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Liquid-phase oxidation of 3,5-di-tert-butylcatechol (3,5-DtBC) by molecular oxygen was carried out in the presence of homogeneous Cu(II) chelates or heterogeneous Cu(II)-poly(4-vinylpyridine) (Cu(II)-PVP) catalytic systems. The oxidation product in both cases is 3,5-di-tert-butyl-o-benzoquinone (3,5-DtBQ). The catalytic activity of the oxidation of 3,5-DtBC catalyzed by the homogeneous Cu(II) system was found to be affected by the Cu(II) chelates used as the catalyst, the addition of pyridine derivatives, and their amounts added. The oxidation activity was found to increase with the basicity of the added pyridine derivatives. The kinetic data obtained from the formation rate of 3,5-DtBQ by the homogeneous bis(acetylacetonato)Cu(II)-pyridine catalytic system showed that the rate was independent of the 3,5-DtBC concentration, second order in the concentration of the catalyst, and first order with respect to the partial pressure of oxygen. The homogeneous copper(II) chelate-catalyzed oxidation of 3,5-DtBC confirmed the stoichiometric equation 3,5-DtBC + 1 2O2 = 3,5-DtBQ + H2O. On the basis of these data, possible mechanistic interpretations are discussed, in which a dimeric Cu(II) complex is assumed to be the active species. The kinetics of 3,5-DtBC oxidation by molecular oxygen in the presence of the heterogeneous Cu(II)-PVP catalyst revealed that both the oxygen absorption rate and effectiveness factor decreased with increasing particle size of the Cu(II)-PVP catalyst. The increase of the particle size of the catalyst was found to cause an increase in the fraction of mass transfer resistance in the total (mass transfer + reaction) resistance of the oxidation reaction.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Nanocrystals of multicomponent chalcogenides, such as Cu 2ZnSnS4 (CZTS), are potential building blocks for low-cost thin-film photovoltaics (PVs). CZTS PV devices with modest efficiencies have been realized through postdeposition annealing at high temperatures in Se vapor. However, little is known about the precise role of Se in the CZTS system. We report the direct solution-phase synthesis and characterization of Cu 2ZnSn(S1-xSex)4 nanocrystals (0 ? x ? 1) with the aim of probing the role of Se incorporation into CZTS. Our results indicate that increasing the amount of Se increases the lattice parameters, slightly decreases the band gap, and most importantly increases the electrical conductivity of the nanocrystals without a need for annealing.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Simple copper(ii) hydroxide Cu(OH)2 could act as an efficient heterogeneous catalyst for selective oxidative cross-coupling of a broad range of terminal alkynes and amides using air as a sole oxidant, giving the corresponding ynamides in moderate to high yields (56-93% yields). The Royal Society of Chemistry 2012.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Bis[ethyl (trifluoroacetyl)acetato]copper(II), [Cu(etfac)2], has been prepared and studied by X-ray crystallography and EPR spectroscopy. The complex is centrosymmetrical and crystallizes in the P21/c space group with two formula units per unit cell. After dissolving of the complex in solid matrix or in suitable solvents some changes are detected in the EPR spectra and are discussed. The EPR spectra of the complex magnetically diluted in the corresponding Pd(II) complex reveal the presence of only one paramagnetic species further denoted as B. However, EPR spectra measured in solution indicate the presence of two different paramagnetic species: (i) non-distorted parent species B, and (ii) rhombic-distorted species A, which prevail in solutions. The A:B species ratio is a function of the solvent and temperature. The [Cu(etfac)2] adduct with 4-(dimethylamino)pyridine has also been studied and found to crystallize in the C2/c space group. The adduct EPR spectrum monitored in solution shows the presence of only one paramagnetic species.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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In this study, (E)- and (Z)-enones carrying only a phenyl substituent at their C(beta) atom were treaced with dimethyl diazomalonate in the presence of (acetylacetonato)copper(II). According to the configuration of the starting enones, the products were dioxole or dihydrofuran derivatives, significant heterocycles in natural products.