反相色谱和离子交换色谱测定三聚氰胺氰尿酸中三聚氰胺与硫脲的对比研究

分别采用反相色谱和离子交换色谱检测三聚氰胺氰尿酸(MCA)中三聚氰胺和硫脲,并对检测方法进行了对比研究。实验分别使用盛瀚SH-CC-4柱,流动相为甲醇∶5mmol·L^-1甲基磺酸(10∶90,V∶V)和AgilentTC-C18柱,流动相为乙腈∶5mmol·L^-1醋酸铵(3∶97,V∶V)为流动相对其进行分离,紫外检测。结果表明,反相色谱法中三聚氰胺在0.5~8.0mg·L^-1范围内线性关系良好,相关系数R2为0.9995,检测限和定量限分别为2.2×10^-3 mg·L^-1和7.5×10^-3 mg·L^-1,方法精密度(重复性)RSD=1.41%(n=7),样品回收率91.3%。硫脲在0.05-0.8mg·L^-1范围内线性关系良好,相关系数R2为0.9993,检测限和定量限分别为2×10^-4 mg·L^-1和7×10^-4 mg·L^-1,方法精密度(重复性)RSD=0.68%(n=7),离子交换色谱法峰形对称,三聚氰胺在0.5~8.0mg·L^-1范围内线性关系良好,相关系数R2为0.999,检测限和定量限分别为1.7×10^-3 mg·L^-1、6.1×10^-3mg·L^-1,分析方法(重现性)RSD=1.12%(n=11),样品回收率95.8%,硫脲在0.5~8.0mg·L^-1范围内线性关系良好,相关系数R2为0.999,检测限和定量限分别为1.6×10^-3 mg·L^-1和5.1×10^-3 mg·L^-1,方法精密度(重复性)RSD=1.5%(n=5)对测定结果的F检验(方法精密度)表明两者无显著性差异,但t检验(方法系统误差)表明两者有显著差异。两种方法均能较好地对样品中的三聚氰胺和硫脲进行定性和定量分析,但两者存在系统误差,原因需进一步探索。

Solvent-free aerobic oxidation of ethylbenzene over supported Ni catalysts using molecular oxygen at atmospheric pressure

We investigated the aerobic oxidation of ethylbenzene in the absence of solvent or any additive carried out over Ni on different types of supports namely SiO2, hydroxyapatite, SBA-15, and USY Zeolites. The oxidation of ethylbenzene activities was measured in a round bottom flask immersed in oil bath at known reaction temperature. The physicochemical characteristics of the catalysts were examined by BET surface area, XRD, FT-IR and the oxidation activities were correlated with the acidities of the catalysts obtained by TPD of NH3. It was observed that both hydroxyapatite and USY （13% Na2O） supported Ni catalysts displayed higher ethylbenzene conversion and 80% selectivity towards acetophenone.

非负载和氧化铝负载的纳米CeO_2-ZrO_2和CeO_2-Te_2O_3固溶体催化CO氧化(英文)

Ceria-zirconia(CZ)and ceria-terbia(CT)and alumina-supported ceria-zirconia(CZA)and ceria-terbia(CTA)solid solutions were synthesized by coprecipitation and deposition precipitation methods,respectively.Structural characteristics and catalytic activity of the synthesized samples have been investigated using X-ray diffraction(XRD),high resolution transmission electron microscopy(HRTEM),X-ray photoelectron spectroscopy(XPS),Raman spectroscopy(RS),and Brunauer-Emmett-Teller(BET)surface area measurements.To evaluate the catalytic properties,total oxygen storage capacity and CO oxidation activity measurements were carried out.The XRD analyses revealed the formation of Ce0.75Zr0.25O2 phase for CZ and Ce0.5Zr0.5O2 and Ce0.6Zr0.4O2 phases for CZA samples,respectively.While the formation of only Ce0.8Tb0.2O2-δphase was noted for both CT and CTA samples.All the supported and unsupported samples adopted a fluorite-type structure and exhibited cell parameters with respect to Vegard's rule.The HRTEM results indicated well-dispersed particles of the size around 5 nm.The RS measurements suggested the presence of oxygen vacancies due to defective structure formation.The XPS studies revealed the presence of cerium in both Ce 4+ and Ce 3+ oxidation states in different proportions.It was found that CO oxidation for CTA occurs at very much lower temperature than CT,CZ,and CZA samples.Details of these findings by correlating with the structural characterization studies are consolidated.

