The State of Copper Ions in Aqueous and Aqueous Ammonia Solutions of Copper Acetate

Stabilization of Cu²⁺ ions in aqueous and aqueous ammonia solutions of copper acetate was studied for a wide range of ammonia concentrations. The structure of copper acetate hydrate complexes was shown to markedly change upon dissolution in water. In aqueous solutions, copper is stabilized as strongly bound Cu²⁺ associates (dimers) in a distorted octahedral environment composed of water molecules and acetate groups oxygen atoms in equatorial positions with strong exchange interaction via acetate groups. In solutions of copper acetate in aqueous ammonia, the concentration of ammonia has a crucial effect on the ordering of Cu²⁺ ions in associates. At high ammonia concentration, disordered copper tetra-ammoniate associates with the \({d_{{x^2} - {y^2}}}\) ground state are formed, whereas at low ammonia concentration, bulky Cu²⁺ ion associate structures are generated, with the \({d_{{x^2} - {y^2}}}\) ground state, hydroxyl groups in the equatorial plane, and water molecules in the axial positions.     

Synthesis of Quinazolines and Tetrahydroquinazolines: Copper‐Catalyzed Tandem Reactions of 2‐Bromobenzyl Bromides with Aldehydes and Aqueous Ammonia or Amines

An efficient synthesis of diversely substituted quinazolines and 1,2,3,4‐tetrahydroquinazolines through copper‐catalyzed tandem reactions of the readily available 2‐bromobenzyl bromides, aldehydes, and aqueous ammonia or amines has been developed. By using ammonia and simple aliphatic amines as the nitrogen source, the present method provides a versatile and practical protocol for the synthesis of quinazolines and 1,2,3,4‐tetrahydroquinazolines.     

Zeolite ZSM-5 containing copper ions: The effect of the copper salt anion and NH<Subscript>4</Subscript>OH/Cu<Superscript>2+</Superscript> ratio on the state of the copper ions and on the reactivity of the zeolite in DeNO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Isotherms of copper cation sorption by H-ZSM-5 zeolite from aqueous and aqueous ammonia solutions of copper acetate, chloride, nitrate, and sulfate are considered in terms of Langmuir’s monomolecular adsorption model. Using UV-Vis diffuse reflectance spectroscopy, IR spectroscopy, and temperatureprogrammed reduction with hydrogen and carbon monoxide, it has been demonstrated that the electronic state of the copper ions is determined by the ion exchange and heat treatment conditions. The state of the copper ions has an effect on the redox properties and reactivity of the Cu-ZSM-5 catalysts in the selective catalytic reduction (SCR) of NO with propane and in N₂O decomposition. The amount of Cu²⁺ that is sorbed by zeolite H-ZSM-5 from aqueous solution and is stabilized as isolated Cu²⁺ cations in cationexchange sites of the zeolite depends largely on the copper salt anion. The quantity of Cu(II) cations sorbed from aqueous solutions of copper salts of strong acids is smaller than the quantity of the same cations sorbed from the copper acetate solution. When copper chloride or sulfate is used, the zeolite is modified by the chloride or sulfate anion. Because of the presence of these anions, the redox properties and nitrogen oxides removal (DeNO _x ) efficiency of the Cu-ZSM-5 catalysts prepared using the copper salts of strong acids are worse than the same characteristics of the sample prepared using the copper acetate solution. The addition of ammonia to the aqueous solutions of copper salts diminishes the copper salt anion effect on the amount of Cu(II) sorbed from these solutions and hampers the nonspecific sorption of anions on the zeolite surface. As a consequence, the redox and DeNO _x properties of Cu-ZSM-5 depend considerably on the NH₄OH/Cu²⁺ ratio in the solution used in ion exchange. The aqueous ammonia solutions of the copper salts with NH₄OH/Cu²⁺ = 6–10 stabilize, in the Cu-ZSM-5 structure, Cu²⁺ ions bonded with extraframework oxygen, which are more active in DeNO _x than isolated Cu²⁺ ions (which form at NH4OH/Cu2+ = 30) or nanosized CuO particles (which form at NH₄OH/Cu²⁺ = 3).     

Unprecedented copper(I)-catalyzed in situ double cycloaddition reaction based on 2-cyanopyrimidine

The solvothermal in situ double cycloaddition reaction of 2-cyanopyrimidine, Cu(2)O and NaN(3) with aqueous ammonia additive generated a two dimensional copper(I) coordination polymer with 5-pyrimidyl-tetrazolate, 3,5-bispyrimidyl-1,2,4-triazolate and the cyano group as the ligands. This reaction can be tuned to yield two dimensional coordination polymers solely based on tetrazolate or 1,2,4-triazolate ligands.     

