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1.
Highly ordered 2D-hexagonal mesoporous silica has been functionalized with 3-aminopropyltriethoxysilane (3-APTES). This is followed by its condensation with a dialdehyde, 4-methyl-2,6-diformylphenol to produce an immobilized Schiff-base ligand (I). This material is separately treated with methanolic solution of copper(II) chloride and nickel(II) chloride to obtain copper and nickel anchored mesoporous materials, designated as Cu-AMM and Ni-AMM, respectively. The materials have been characterized by Fourier transform infrared (FT-IR) and UV-vis diffuse reflectance (DRS) spectroscopy, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), N(2) adsorption-desorption studies and (13)C CP MAS NMR spectroscopy. The metal-grafted mesoporous materials have been used as catalysts for the efficient and selective epoxidation of alkenes, viz. cyclohexene, trans-stilbene, styrene, α-methyl styrene, cyclooctene and norbornene to their corresponding epoxides in the presence of tert-butyl hydroperoxide (TBHP) as the oxidant under mild liquid phase conditions.  相似文献   

2.
3.
Copper and manganese oxides supported on activated carbon have been studied in the reaction of methanol decomposition to H2 and CO. XRD, EPR, TPR with CO and magnetic measurements have been used for their characterization. The nature of the catalytically active complex is also discussed. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

4.
A new functionalized nanoporous silica gel with dipyridyl group (DPNSG) was synthesized. Then, the potentiometric response of the copper(II) ion was investigated at a carbon paste electrode chemically modified with this newly designed functionalized nanoporous silica gel. The electrodes with DPNSG proportions of 15.0% (w/w) demonstrated very stable potentials. Calibration plots with Nernstian slopes for Cu2+ were observed, 28.4 (±1.0) mV decade−1, over a wide linear concentration range (1.0 × 10−7 to 1.0 × 10−2 M). The electrode exhibited a detection limit of 8.0 × 10−8 M. Moreover, the selectivity coefficients measured by the match potential method in acetate buffer, pH 5.5, were investigated. The electrode presented a response time of ∼50 s, high performance, high sensitivity in a wide range of cation activities and good long-term stability (more than 9 months). The method was satisfactory and was used to determine the copper ion concentration in waste waters, contaminated by this metal.  相似文献   

5.
利用量子化学方法对第一激发态HOOO的裂解反应进行了理论研究.所有驻点(反应物、产物和过渡态)的几何结构优化和振动分析都是在CASSCF/6-31 G(d,p)理论水平下进行的.反应路径上的选择点及驻点都在CASPT2/6-31 G(d,p)//CASSCF(19,13)/6-31 G(d,p)和MRCI/6-31 G(d,p)//CASSCF(19,13)/6-31 G(d,p)理论水平下进行单点能量校正.CASSCF,CASPT2和MRCI水平的理论计算结果显示,第一激发态HOOO的裂解反应包含一个对称性变化的过程.它首先通过了一个Cs对称性的过渡态,然后逐渐变化为线性结构,最终生成产物O2(3Σg-)和OH(2Π).  相似文献   

6.
The HOOO radical plays a crucial role in atmospheric processes involving the OH radical and O(2) molecule. We present an ab initio molecular orbital theory study on the decomposition reaction of the first excited state HOOO((2)A') with respect to OH and O(2). The geometries and harmonic vibrational frequencies of all stationary points are calculated at the CASSCF and MRCI levels of theory in conjunction with the 6-31+G(d,p) basis set. The potential energy profile of the decomposition reaction is studied at the CASSCF/6-31+G(d,p) level of theory, in which the complete valence orbitals and electrons are included in the active space. The energies of the potential energy profile are further refined at the CASPT2 and MRCI levels of the theory. Additionally, we have determined the interesting reaction process: the HOOO((2)A') radical with C(s) symmetry does not dissociate to OH((2)Pi) and O(2)((3)Sigma(-)(g)) directly as this is forbidden by orbital symmetry, but dissociates to OH((2)Pi) and O(2)((3)Sigma(-)(g)) via the change in symmetry from C(s) to C(infinity v) symmetry with a low barrier.  相似文献   