Characteristics of La-modified Ni-Al_2O_3 and Ni-SiO_2 catalysts for CO_x-free hydrogen production by catalytic decomposition of methane

Hydrotalcite precursors of La modified Ni-Al2O3 and Ni-SiO2 catalysts prepared by co-precipitation method and the catalytic activities were examined for the production of COx-free H2 by CH4 decomposition. Physico-chemical characteristics of fresh, reduced and used catalysts were evaluated by XRD, TPR and O2 pulse chemisorptions, TEM and BET-SA techniques. XRD studies showed phases due to hydrotalcite-like precursors in oven dried form produced dispersed NiO species upon calcination in static air above 450 C. Raman spectra of deactivated samples revealed the presence of both ordered and disordered forms of carbon. Ni-La-Al2O3catalyst with a mole ratio of Ni : La : Al = 2 : 0.1 : 0.9 exhibited tremendously high longevity with a hydrogen production rate of 1300 molH2 mol 1 Ni. A direct relationship between Ni metal surface area and hydrogen yields was established.

Vertically aligned one-dimensional ZnO/V2O5 core-shell hetero-nanostructure for photoelectrochemical water splitting

The vertically aligned one-dimensional(1 D)core-shell structure can maximize the exposure and use of the functionally active surface while maintaining the geometric effects caused by the underlying structure.Herein,we have fabricated 1 D vertically aligned ZnO/V2O5 core-shell hetero-nanostructure nanorod arrays(NRs)for photoelectrochemical(PEC)water splitting.ZnO/V2O5 NRs were prepared through the hydrothermal growing of ZnO NRs and then radio frequency(RF)magnetron sputtering deposition of V2O5 for 300,600 and 900 s.The photocurrent density of ZnO/V2O5-based photoanodes was gradually increased with the sputtering time,reaching the maximum value of 1.21 m A/cm^2 at 1.23 V vs.reversible hydrogen electrode(RHE)for ZnO/V2O5-600,whereas for pure ZnO-based photoanode was 0.42 mA/cm^2.The incident photon to electron conversion efficiency(IPCE)of ZnO/V2O5-600 evaluated to be 82.3%which was 2.3 times higher than that of ZnO(36.4%).The improved PEC performance of ZnO/V2O5-600 is because the core-shell structure with a moderate thickness of the V2O5 layer has the extremely high carrier density,largest electrochemically active surface area(ECSA),largest carrier density,lowest charge recombination rate,and the longest lifetime of e-h pairs due to the formation of the staggered gap junction.This study provides an effective way to design and fabrication of hetero-nanostructures for highefficiency photoelectrodes.

Catalytic decomposition of CH_4 over Ni-Al_2O_3-SiO_2 catalysts:Influence of pretreatment conditions for the production of H_2

This article reports the production of COx free hydrogen and carbon nanofibers by the catalytic decomposition of methane over Ni-Al2O3-SiO2 catalysts. The influence of reaction temperature, pretreatment temperature, and effect of reductive pretreatment on the decomposition of methane activity is investigated. The physico-chemical characteristics of fresh and deactivated samples were characterized using BET-SA, XRD, TPR, SEM/TEM, CHNS analyses and correlated with the methane decomposition results obtained. The Ni-Al-Si （4 ： 0.5 ： 1.5） catalyst reduced with hydrazine hydrate produced better H2 yields of ca. 1815 mol H2/mol Ni than the catalyst reduced with 5% H2/N2.

Enhanced hydrogen production activity over BiOX–TiO2 under solar irradiation:Improved charge transfer through bismuth oxide clusters

A series of titania nanoparticles and nanotubes deposited with various quantities of bismuth（Bi） were prepared via sol-gel and hydrothermal methods, respectively. They were then characterized using X-ray diffraction spectroscopy（XRD）, X-ray photo electron spectroscopy（XPS）, UV–Vis diffused reflectance spectra（DRS）, photoluminescence spectra（PLS）, transmission electron microscopy（TEM）, energy dispersive analysis of X-rays（EDAX）, and BET surface analysis. These catalysts were employed for the photocatalytic production of hydrogen from a mixture of pure water and glycerol under solar light irradiation. The presence of the Bispecies was found to play a vital role in enhancing activity while minimizing electron hole recombination（relative to bare TiO）. The nanotubes exhibited better activity than the nanoparticles of Bi-deposited TiO, showing the significance of the morphology; however, photocatalytic activity is predominantly dependent on the deposition of bismuth. The activity increased by approximately an order of magnitude at the optimum concentration of Bi deposited over TiO（2 wt%）. The presence of the Bispecies played a vital role in minimizing electron hole recombination, resulting in higher activity compared to bare TiO.

