The Kinetics of Complexed and Free Ho2 Radical in the Reaction of Ce+4 and H2O2

The intermediates formed in the reaction of Ce⁺⁴ with H₂O₂ in 0.5 M perchloric acid were studied, spectrophotometrically and through the quenching method, using a stopped-flow system. The spectrum in the UV range and the kinetics of the generated radicals and their dependence on Ce⁺³ concentration were investigated. On adding Ce⁺³ to the mixture, a change in the spectrum as well as in the recombination rate constant was observed. This behaviour was attributed to the formation of a complex between the cerous ion and the HO₂ radical. The values of the recombination rate constant of the complexed radical is 4.0 ± 0.4·10⁶ F^?1 sec^?1 while that of the free HO₂ radical is 0.9 ± 0.1·10⁶ F^?1 sec^?1. The stabilization constant of the complex was found to be 60 ± 18 F^?1.     

Oxidation of Ce3+ by HO2 Radical and Ce3+-HO2 Complex Formation

The reaction of Ce⁴⁺ with H₂O₂ in H₂SO₄ is studied as a function of pH, Ce³⁺, SO₄⁼ and the ionic strength. The reaction mechanism proposed assumes the existence of a Ce³⁺ -HO₂ complex. Direct evidence for the reaction, Ce³⁺ + HO₂ + H⁺ → Ce⁴⁺ + H₂O₂ is presented.     

Thin-Layer Chromatography of Metal Ions in Formic Acid Medium on Impregnated and Unimpregnated Silica Gel G: Semiquantitative Determination of Fe3+, Cd2+, Th4+, Al3+, Zn2+, UO2+ 2, VO2+, Ce4+, and Ni2+

Abstract

The adsorption behavior of metal ions in the formic acid-sodium formate system using unimpregnated as well as impregnated silica gel G as thin layers has been studied. A remarkable result of this study is the dramatic selectivity of impregnated silica gel G thin layers when compared to the corresponding unimpregnated silica gel G thin layers. This impregnation effect provides us with a new adsorbent phase which is sufficiently stable in the formic acid-sodium formate medium. Some important ternary separations have been achieved on silica gel G thin layers. Al³⁺, Ni²⁺, Fe³⁺, and Pb²⁺ have been qualitatively separated from mixtures of other ions. Cu²⁺ has been selectively separated on impregnated silica gel G thin layers. The semi-quantitative determination of nine metal ions on impregnated silica gel G layers has also been attempted.     

纳米粉体Y2O3:Ti3+,Pr3+的光谱性能

采用共沉淀法在氮氢气氛中制备出Y2O3:Ti3+,Pr3+纳米粉体,通过XRD、TEM方法确认了它的晶相与晶粒尺寸,测量了它的激发与发射谱,并与Y2O3:Ti3+纳米粉体的光谱进行了比较。结果显示:共掺Pr3+仅在281nm处产生了激发峰,而在蓝绿光区没有产生激发峰,以致365～480nm的光激发不出Pr3+的特征红荧光。表明:共掺Pr3+的Y2O3:Ti3+用作白光LED荧光粉,难以改善发光性能。     

Influence of the Metal Ions Cr3+, Fe3+, Ni2+ and Cu2+ on the Stability and Oxygen Consumption of Acrylic and Methacrylic Acid

For the safe and trouble‐free operation of a manufacturing plant and the safe storage of acrylic, as well as methacrylic monomers, it is important to know the polymerization stability as a function of the process parameters (temperature, oxygen concentration, and impurities, e.g., metal ions). Contamination with metal ions can be caused by the corrosion of steel units. Therefore, the influence of the metal ions Cr³⁺, Fe³⁺, Ni²⁺ and Cu²⁺ in the concentration range of 0–10 ppm (g g^–1) on the polymerization behavior and the oxygen consumption of acrylic and methacrylic acid were examined in this work. It was shown that Cr³⁺, Ni²⁺, and Cu²⁺ ions extend the inhibition period of acrylic acid (AA) and methacrylic acid (MAA) and reduce the O₂ consumption. Fe³⁺ ions, however, cause a decrease of the inhibition period and in the case of AA an increase of the O₂ consumption, which leads, in the end, to a faster unintentional polymerization. Therefore, alloys which contain iron should be avoided as far as possible in the construction of AA plants. Fe³⁺‐ions show the opposite influence towards MAA, here the presence of Fe³⁺ shows a stabilizing effect.     