7.
Following our work on the study of helium droplets and film doped with one electronically excited rubidium atom Rb(?) ((2)P) [M. Leino, A. Viel, and R. E. Zillich, J. Chem. Phys. 129, 184308 (2008)], we focus in this paper on the second excited state. We present theoretical studies of such droplets and films using quantum Monte Carlo approaches. Diffusion and path integral Monte Carlo algorithms combined with a diatomics-in-molecule scheme to model the nonpair additive potential energy surface are used to investigate the energetics and the structure of Rb(?)He(n) clusters. Helium films as a model for the limit of large clusters are also considered. As in our work on the first electronic excited state, our present calculations find stable Rb(?)He(n) clusters. The structures obtained are however different with a He-Rb(?)-He exciplex core to which more helium atoms are weakly attached, preferentially on one end of the core exciplex. The electronic absorption spectrum is also presented for increasing cluster sizes as well as for the film.  相似文献   

8.
Features of the kinetics of ozone decomposition in water at pH 2 are studied depending on the concentration of silver and copper ions that are present. The existence of a critical concentration of metal ions (??3?6 × 10?6 M) is established, below which ions slow the rate of ozone decomposition and above which the accelerate the process. It is concluded that the first region is due to the capture of hydroxyl and other radicals by metal ions, inhibiting the chain of ozone decomposition in water. A further increase in the concentration of ions leads to dominance of their direct interaction with molecules of ozone. A mechanism for the process is proposed and the rate constants of reaction of ozone with silver ions and copper are calculated (0.033 and 0.06 M?1 s?1, respectively).  相似文献   

9.
Planar binuclear copper(II) complexes generally showed high catalytic activities for the decomposition of hydrogen peroxide compared with the relevant planar mononuclear copper(II) complexes. This result was explained on the assumption that the two-electron transfer occurs between H2O2 molecules via an intervening binuclear copper(II) complex.  相似文献   

10.
Hulanicki A  Lewenstam A 《Talanta》1976,23(9):661-665
The diffusion-layer model for the chalcocite (Cu(2)S) membrane electrode is discussed. It is equivalent to a simpler model based on exchange reactions at the electrode surface. The chalcocite is sensitive to copper(I) and copper(II) ions and the theoretically predicted response is in good agreement with experimental data. The membrane is a conductor, but this does not significantly affect its function as an ion detector. The limitation of the electrode is the membrane solubility as shown when Cu(II) ions in contrast to copper(I) ions are strongly complexed.  相似文献   

11.
Magnesium formate dihydrate has been synthesized by the action of formic acid on anhydrous magnesium oxide. This product analysed as Mg(COOH)2 · 2H2O. Its mode of thermal decomposition has been studied by thermal methods of analysis including simultaneous DTA/mass spectrometry. Nitrogen adsorption surface area of the solid products at various stages of its decomposition have been obtained. X-Ray diffraction and scanning electron micrographs have also been used to interpret the results. The decomposition of magnesium formate took place in three stages, which includes a phase change, at 265°C. The endotherm at 430°C changed to an exotherm in the presence of air; it corresponded to the decomposition of a new anhydrous phase of magnesium formate. The effect of the sample holder and changing atmospheres on the DSC analysis has been investigated. A scheme is presented for the thermal decomposition.  相似文献   