Surface Analysis of Carbon Steel Protected from Corrosion by a New Ternary Inhibitor Formulation Containing Phosphonated Glycine, Zn²⁺and Citrate

Studies on surface analysis of carbon steel protected from corrosion in low chloride and nearly neutral aqueous environment by a synergistic mixture containing N,N-bis(phosphonomethyl) glycine (BPMG), zinc ions and citrate ions are presented. The effect of addition of citrate to the binary system, BPMG-Zn2+, is quite significant and is well explored through various studies. The surface protective nature is maintained in the pH range 5 - 9. Potentiodynamic polarization studies inferred that the ternary inhibitor is a mixed inhibitor. Impedance studies of the metal/solution interface indicated that the surface film is highly protective against the corrosion of carbon steel in the chosen environment. X-ray photoelectron spectroscopic (XPS) analysis of the surface film showed the presence of the elements namely iron, phosphorus, nitrogen, carbon, oxygen and zinc. Deconvolution spectra of these elements in the surface film inferred the presence of oxides/hydroxides of iron(III), Zn(OH)2 and [Fe(III), Zn(II)-BPMG-citrate] heteropolynuclear multiligand complex. This inference is further supported by the reflection absorption Fourier transform infrared spectrum of the surface film. Analysis by scanning electron microscopy (SEM) is presented for both the corroded and protected metal surfaces. Based on all these results, a plausible mechanism of corrosion inhibition is proposed.

A Green Approach towards the Synthesis of Enantio Pure Diols Using Horse Radish Peroxidase Enzyme Immobilized on Magnetic Nanoparticles

Enantiopure epoxides and their corresponding chiral vicinal diols serve as valuable intermediates in the synthesis of biologically active pharma and agro-compounds and also value added fine chemicals. Biocatalysts are well known for their selective hydrolysis of racemic epoxides to give optically pure chiral diols. This study highlights an efficient process of synthesis of chiral vicinal diols in good yields and enantioselectiviy using horse radish peroxidase enzyme immobilized on the amine functionalized magnetic nano particles (Fe3O4 nanoparticles) as enzyme carriers. It also facilitates separation of MNP-immobilized enzymes by applying external magnetic field. The immobilization of magnetic nano particles was confirmed by transmission electron microscope (TEM) and scanning electron microscope (SEM). The MNP-immobilized peroxidase enzyme improved stability of the enzyme and has shown broader substrate specificity in enantioselective hydrolysis of racemic epoxides, under mild and environmentally friendly conditions. The methodology MNP-immobilized enzyme developed in the synthesis of chiral diols has a potential for use in large-scale applications.

Simplified Step-by-Step Nonlinear Static Program Investigating Equilibrium Conditions of Electrons in Atom and Ionization Energies: Case Study on Argon

For investigation of equilibrium conditions of electrons in an atom, and Ionization Energies of Elements, a simplified deterministic static model is proposed. The electrons are initially uniformly and sparsely arranged on the outer surface of nucleus. Then, by taking into account the nucleus-electron interaction (attractive and repulsive) and the mutual electron-electron repulsions, and by a simple step-by-step nonlinear static analysis program, all the electrons are found to equilibrate on the outer surface of the same sphere, which is concentric and larger than nucleus. In a second stage, starting from an equilibrium sphere of electrons, one of the electrons is subjected to gradual forced removal, radially and outwards with respect to nucleus. Within each removal step, the produced work increment is determined and the increments are summed. When no more significant attraction is exerted by nucleus to removed electron, the total work gives the Ionization Energy. After removing of single electron, the remaining electrons fall on a lower shell, that is, they equilibrate on the outer surface of a smaller concentric sphere. For nucleus-electron interaction, an L-J (Lennard-Jones) type curve, attractive and repulsive, is adopted. When the parameter of this curve is n > 1.0, the Ionization Energy exhibits an upper bound. As parameter n increases from 1.0 up to 2.0, the attractive potential of L-J curve is gradually weakened. The proposed model is applied on Argon. It is observed that, as the number of electrons increases, the radius of equilibrium sphere increases, too, whereas the attractive nucleus-electron potential is reduced;thus the Ionization Energy is reduced, too. Particularly, as the number of electrons and the radius of equilibrium sphere exceed some critical values, the above two last quantities exhibit abrupt falls. A regular polyhedron is revealed, which can accommodate Elements up to atomic number Z = 146, that is 28 more than Z = 118 of existing last Element, as guide for initial locations of electrons in the above first program.