Electrochemical behaviour of Mn3+/Mn2+, Co3+/Co2+ and Ce4+/Ce4+ redox mediators in methanesulfonic acid

The redox behaviour of Mn³⁺/Mn²⁺, Co³⁺/Co²⁺ and Ce⁴⁺/Ce³⁺ mediators commonly used in indirect oxidation of organic compounds were evaluated in methane sulfonic acid on a glassy carbon working electrode employing cyclic voltammetry. Manganic methanesulfonate exhibits higher instability in dilute methanesulfonic acid. The solid MnO₂ formed during disproportionation on the glassy carbon electrode further affects the reproducibility. Cobaltic methanesulfonate formation occurs only at oxygen evolution region rendering the overall oxidation process less efficient. Ceric methane sulfonate formation is highly efficient over a wide acid concentration range. Ceric methanesulfonate can also be employed over a wide temperature range to oxidize different aromatic compounds.     

The effect of Co2+, Cu2+, Fe2+ and Fe3+ during electrowinning of nickel

The effects of the impurities Co²⁺, Cu²⁺, Fe²⁺, Fe³⁺ on the current efficiency, physical appearance, purity, crystallographic orientation and surface morphology of the deposit and on nickel deposition polarization behaviour during nickel electrowinning were determined. The current efficiency did not change significantly in the presence of these impurities over the concentration range studied, but certain changes in the purity and physical appearance of the deposit were observed. Based on the physical appearance of the electrodeposited nickel, the tolerance limits of the impurities in the electrolyte are reported. The tolerance limit of Co²⁺ was a maximum at 500 p.p.m. and a minimum at 5 p.p.m. in the case of Fe²⁺. No deviation of nickel structure from fcc was observed in the presence of any of these impurities but the peak height values for different orientations showed variations with all the impurities and the values also changed with increase in the impurity concentrations. The surface morphology of electrodeposited nickel also changed in the presence of the impurities. The potentiodynamic scan curves for electrodeposition of nickel showed deviations in the presence of all the impurities except Cu²⁺. Based on the results, an attempt is made to correlate the effects of the various factors investigated.     

Tunable luminescence and energy transfer properties of MgY4Si3O13: Ce3+, Tb3+, Eu3+ phosphors

The tricolor-emitting MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺ phosphors for ultraviolet-LED have been prepared via a high-temperature solid-state method. X-ray diffraction, photoluminescence emission, excitation spectra and fluorescence lifetime were utilized to characterize the structure and the properties of synthesized samples. Two different lattice sites for Ce³⁺ are occupied from the host structure and the normalized PL and PLE spectra. The emissions of single-doped Ce³⁺/Tb³⁺/Eu³⁺ are located in blue, green and red region, respectively. The energy transfer from Ce³⁺ to Tb³⁺ and from Tb³⁺ to Eu³⁺ has been validated by spectra and decay curves and the energy transfer mode from Tb³⁺ to Eu³⁺ was calculated to be electric dipole-dipole interactions. By adjusting the content of Tb³⁺ and Eu³⁺ in MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺, the CIE coordinates can be changed from blue to green and eventually generate white light under UV excitation. All the results indicate that the MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺ phosphors are potential candidates in the application of UV-WLEDs.     

H_2O_2和Fe~(3+)处理含甲醛有机废水的研究

本研究以含甲醛有机废水为对象,采用双氧水和三价铁对其进行处理,以达到技术上可行、经济上合理的目的。主要研究了H_2O_2、Fe~(3+)处理含甲醛有机废水的反应机理和影响因素。试验结果表明各影响因素的适宜条件为:在原水甲醛浓度约为1800 mg/L时,处理100 mL的废水水样,反应温度50℃,反应时间30 min,pH=3,H_2O_2投加量为1.20 mL,Fe_2(SO_4)_3的投加量为0.2 g。此时甲醛的去除率达到96%。     

H2O2与O2协同引发的TiO2/Fe3+光催化降解苯酚

以玻璃纤维为载体,将TiO2/Fe3+负载到其表面制成了空间玻璃纤维反应器。利用该反应器以高压汞灯为光源进行了光催化降解水中苯酚的试验研究,重点考察了H2O2及O2的协同作用对光催化氧化的影响。试验发现,H2O2的加入对HO.的产生有显著的引发作用,同时向溶液中充入O2可明显提高光催化效率,降低H2O2用量。试验结果表明,以UV365-250 W光源照射,在初始pH为3~5,O2通入量为1.0 L/(min.L),上升流速为0.7 m/min,H2O2浓度为0.1 mmol/L等试验条件下,初始质量浓度为30 mg/L的苯酚废水经120 min光催化反应后,其矿化率可达83%左右。     