The Physicochemical Properties of the Surface of Copper Nanopowders Prepared by the Electroexplosion and Gas-Phase Methods

The temperature-programmed ammonia desorption, IR spectroscopy, differential thermal analysis, and inorganic test-reagent methods were used to study the properties of copper nanopowders prepared under various conditions of wire electroexplosion and gas-phase synthesis. Electroexplosion in nitrogen was shown to favor the formation of copper nanopowders with acid surface properties. Explosion in argon produced powders with reducing surface properties, which could be detected in aqueous solutions of ammonia and iodine during several minutes.     

Hemilabile‐coordinated copper promoted amination of aryl halides with ammonia in aqueous ethylene glycol under atmosphere pressure

Direct amination of aryl iodides and bromides with ammonia under 1 atm pressure has been effected using in situ‐generated hemilabile coordinated copper(I) species from copper(I) halides or copper metal in aqueous ethylene glycol, producing primary aromatic amines in good yields. Ammonia pressure and water were found to accelerate the copper‐mediated reaction while strong chelating ligands showed a suppression effect. A rationale for the copper‐mediated amination of aryl halides with ammonia is given based on a double‐face role of chelating effect. Copyright © 2009 John Wiley & Sons, Ltd.     

Correlation between the Cu/Al Value and Activity of Cu-ZSM-5 Catalysts and the Chemical Nature of the Starting Copper Salt

Cu-ZSM-5 catalysts for the selective reduction of NO with propane were obtained by ion exchange between H-ZSM-5 zeolite and an aqueous or aqueous ammonia solution of a copper salt (acetate or nitrate). Their Cu/Al values (%) defined as 2 × 100 (Cu : Al), where Cu : Al is the copper-to-aluminum atomic ratio, were determined as a function of ion exchange pH, which was varied by changing the copper salt and solution concentration. Cu/Al is primarily determined by the chemical nature of the starting copper salt. For a given salt, it is governed by the salt concentration in the solution. At a fixed salt concentration, Cu/Al is always larger for copper acetate than for copper nitrate. It can be raised to ≫100% by using an aqueous ammonia solution of a copper salt. Furthermore, it increases with increasing Si/Al in the starting zeolite if the other ion exchange conditions are equal. Irrespective of preparation conditions, the catalytic activity of Cu-ZSM-5 grows in proportion to Cu/Al. It peaks at Cu/Al ∼ 100% and then remains constant up to Cu/Al ∼ 400%. In order to achieve Cu/Al ∼ 100%, it is most appropriate to use a copper acetate solution.__________Translated from Kinetika i Kataliz, Vol. 46, No. 4, 2005, pp. 652–656.Original Russian Text Copyright © 2005 by Tsikoza, Matus, Ismagilov, Sazonov, Kuznetsov.     

Synthesis and characterisation of copper(II) hydroxide gels

The formation of copper(II) hydroxide gels from aqueous precursors requires very critical conditions. Gels have been obtained by adding ammonia to aqueous solutions of copper(II) acetate, in the presence of a small amount of sulphate ions. Other salts (chloride, nitrate, sulphate) or bases (NaOH, KOH) lead to precipitation rather than gelation. These gels are actually made of an intimate mixture of acetate-based organic/inorganic polymers and nanometric posjnakite crystals Cu₄(OH)₆(SO₄) · H₂O. Acetate ions and ammonia can be partially removed upon washing, which after drying leads to crystalline copper(II) hydroxide needles deposited on a strongly oriented layer of posjnakite crystals. A theoretical model based on the electronegativity equalisation principle is used to describe these experimental results. It provides a better understanding of the role of complexing anions during the formation of condensed phases.     

Synthesis of 3-amino-4-nitropyrazoles

3-Bromo-1,5-dimethyl-4-nitropyrazole does not react upon heating with aqueous ammonia, while 1,5-dimethyl-3,4-dinitropyrazole under the same conditions yields 3-amino-1,5-dimethyl-4-nitropyrazole, which is formed from 3-bromo-1,5-dimethyl-4-nitropyrazole in the presence of a copper catalyst. The amination of 1-methyl-3,4-dinitropyrazole-5-carboxylic acid is accompanied by decarboxylation, which is characteristic for 4-substituted 1-methylpyrazole-5-carboxylic acids upon heating in aqueous ammonia or water.     

Synthesis of Cu(II)-containing TiO2-SiO2 binary xerogels by hydrolysis of a mixture of tetrabutoxytitanium, tetraethoxysilane, and copper(II) chloride in a water-ammonia atmosphere

A Cu(II)-containing binary xerogel TiO₂-SiO₂ was synthesized by joint hydrolysis of tetrabutoxytitanium, teraethoxysilane and copper(II) chloride dissolved in their mixture. The synthesis was performed in a vapor of 10% aqueous ammonia under static conditions. EPR spectroscopy was used to examine the state of Cu(II) in the xerogel matrix. Data on specific features of the behavior of saccharose within xerogel pores under heating were obtained. The catalytic activity of the xerogel was tested by the kinetic method on model reactions of hydrogen peroxide decomposition and oxidative dehydrogenation of trimethylhydroquinone.     