Study of Ionic Conduction and Dielectric Behavior of Pure and K⁺Doped Ag₂CdI₄

The ionic conductivity of 8, 9 and 10 mol% K+ doped Ag2CdI4 showed slight decrease whereas the phase transition was observed almost at the same temperature as it reported for pure Ag2CdI4. This decrease in conductivity likely results from decrease in free volume because of the larger K+ ions (rK+ = 133 pm and rAg+ = 129 pm) entering Ag2CdI4 lattice which is unchanging in size. The dielectric constant of Ag2CdI4 was found to increase with increasing temperature as the orientation of dipoles is facilitated in rising temperature.

Synthesis and Characterisation of In2O3 Na-noparticles from Astragalus gummifer

Exploitation of green chemistry approach for the synthesis of Indium Oxide nanoparticles using green synthesis has received a great attention in the field of nanotechnology. To demonstrate a biogenic method that involves the Katira gum (Astragalus gummifer) leading to the formation of different morphological In2O3 using the precursor Indium (III) Acetylacetonate and TG-DTA is characterised for calcination temperature and it is found to be above 500℃. Different techniques such as XRD, UV-VIS, SEM and EDAX have been used for the characterisation of In2O3 nanoparticles. The average crystallite size of Indiumoxide nanoparticles is determined as 19 nm by using Scherrer’s Equation and PSA and studying optical properties.

过氧化氢氧化与阀切换离子色谱法检测食盐中的亚硝酸盐

目的:利用过氧化氢氧化与阀切换离子色谱法测定食盐中亚硝酸盐含量。方法:利用氧化剂(过氧化氢)将食盐样品溶液中的NO_(2)^(-)氧化为NO_(3)^(-),再通过阀切换,洗脱大部分Cl^(-)和Br^(-),收集氧化生成的NO_(3)^(-)于定量环中,定量环中的NO_(3)^(-)经氢氧化钾淋洗液进入AS11-HC保护柱(50 mm×4 mm)和分析柱(250 mm×4 mm)进行分离,再进行电导检测,通过检测NO_(3)^(-)的含量间接得到NO_(2)^(-)的含量。结果:在0.01~1.00 mg·L^(-1)的线性范围内,r=0.9999,RSD(n=7)为2.3%,检测限为8.57×10^(-4)mg·L^(-1),回收率为85.2%~111.0%。22个样品中5个样品未检出NO_(2)^(-),其他样品介于6.94~88.70μg·g^(-1)。结论:该实验方法准确、灵敏,可应用于食盐中亚硝酸盐的检测。

阀切换循环离子色谱法测定高盐基体中的亚硝酸盐

建立了一种循环阀切换离子色谱技术检测高盐基体中的亚硝酸盐的方法。通过设置合适的阀切换时间,除去高盐基体中大部分高浓度Cl-,NO2-收集于六通阀中的定量环,经KOH淋洗液进入Dionex Ion Pac AS11-HC (4 mm×50 mm)保护柱和AS11-HC (4 mm×250 mm)分析柱分离后进行电导法检测。实验结果表明,在0. 01~1. 00 mg/L的线性范围内,相关系数r2=0. 9994,相对标准偏差为7. 0%,检出限为2. 67μg/L,所得样品的加标回收率为87. 8%~116. 9%。该方法可用于高盐基体中NO2-的检测。

Bismuth Modified Porous Silica Preparation,Characterization and Photocatalytic Activity Evaluation for Degradation of Isoproturon