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Preparation of epitaxial YBa2Cu3O7 (YBCO) films on cerium oxide-buffered sapphire (r-cut alpha-Al2O3) substrates by an excimer-laser-assisted metalorganic deposition (ELAMOD) is reported. The ELAMOD process has been developed to bring about the advantage of shorter heating time than that in the conventional metalorganic deposition; the coated films are irradiated by an excimer laser beam before firing. We initiated the ELAMOD-YBCO process using a homogenized 8-mm-square laser beam which irradiates the coated surface in a fixed substrate mode. In order to extend the process applicable to large-area films, a scan irradiation mode was employed and a high critical-current density over 6 MA/cm2 has been observed. In the process, an appropriate choice of laser energy is difficult but crucial to obtain YBCO films with high superconducting properties. Then, laser irradiation from backside of the substrate was examined and proved to be beneficial to extend the experimental window of the laser energy. Moreover, a newly developed ELAMOD process using a 90-mm-wide line-beam is also reported which has a potential ability for large-area applications.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Cubic CuFeS2 nanocrystals (NCs) have been obtained via a facile colloidal chemistry approach and they show remarkable catalytic activity in the reduction of I3-. Dye sensitized solar cells (DSSCs) with CuFeS2 NCs as counter electrodes (CEs) display a power conversion efficiency of 8.10% comparable to that of a cell with Pt as the CE (7.74%) under the same conditions.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Several mixed ligand complexes of copper(II) and nickel(II) having the compositions and , where aaH is acetylacetone, tcaH is trichloroacetic acid; L is gamma-picoline, imidazole, 2-picoline-N-oxide or thiourea and M is Cu(II) or Ni(II), have been isolated and characterised on the basis of their analyses, molar conductance, magnetic susceptibility, infrared, electronic spectral data and thermogravimetric measurements.The infrared spectra reveal the presence of uninegative bidentate acetyl acetonate and trichloroacetate groups in all these complexes.As the temperature increases, the mixed ligand complexes start decomposing with the loss of neutral donor ligand, followed by trichloroacetate ion and acetylacetonate ion in definite steps and ultimately forming MO at 600-675 deg .Square planar, tetrahedral, distorted octahedral and octahedral structures have been proposed for the complexes, , , and , respectively.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Supported PdCu catalysts prepared from layered double hydroxides (LDHs) as precursors were evaluated in the gas phase reaction of acetone with hydrogen to methyl isobutyl ketone (MIBK). Two series of catalysts containing ca. 0.2 wt.% Pd and various amounts of Cu (Cu/Pd molar ratio of ca. 0.25, 0.5 and 1) were elaborated according to different methods. One series of precursors was obtained by impregnation of calcined Mg(Al)O mixed oxide with heterobinuclear Pdx Cu1-x acetylacetonates. A second series of precursors was synthesized by coprecipitation of Mg/Pd/Cu/Al LDHs. After calcination, both series were reduced at 473 K. The extends of basic, acid and metal functions were evaluated through microcalorimetric adsorption of CO2, TPD of NH3 and TPR of H2. It was found that the multifunctional transformation of acetone to MIBK was rate determined by the basic function. However, the way by which the catalysts were prepared, impregnation or coprecipitation, controls the extend of hydrogenated by-products, isopropyl alcohol and 4-methyl-2-pentanol. The extensive dilution by migrating MgAlOx species onto the metallic particles makes the coprecipitated catalysts highly selective by decreasing selectively the rate of C=O bond hydrogenation.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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The hexagonal copper-tin alloy (Cu-Sn) nanoplates were synthesized using a high temperature solvent method, the length of six equilateral edges of hexagonal Cu-Sn nanoplates was 23 nm, and the thickness was 13 nm. The obtained hexagonal Cu-Sn nanoplates were highly monodisperse and allowed the formation of nanoarrays arranged with long-range order. The hexagonal Cu-Sn nanoplates exhibited high catalytic activity on catalytic hydrogenation of 4-nitrophenol to 4-aminophenol. Due to the promotion effect of Sn, the apparent rate constant (ka) of hexagonal Cu-Sn nanoplates was three times that of Cu nanoparticles. The density functional theory (DFT) calculations and experimental results demonstrated that Sn could promote the coordination process of -NO2 of 4-nitrophenol with Cu-Sn nanoplates and contribute to activation of 4-nitrophenol. In addition, the hexagonal Cu-Sn nanoplates showed high stability and reusability for the reduction reaction, good adaptability in different pH and the ionic strength, and wide applicability for the degradation of methylene blue, methyl orange, and rhodamine B, even in the industrial wastewater, suggesting that the Cu-Sn nanoplates are promising catalysts in organic industry wastewater treatment.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”