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A selective CVD system used to deposit the central metal of a volatile complex preferentially on catalytically active substrate surfaces was examined.Copper(II) acetylacetonate was vaporized in a flow of hydrogen and decomposed on Ni, Pd, and Al plates in order to deposit metallic copper.When a Ni plate was used as the substrate, deposition of metallic copper occurred at temperatures in the range 130-180 deg C only on the substrate surfaces.The formation of an ultrathin film of Cu of uniform thickness was confirmed.On a Pd substrate, the formation of an ultrathin Cu film of uniform thickness was also observed.On an Al substrate, however, deposition occurred nonselectively at temperatures above 160 deg C, not only on the substrate surface, itself, but also on the wall of the glass tube as well as the quartz wool surrounding the Al plate.In addition, the formation of fine particles of Cu, instead of thin film, was found to exist on the substrate.Because the deposition of Cu took place on catalytically active surfaces selectively, the deposition was considered to proceed by a catalytic hydrogenation of the C=O bond of the ligand, thus detaching it from the Cu ion and allowing it to decompose the complex and deposit Cu metal.

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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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We synthesized uniform Cu2O coated Cu nanoparticles from the thermal decomposition of copper acetylacetonate followed by air oxidation and used these nanoparticles as catalysts for Ullmann type amination coupling reactions of aryl chlorides.

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

 

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Copper thin films were prepared by a low-temperature atmospheric pressure chemical vapour deposition method. The raw material was copper (II) acetylacetonate. At a reaction temperature above 220 C, polycrystalline copper films can be obtained by hydrogen reduction of the raw material. The resistivity of the film was close to that for bulk copper.

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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 electronic structures of Ni(II) and Cu(II) bis(acetylacetonates) and some of their gamma-substituted analogues (X = Cl, Me) are studied by photoelectron spectroscopy (PES). The vertical ionization energies of the compounds are determined, and the spectra are interpreted based on the trends of changes in the electronic structure and photoelectron spectra of acetylacetonates upon gamma-substitution. The suggested interpretation of the photoelectron spectra is confirmed by the quantum chemical INDO calculations of the electronic structure of the Cu(II) compounds.

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

 

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Reactions of the Schiff base ligand OH-C6H4-CH[dbnd]NC(CH2OH)3 (H4L) with copper(II) salts in various reaction media afforded complexes [Cu4(H2L)4]·MeOH (1·MeOH), [Cu2(O2CMe)2(H3L)2] (2), [Cu4(H2L)4(H2O)2]·1.5dmf (3·1.5dmf), [Cu4(H2L)4(H2O)]·MeOH (4·MeOH) and [Cu4(H2L)4]2·2H2O·7MeOH (5·2H2O·7MeOH). Compounds 1, 3 and 4 consist of neutral tetranuclear entities in which the CuII ions are coordinated by the tridentate Schiff base ligands, forming a tetranuclear Cu4O4 cubane-like configuration. Compound 5 contains similar cubane-like tetranuclear entities which are further linked through the hydroxyl groups of the ligands thus forming dimers of cubanes. Compound 2 contains a neutral dinuclear entity in which the CuII ions are bridged through the Schiff base and the acetate ligands, comprising distorted Cu2O2 core. The Schiff base ligand adopts five different coordination modes and two deprotonation states in the structures of 1?5 acting simultaneously as chelating and bridging agent between the metal ions. The lattice structures of 1?5 exhibit interesting 3D networks based on hydrogen bonded metal clusters and they are studied with Hirshfeld Surface analysis methods.

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

 

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We have created a facial self-templated method to synthesize three distinct nanostructures, including the unique edge-cut Cu@Ni nanocubes, edge-notched Cu@Ni nanocubes, and mesoporous Cu-Ni nanocages by selective wet chemical etching method. Moreover, in the synthesis process, the corners of edge-cut Cu@Ni nanocubes and mesoporous Cu-Ni nanocages can be etched to produce the highly catalytically active (111) facets. Impressively, compared to edge-notched Cu@Ni nanocubes and edge-cut Cu@Ni nanocubes, the Cu-Ni nanocages exhibit higher electrocatalytic activity in the hydrogen evolution reaction (HER) under alkaline conditions. When obtained overpotential is 140 mV, the current density can reach 10 mA cm-2 meanwhile, the corresponding Tafel slope is 79 mV dec-1. Moreover, from the calculation results of density functional theory (DFT), it can be found that the reason why the activity of pure Ni is lower than that of Cu-Ni alloy is that the adsorption energy of the intermediate state (adsorbed H?) is too strong. Meanwhile the Gibbs free-energy (|DeltaGH?|) of (111) facets is smaller than that of (100) facets, which brings more active sites or adsorbs more hydrogen.

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

 

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Facile and rapid one-pot synthesis of nearly monodisperse Cu 2SnS3 and Cu2ZnSnS4 nanocrystals was developed using a heating up method. Their crystalline phase and size were simultaneously controlled by judiciously choosing the sulfur precursor reactivity and the oleic acid content. This journal is the Partner Organisations 2014.

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

 

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There were studied polyamide composites containing copper(II) oxide (CuO) and copper(II) acetoacetate Cu(acac)2, which after laser irradiation became fully prepared for an electroless metallization process. The composites were produced by use of typical processing methods such as extrusion and injection moulding. They were then irradiated with various numbers of ArF excimer laser pulses (lambda = 193 nm) at different fluences. The metallization procedure of the laser-irradiated samples was performed by use of a commercial metallization bath and formaldehyde as a reducing agent. The samples were examined using the FTIR and XPS techniques. Examinations were focused on elucidation of possible chemical reactions between CuO and Cu(acac)2, affected by both thermal processing and laser irradiation. It was found that CuO was efficiently reduced to Cu(0) and that surface became highly active for the direct electroless metallization. A chemical reaction model for this reduction is proposed as well.

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

 

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Treatment of [M(H2Li)] with U(acac)4 in refluxing pyridine led to the formation of the trinuclear complexes [{MLi(py)x}2U] [L1 = N,N?-bis(3-hydroxysalicylidene)-2,2-dimethyl-1,3-propanediamine and M = Ni, Cu or Zn; L2 = N,N?-bis(3-hydroxysalicylidene)-1,3-propanediamine and M = Cu or Zn; L3 = N,N?-bis(3-hydroxysalicylidene)-2-methyl-1,2-propanediamine and M = Ni, Cu or Zn; x = 0 or 1]. The dinuclear compounds [ML3(py)U(acac)2] (M = Cu, Zn) were isolated from the reaction of [M(H2L3)] and U(acac)4 in pyridine at 60C. The crystal structures of the trinuclear complexes are built up by two orthogonal MLi(py)x units which are linked to the central uranium ion by the two pairs of oxygen atoms of the Schiff base ligand; the U(IV) ion is found in the same dodecahedral configuration but the Cu(II) ion coordination geometry and the Cu … U distance are different by passing from L1 or L2 to L3, due to the shortening of the diimino chain of L3. These geometrical parameters seem to have a great influence on the magnetic behaviour of the complexes since the Cu-U coupling in [{CuLi(py)x}2U] (i = 1, 2) is ferromagnetic while it is antiferromagnetic in [{CuL3(py)x}2U]. In the compounds [{CuL3(py)x}2U] and [CuL3(py)U(acac)2], the Cu coordination and the Cu … U distance are very similar, and both exhibit an antiferromagnetic interaction.

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