CuNaY分子筛的制备及其催化甲醇氧化羰基化

采用多种铜盐溶液与NaY分子筛离子交换制备了CuNaY催化剂,通过加入氨水提高溶液pH值以及高温活化,显著提高了该催化剂对甲醇氧化羰基化合成碳酸二甲酯的反应活性。不同的铜盐水溶液交换制备的CuNaY催化剂催化活性不同,添加氨水将溶液pH值调节为11后,离子交换制备的CuNaY催化剂的催化活性和DMC选择性明显升高且趋于一致。经元素分析、XRD、XPS和H₂-TPR表征可知,加入氨水可促进Cu²⁺离子交换的进行,提高CuNaY催化剂中Cu的交换量,催化剂中约75%的Cu²⁺定位于分子筛的超笼中。     

Solution Characteristics for Adsorption of Copper Ion with Iron(III) Hydroxide from Aqueous Ammonia Solution

The distribution of copper ion species in aqueous ammonia solution is evaluated as a function of pH by a numerical approach. Adsorption of copper on colloidal iron(III) hydroxide in solutions of total ammonia (0.14-1.2 M) are performed at various values of pH. The maximum efficiency of adsorption occurs when the sum of the fractions of the species Cu(NH₃)²⁺, Cu(NH₃)₂²⁺ and Cu(NH₃)₃²⁺ in the solution reaches its maximum. With varied solution pH, the distribution of copper species is the determining factor for maximum adsorption, whereas the surface properties of the adsorbing particles show smaller effects under the test conditions.     

State of the copper-containing component and the catalytic properties of Cu/ZSM-5 in selective NO reduction with propane

Supported Cu/ZSM-5 catalysts have been synthesized by ion exchange and impregnation using aqueous ammonia solutions of copper nitrate containing orbital-ordered copper ions. The state of the copper-containing component in the pore space of the catalysts and copper sorption in the catalysts have been investigated by a complex of physicochemical methods. The catalytic properties of Cu/ZSM-5 in the selective catalytic reduction of NO with propane are reported. The catalytic properties depend on the copper precursor structure and deposition method, which determine the size of the copper oxide clusters on the outer surface of zeolite crystals.     

Probing the influence of X-rays on aqueous copper solutions using time-resolved in situ combined video/X-ray absorption near-edge/ultraviolet-visible spectroscopy

Time-resolved in situ video monitoring and ultraviolet-visible spectroscopy in combination with X-ray absorption near-edge spectroscopy (XANES) have been used for the first time in a combined manner to study the effect of synchrotron radiation on a series of homogeneous aqueous copper solutions in a microreactor. This series included both non biologically relevant (pyridine, bipyridine, neocuproine, terpyridine, dimethylpyridine, ammonia, ethylenediamine, and 1,10-phenanthroline) and biologically relevant (histidine, glycine, and imidazole) ligands. It was found that when water is present as solvent, gas bubbles are formed under the influence of the X-ray beam. At the liquid-gas interface of these bubbles, in particular cases colloidal copper nanoparticles are formed. This reduction process was found to be influenced by the type of copper precursor salt (SO(4)(2-), NO(3)(-), and Cl(-)), the ligands surrounding the copper cation, and the redox potential of the copper complexes (ranging between +594 and -360 mV). In other words, in some cases, no reduction was encountered (e.g., ammonia in the presence of SO(4)(2-) and NO(3)(-)), whereas in other cases reduction to either Cu(+) (neocuproine with SO(4)(2-)) or Cu(0) (e.g., histidine and imidazole both with SO(4)(2-), NO(3)(-), and Cl(-)) was observed. These results illustrate the added value of video spectroscopy for the interpretation of in situ XANES studies. Not only do the results give an illustration of the parameters that are important in the redox processes that occur in biological systems, they also show the potential problems associated with studying catalytic processes in aqueous solutions by XANES spectroscopy.     

Liquid chromatography of palladium and non-ferrous metal chelates with 1-(2-pyridylazo)-2-naphthol

1-(2-Pyridylazo)-2-naphthol has been used for extraction concentration of palladium, copper, cobalt and nickel from aqueous solutions and subsequent separation of the chelates obtained, by means of high-pressure liquid chromatography. A technique for determining microamounts of palladium in aqueous solutions in the presence of 100-fold ratio of copper and 80-fold ratio of cobalt has been developed.     