Porous silica prepared by using an acrylic emulsion has been impregnated with bismuth ion resulting in Bi2Si05 species containing surface. The as-prepared materials have been characterized by X-ray diffraction spectroscopy （XRD）, X-ray photoelectron spectroscopy （XPS）, UV-Vis diffuse reflectance spectroscopy （UV-Vis DRS）, scanning electron microscopy （SEM）, energy dispersive analysis of X-ray （EDAX）, transmission electron microscopy （TEM）, Fourier transform infrared spectroscopy （FTIR） and N2 adsorption/desorption techniques. EDAX analysis confirms the penetration of bismuth ions into the framework of silica to form Bi2SiO5, which is substantiated by XRD. The UV-Vis DRS shows that the catalysts are optically active and XPS confirms the inclusion of bismuth into the framework of silica. FTIR spectra illustrate the formation of Bi-O-Si linkages in the porous silica framework. SEM and TEM show the spherical morphology, whereas N2 adsorption/desorption study confirms the porosity of the prepared materials. The photocatalytic activity of the material is evaluated for the degradation of isoproturon herbicide and it is found that the material is active as compared to the commercial P-25 Degussa TiO2.

Rare earth metal doped CeO_2-based catalytic materials for diesel soot oxidation at lower temperatures

In this work, the influence of trivalent rare-earth dopants（Sm and La） on the structure-activity properties of CeO2 was thoroughly studied for diesel soot oxidation. For this, an optimized 40% of Sm and La was incorporated into the CeO2 using a facile coprecipitation method from ultra-high dilute aqueous solutions. A systematic physicochemical characterization was carried out using X-ray diffraction（XRD）, transmission electron microscopy（TEM）, Brumauer-Emmett-teller method（BET） surface area, X-ray photoelectron spectroscopy（XPS）, Raman, and H2-temperature programmed reduction（TPR） techniques. The soot oxidation efficiency of the catalysts was investigated using a thermogravimetric method. The XRD results suggested the formation of nanocrystalline single phase CeO2-Sm2O3 and CeO2-La2O3 solid solutions. The Sm- and La-doped CeO2 materials exhibited smaller crystallite size and higher BET surface area compared with the pure CeO2. Owing to the difference in the oxidation states of the dopants（Sm3＋ and La3＋） and the Ce4＋, a number of oxygen vacancies were generated in CeO2-Sm2O3 and CeO2-La2O3 samples. The H2-TPR studies evidenced the improved reducible nature of the CeO2-Sm2O3 and CeO2-La2O3 samples compared with the CeO2. It was found that the addition of Sm and La to the CeO2 outstandingly enhanced its catalytic efficiency for the oxidation of diesel soot. The observed 50% soot conversion temperatures for the CeO2-Sm2O3, CeO2-La2O3 and CeO2 were ~790, 843 and 864 K（loose contact）, respectively, and similar activity order was also found under the tight contact condition. The high soot oxidation efficacy of the CeO2-Sm2O3 sample was attributed to numerous catalytically favourable properties, like smaller crystallite size, larger surface area, abundant oxygen vacancies, and superior reducible nature.

High viscosity of ionic liquids causes rate retardation of Diels-Alder reactions

Second order rate constants, ka have been determined for three bi-molecular Diels-Alder reactions to demonstrate that the high viscosity of ionic liquids can be a detrimental property in carrying out Diels-Alder reactions, if ionic liquids are employed as solvent media. It is possible to enhance the reaction rates of the reaction if a co-solvent is mixed in pure ionic liquid used as a solvent.

Lactobionic Acid as a New Synergist in Combination with Phosphonate-Zn(Ⅱ)System for Corrosion Inhibition of Carbon Steel

Studies on lactobionic acid introduced as a synergist in the presence of phosphonobutane-1,2,4-tricarboxylic acid （PBTC） and zinc ions for corrosion control of carbon steel in aqueous environment are presented. The investigations revealed that lactobionic acid （LBA） acts as an excellent synergist in corrosion inhibition. Optimum concentrations of all the three components of the ternary formulation are established by gravimetric studies. Potentiodynamic polarization studies indicate that the new ternary system is a mixed inhibitor. Impedance studies show that a protective film is formed on the metal surface in the presence of the inhibitor formulation. The film is found to exhibit its protective nature even at higher temperatures up to 60 ~C. Analysis of the protective film by X-ray photoelectron spectroscopy （XPS） and reflection absorption Fourier transform infrared （FTIR） spectroscopy infers the presence of Zn（OH）2, oxides and hydroxides of iron and the inhibitor molecules in the surface film probably in the form of a complex, [Zn（II）-PBTC-LBA]. The morphological studies by scanning electron microscopy （SEM） and the topographical studies by atomic force microscopy （AFM） also indicate the presence of protective film on the metal surface. A plausible mechanism of corrosion inhibition is proposed.