纯Ti2O3中Ti3+含量的测定

使用容量法和重量法,测定了ＴｉＯ２还原产物中的Ｔｉ２Ｏ３含量。随着Ｔｉ２Ｏ３含量的增高,方法的准确性也提高。两种方法都具有很好的精密度。     

Fe3O4/丙烯酸系磁性微球的制备及对Hg2+、Cu2+、Ni2+的吸附

以二乙烯苯为交联剂,采用悬浮聚合法制备了Fe3O4/丙烯酸系磁性吸附剂。聚合条件为:n(丙烯酸甲酯)∶n(二乙烯苯)=17∶1、w(引发剂)=1%、反应温度75~80℃、反应时间6 h。采用X射线衍射(XRD)、红外(IR)、热重分析(TGA)等对其进行了表征,并考察了它对金属离子的吸附性能。结果表明,制备的磁性吸附剂粒径35~55μm,w(Fe3O4)≈18%。吸附容量随pH升高而增加。饱和吸附容量qm(mmol/g)为:Hg2+2.3,Cu2+2.2,N i2+1.1。采用Lagergrent方程计算的吸附速率常数kad(m in-1)分别为:Hg2+0.023,Cu2+0.034,N i2+0.036。吸附剂可用c(H2SO4)=1 mol/L或c(HNO3)=0.5 mol/L再生。     

ESR study of reactions of cellulose with ·OH generated by Fe+2/H2O2

It was demonstrated by ESR spectroscopy that the Fe⁺²/H₂O₂ system gave a reactive species which generated an ESR triplet spectrum or sorbitol similar to that generated by hydroxyl radicals from the Ti⁺³/H₃O₂ system. An ESR spectrum was obtained for the hydroxyl radicals generated by the latter system. However, the lifetime of hydroxyl radicals, generated by the Fe⁺²/H₂O₂ system, was apparently very short, and an ESR spectrum for the hydroxyl radicals, generated by this system, was not observed. The Fe⁺²/H₂O₂ system also generated triplet spectra with cotton cellulose I, cotton cellulose II, and microcrystalline cellulose, suggesting that a hydrogen atom had been abstracted from the hydroxyl group on carbon C₆, or possibly the hydrogen atom on carbon C₅. The ESR spectrum generated on microcrystalline cellulose was less intense than those generated on cellulose I and II. On initiation of graft polymerization of the activated cellulose with acrylonitrile, the triplet spectrum disappeared and was replaced by two strong singlet spectra. One of the singlet spectra was likely generated on carbon C₁ or C₄ on depolymerization of the cellulose molecule, and the other was probably generated on the end of the growing polyacrylonitrile molecular chain. The absence of a triplet spectrum gave direct evidence for the order in which the acrylonitrile monomer was being grafted onto the cellulose molecule. The mechanisms proposed by Haber and Weiss for the reactions generated in the Fe⁺²/H₂O₂ system were generally supported.     

Optimization of Ce3+ concentration and Y4MgSi3O13 phase in Mg2+-Si4+ Co-doped Ce: YAG ceramic phosphors

As a promising replacement for nitride red phosphors, Ce: Y₃(Mg_1.8Al_1.4Si_1.8)O₁₂ (Ce: YMASG) ceramic phosphors have attracted significant attention recently for their advantages in inorganic encapsulation and massive red-shifting of Ce³⁺ emission. In this work, Ce: YMASG with different doping concentrations of Ce³⁺ and Al₂O₃, was fabricated by vacuum sintering to investigate its effects on the elimination of the impurity phase and the enhancement of the luminescent properties of white light-emitting diodes (w-LEDs). It was discovered that the emission wavelength redshifts from 592 to 606 nm as the Ce³⁺ concentration increases, while at 450 K, the emission intensity deteriorates from 0.47 to 0.36 of its initial value. The Rietveld analysis revealed the presence of an impurity phase of Y₄MgSi₃O₁₃ with a concentration of 17.021 wt% in Ce: YMASG. With the introduction of Al₂O₃, the impurity phase was eliminated from the matrix completely, the emission peak shifted to a shorter wavelength, and the thermal stability was greatly improved. When the correlated color temperature was controlled at around 3000 K in the packaged w-LEDs, the commission international de l'éclairage (CIE) chromaticity coordinates shifted toward the bottom left corner of the diagram with increasing concentration of Ce³⁺. Conversely, the luminous efficiency (LE) increased from 36 lm/W to 58.6 lm/W as the concentration of Al₂O₃ increased from 0 to 10 wt%, which demonstrated the application prospect of the fabricated phosphor in warm w-LEDs.     