12.
Micron-sized silica gel particles were chemically modified on their surfaces with the coupling agent, γ-methacryloxypropyl trimethoxysilane (MPS), double bond was introduced onto the surfaces of silica gel particles, and the modified particles MPS–SiO2 were obtained. Then, poly(4-vinylpyridine) (P4VP) was grafted from the silica gel surfaces, and grafting particles P4VP/SiO2 was prepared. Finally, the coordination between grafted P4VP and cupric ions Cu2+ was performed, and the supported complex Cu(II)–P4VP/SiO2 was obtained. The grafting particles P4VP/SiO2 and the supported complex Cu(II)–P4VP/SiO2 were characterized with infrared spectra (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). Cu(II)–P4VP/SiO2 was used as a catalyst for the oxidation of ethyl benzene into acetophenone with molecular oxygen under ordinary pressure. The experimental results show that the supported complex Cu(II)–P4VP/SiO2 can be successfully prepared via grafting polymerization of 4VP and coordination between the grafted P4VP and cupric ions Cu2+. In oxidation of ethyl benzene into acetophenone by molecular oxygen under ordinary pressure, the supported complex Cu(II)–P4VP/SiO2 displayed high catalytic activity and excellent catalytic selectivity up to more than 98% for the transformation of ethyl benzene to acetophenone.  相似文献   

13.
以十六烷基三甲基溴化铵为模板剂,通过水解钛酸正丁酯合成了介孔二氧化钛分子筛,探讨了合成条件的影响。采用X射线粉末衍射(XRD)、红外光谱(FT-IR)、透射电子显微镜(TEM)和N2吸附-脱附等技术对介孔二氧化钛的晶相、结构、形貌、比表面积和孔径分布进行了表征。实验结果表明:得到的介孔二氧化钛分子筛的孔径为4-4.3nm,用抽提的方法去除模板剂得到的介孔二氧化钛的比表面积比焙烧的要高。以甲基橙为模型污染物,检验了所合成介孔二氧化钛的光催化性质。  相似文献   

14.
A copper(II) and iron(III) co-modified titanium dioxide nano material was prepared by a simple sol–gel process using titanium(IV) isopropoxide plus copper(II) and iron(III) nitrates as raw materials. The as-prepared nanocomposites were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy and photoluminescence spectra. The XRD results showed that the undoped TiO2 nanoparticles mainly include anatase phase while the Cu, Fe-codoped TiO2 nanoparticles showed a mixture of anatase phase with a small fraction of rutile phase displaying higher activity than the pure anatase phase. Optical characterization showed that the codoping with copper(II) and iron(III) resulted in a red shift of adsorption and lower recombination probability between electrons and holes, which were associated with high photocatalytic activity of the Cu, Fe-codoped TiO2 nanoparticles under visible light (λ > 400 nm). The photocatalytic activity of the samples was tested by aqueous methyl orange degradation. The capability of the codoped catalyst was much higher than that of the pure TiO2 catalyst under visible irradiation. A mechanism is proposed in order to account for the enhanced catalytic activity.  相似文献   

15.
Cr catalysts supported on silica, zeolite NaY, and charcoal were prepared with two different methods. They were characterized and examined in the polymerization of ethene. Cyclic voltammetry, electron spin resonance, X‐ray photoelectron spectroscopy and silicon‐29 magic‐angle spinning nuclear magnetic resonance spectroscopy were used to characterize them, demonstrating that Cr is not in a single oxidation state, that the distribution among the various oxidation states depends on the history of the sample, and that even for a single oxidation state a variety of different environments can occur. In the polymerization of ethene, the supported Cr catalysts exhibited activity values varying from 103 to 105 gPE · molCr?1 · [M]?1 · h?1, depending on the choice of the support and on the method by which the Cr is placed on it. Silica seemed to be the most efficient support for Cr for this reaction. However, the zeolite‐supported catalysts also showed reasonable activity values (Ap ? 104 units) and presented the advantage of having a strong interaction between the Cr and the support, which may prevent leaching of the cation into the surrounding environment. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3768–3780, 2003  相似文献   