Synthesis and characterization of cuprous selenide nanocrystals at room temperature

A simple method has been developed to prepare cuprous selenide nanocrystals by the reaction of copper nitrate trihydrate with selenium and sodium mercaptoacetate in aqueous ammonia system. Cu_2Se nanocrystals were characterized by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), electron diffraction (ED), fluorescence spectrum and ultraviolet-visible absorption spectrum. Cu_2Se nanocrystals showed berzelianite structure with 20-40 nm in length and 10-20 nm in width. A possible mechanism is also discussed.     

Conditions for the formation of copper nanoparticles by reduction of copper(II) ions with hydrazine hydrate solutions

Optimal conditions were found for the preparation of copper nanoparticles in aqueous solution via reduction of copper(II) ions with hydrazine hydrate. The effects of ligand environment of copper(II) in the initial solution (hydrate, ammonia, citrate, and glycine complexes), concentration, pH, surfactants, temperature, and mode of heating were examined. The obtained colloidal systems were studied by optical spectroscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction, and atomic force microscopy. The examined colloids were found to contain generally spherical copper nanoparticles with a diameter of about 10 nm, which were coated with a copper(I) or copper(II) oxide and hydroxide film.     

蒸氨压力对Cu/SiO_2催化剂的影响及其草酸二甲酯加氢性能

以Si O2为载体,铜氨溶液为前驱体,采用蒸氨法在不同蒸氨压力下制备了系列铜负载量质量分数为20.0%的Cu/Si O2催化剂。采用X射线衍射(XRD)、H2-程序升温还(H2-TPR)、高分辨透射电子显微镜(HRTEM)、X射线诱导俄歇电子能谱(XAES)等技术手段对催化剂的物理化学性能进行了表征。考察了蒸氨速率对催化剂物化结构及其草酸二甲酯催化加氢制乙二醇的催化性能影响。在反应温度200℃、压力3.0 MPa、液时空速LHSV=0.4 h-1、氢气草酸二甲酯摩尔比80∶1的反应条件下测定了催化剂的活性。结果表明,在蒸氨压力为31.3 k Pa条件下制备的催化剂表现出了最佳活性和选择性,草酸二甲酯转化率达到了99.9%,乙二醇选择性达94.4%。H2-TPR、XRD、TEM、FTIR及XAES表征结果表明,较低蒸氨压力有利于铜氨离子快速分解负载在载体上,避免铜粒子聚集长大,还原后形成Cu2O和Cu0物种颗粒尺寸较小,分散比较均匀,催化活性,尤其是乙二醇的选择性更佳。     

铜对Mn/Al_2O_3氨还原SO_2到单质硫催化性能的影响

ＳＯ2 是危害最为严重的大气污染物之一 ,也是造成酸雨的元凶。将ＳＯ2 选择性还原为单质硫 ,既能消除ＳＯ2 对环境的污染 ,又能回收单质硫 ,具有特别重要的意义。根据所用的还原剂的不同 ,催化还原ＳＯ2 到单质硫可分为Ｈ2 、炭、烃类 (主要是ＣＨ4 )、ＣＯ和ＮＨ3还原法[1] 。氨还原法是基于氨的催化分解生成Ｎ2 和Ｈ2 混合气 ,其中的Ｈ2 再还原ＳＯ2 到硫和Ｈ2 Ｓ ,然后进行高温Ｃｌａｕｓ反应生成单质硫。Ｐａｉｋ[2 ] 等以第四周期过渡金属硫化物载于Ａｌ2 Ｏ3 作为催化剂 ,研究了Ｈ2 还原ＳＯ2 为单质硫的反应 ,认为过渡金属硫化物是…     

An Unprecedented‐Type Intramolecular Redox Reaction of Solid Tetraamminecopper(2+) Bis(permanganate) ([Cu(NH3)4](MnO4)2) – A Low‐Temperature Synthesis of Copper Dimanganese Tetraoxide‐Type (CuMn2O4) Nanocrystalline Catalyst Precursors

Tetraamminecopper(2+) bis(permanganate) ([Cu(NH₃)₄](MnO₄)₂; 1 ) was prepared, and its properties were studied in both aqueous solution and the solid phase. The presence of H‐bond interactions between the ammonia ligand of the complex cation and an O‐atom of the permanganate ion was detected by IR and Raman methods. The solid‐phase thermal deammoniation of 1 led to an unusual intramolecular redox reaction between the Mn O⋅⋅⋅H N linkage with formation of NH₄NO₃ and CuMn₂O₄‐type mixed oxides instead of stepwise deammoniation, even below 100°. The thermal deammoniation of 1 in aqueous solution led, instead of to hydrated copper(2+) bis(permanganate), to the formation of NH₄MnO₄ ( 2 ). Since the temperature of the thermal deammoniation of 1 is lower than the decomposition temperature of the permanganate ion, the regulated solid‐phase decomposition of 1 allowed preparation of CuMn₂O₄‐type oxides with mixing of copper and manganese at the atomic level.