well as the enthalpies and entropies of the dissolution process were determined and discussed. The high apparent activation energy (E_a) value for H₃PO₄ solution in Tafel region is explained by the low aggressivity of PO₄3- ions.