16.
An analysis is made of earlier work by the authors in investigating the catalytic activity of Fe(III) and Cu(II) ions in solution and on different surfaces in certain redox reactions: the decomposition of H2O2, oxidation of ascorbic acid, etc. General principles have been established which provide a means of predicting one or another action of sorption on the catalytic activity: if the reaction proceeds within the ion exchanger phase as in a homogeneous (concentrated) solution, it is most probable to have a decrease (or cessation) of the catalytic activities of the ions. If the ion catalysts are included in a surface complex in whose coordination sphere there are places which the substrate may occupy the reaction is facilitated. The analysis carried out of the influence of sorption on the catalytic activity of the iron and copper ions shows a favorable change in the catalytic activity for these ions during their sorption on different types of surfaces.Translated from Teoreticheskie i Éksperimental'naya Khimiya, Vol. 22, No. 6, pp. 706–711, November–December, 1986.  相似文献   

17.
Ag nanoparticles supported on the surface of three-dimensional (3D) flower-like ZnO nanostructure were synthesized by a microwave-assisted solution method. The obtained products were characterized by X-ray diffraction analysis, field-emission scanning electron microscopy, Fourier-transform infrared spectroscopy, Raman spectrophotometry, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy. The analytical results confirmed homogeneously distributed Ag nanoparticles supported on the surface of flower-like ZnO nanostructure. The photocatalytic effect of the heterostructure Ag/ZnO nanocomposites was investigated using photodegradation under ultraviolet (UV) light of methylene blue as model dye. The heterostructure Ag/ZnO nanocomposites exhibited much higher photocatalytic activity than pure ZnO flowers. The improved photocatalytic properties are attributed to formation of a Schottky barrier at the metal–semiconductor interface of the Ag/ZnO nanocomposites.  相似文献   

18.
Batch biosorption experiments were conducted to investigate the removal of Cu2+ ions from aqueous solutions by a series of bacterial strains isolated from a local activated sludge process. The characteristics of 12 isolates were identified and examined for their ability to bind Cu2+ ions from aqueous solution. Among the isolates, two species exhibited biosorption capacity >40 mg of Cu/g of dry cell. Isotherms for the biosorption of copper on bacterial cells were developed and compared, and the equilibrium data fitted well to the Langmuir and Freundlich isotherm models. The biosorption of copper increased significantly with increasing pH from 2.0 to 6.0 regardless of the species. More than 90% of copper sorbed on the cells of Bacillus sp. could be recovered by washing with 0.1 M HNO3 for 5 min. The performance of two different desorption processes was also tested and compared. The results show that five biosorption and desorption cycles are a better operation process than five successive biosorptions followed by one desorption to remove and recover copper from aqueous solution. The biosorbent could be used for at least five biosorptions and desorption cycles without loss of copper removal capacity. It can be concluded that the activated sludge or sludge-isolated bacteria could be a potential biosorbent for copper removal.  相似文献   

19.
以TiO2为主要成分的光催化剂的研究已日益受到人们的广泛关注[1-6]。但TiO2粉末的回收和流失问题难以解决,固定化TiO2负载催化剂的研制是解决这一问题的有效手段[2-6]。从实际应用的观点看,TiO2的光催化剂活性还有待进一步提高。研究发现,大多数过渡金属离子和少数非金属离子的  相似文献   

20.
Electronic absorption and emission spectral characteristics of two ketocyanine dyes have been studied in solution in the presence of alkaline earth metal ions. Absorption spectral studies indicate complex formation between the ions and the dyes in the ground state. Values of the equilibrium constant and the enthalpy change characterizing dye (S0)-metal ion interaction have been determined from the absorption spectral data. In the presence of the metal ions the fluorescence spectrum of the dyes shows two bands pointing to the existence of two emitting species, viz., the solvated and the complexed dye in solution. Time-resolved studies of the dyes in solution containing the metal ions can be explained by a two-state model and indicate the presence of two emitting species in equilibrium. Values of the equilibrium constant for the interaction of metal ion and the dyes in the S1 state have also been estimated.  相似文献   

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