Luminescence properties and energy transfer investigations of Sr2B2O5:Ce3+,Tb3+ phosphors

Ce³⁺ and Tb³⁺ co-doped Sr₂B₂O₅ phosphors were synthesized by the solid-state method. X-ray diffraction (XRD) was used to characterize the phase structure. The luminescent properties of Ce³⁺ and Tb³⁺ co-doped Sr₂B₂O₅ phosphors were investigated by using the photoluminescence emission, excitation spectra and reflectance spectra, respectively. The excitation spectra indicate that this phosphor can be effectively excited by near ultraviolet (n-UV) light of 317 nm. Under the excitation of 317 nm, Sr₂B₂O₅:Ce³⁺,Tb³⁺ phosphors exhibited blue emission corresponding to the f–d transition of Ce³⁺ ions and green emission bands corresponding to the f–f transition of Tb³⁺ ions, respectively. The Reflectance spectra of the Sr₂B₂O₅:Ce³⁺,Tb³⁺ phosphors are noted that combine with Ce³⁺ and Tb³⁺ ion absorptions. Effective energy transfer occurred from Ce³⁺ to Tb³⁺ in Sr₂B₂O₅ host due to the observed spectra overlap between the emission spectrum of Ce³⁺ ion and the excitation spectrum of Tb³⁺ ion. The energy transfer efficiency from Ce³⁺ ion to Tb³⁺ ion was also calculated to be 90%. The phosphor Sr₂B₂O₅:Ce³⁺,Tb³⁺ could be considered as one of double emission phosphor for n-UV excited white light emitting diodes.     

SrAl2O4:Eu2+,Dy3+,Pr3+纳米长余辉发光材料的制备与表征

以硝酸盐和尿素为基质,采用燃烧法在650℃合成了SrAl2O4:Eu2+,Dy3+,Pr3+长余辉发光粉体.研究了样品的晶体结构、晶粒大小及发光性能.结果表明:Eu2+,Dy3+,Pr3+共掺杂的磷光体没有改变铝酸锶的晶体结构,平均晶粒尺寸为41.5nm;激发和发射光谱分别为360nm和515nm的宽带谱,与SrAl2...     

Fe2O3/H2O2类芬顿法处理阴离子表面活性剂废水的试验

该文采用Fe2O3/H2O2类芬顿试剂处理阴离子表面活性剂——十二烷基苯磺酸钠(SDBS),研究了H2O2浓度、Fe2O3投加量、pH值及反应温度对处理效果的影响,结果表明SDBS的降解率随温度的升高而升高;当H2O2/Fe2O3=1.568(物质的量比)时体系具有较高的降解率;pH对体系降解率影响不大,在2-10的范围内降解率均较高;Fe2O3/H2O2非均相体系类F.nt.n试剂和Fe2+/H2O2均相体系Fenton试剂的降解效果相差不大,但前者具有pH范围宽,易分离,不产生二次污染的特点.     

Electron-Capture Cross Sections of Ground-State O2+ Recoil Ions in Slow Collisions with H2 and O2

We report the measured total charge-transfer (electron-capture) cross sections for the ground state O2+ (X2Πg) ions with H₂ and O₂ molecular gases in the collision energy range between 0.50 and 2 keV. The time-of-flight technique has been used to measure the fast neutral products from O2+ charge transfer reactions. The analyzed process has cross sections that continue to increase slowly, as a function of incident energy. Measured cross sections for O2++H2, O₂ systems are compared with previously available experimental and theoretical results in the literature.     

Fe3O4协同H2O2气相高级氧化单质汞的机理

利用密度泛函理论分别研究了H₂O₂分子在Fe₃O₄（111）、（110）和（001）表面分解特性,并对单质汞在H₂O₂/Fe₃O₄体系的反应特性进行了研究。对比不同构型的结合能、Mulliken电荷转移和分态密度分析,详细讨论了H₂O₂分解产生羟基的规律以及Hg⁰的氧化态中间产物成键特性。结果表明：H₂O₂分子在Fe₃O₄（111）、（001） A和（110） A表面更容易分解产生羟基;不同表面产生的羟基对Hg⁰具有不同的氧化活性;Hg⁰在表面羟基的作用下可有效通过电荷转移实现氧化。对比分析了三种表面汞氧化态中间产物的脱附路径,HO-Hg-OH和Hg-OH的表面脱附是主要的反应路径。