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Synthesis of CZTS nanoparticles for low-cost solar cells

In this work, uniformly sized Cu2ZnSnS4 (CZTS) nanoparticles with easy control of chemical composition were synthesized and printable ink containing CZTS nanoparticles was prepared for low-cost solar cell applications. In addition, we studied the effects of synthesis conditions, such as reaction temperature and time, on properties of the CZTS nanoparticles. For CZTS nanoparticles synthesis process, the reactants were mixed as the 2:1:1:4 molar ratios. The reaction temperature and time was varied from 220C to 320C and from 3 hours to 5 hours, respectively. The crystal structure and morphology of CZTS nanoparticles prepared under the various conditions were investigated by X-ray diffraction (XRD) and field-emission scanning electron microscopy (FE-SEM), and energy dispersive X-ray spectroscopy (EDS) was used for compositional analysis of the CZTS nanoparticles.

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

 

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The “one-pot” synthesis of 4-methyl-2-pentanone (methyl isobutyl ketone) from acetone over PdCu catalysts prepared from layered double hydroxides

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

 

Extracurricular laboratory:new discovery of Bis(acetylacetone)copper

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Synthesis of Ba2YCu3O7-delta Superconductor through Organometallic Route

The chemical synthesis of a high-Tc Ba2YCu3O7-delta superconductor was investigated through the organometallic route, using Ba metal, Y(OPri)3, and Cu-alkoxides or Cu-acetylacetonate as starting materials.Chemically homogeneous submicron powders of single phase Ba2YCu3O7-delta were successfully prepared at 750 deg C by controlled partial hydrolysis metal alkoxides.The utilization of ozone for favorable decomposition of Ba2YCu3O7-delta precursors was found to have a remarkable effect on suppressing the formation of Ba CO3 and lowering the formation temperature of Ba2YCu3O7-delta to about 650 deg C.The single phase Ba2YCu3O7-delta ceramics exhibited superconductivity at approximately 83 K (Tc end).

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

 

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A new protocol for the in situ generation of aromatic, heteroaromatic, and unsaturated diazo compounds and its application in catalytic and asymmetric epoxidation of carbonyl compounds. Extensive studies to map out scope and limitations, and rationalization of diastereo- and enantioselectivities

A variety of metalated tosylhydrazone salts derived from benzaldehyde have been prepared and were reacted with benzaldehyde in the presence of tetrahydrothiophene (THT) (20 mol %) and Rh2(OAc)4 (1 mol %) to give stilbene oxide. Of the lithium, sodium, and potassium salts tested, the sodium salt was found to give the highest yield and selectivity. This study was extended to a wide variety of aromatic, heteroaromatic, aliphatic, alpha,beta-unsaturated, and acetylenic aldehydes and to ketones. On the whole, high yields of epoxides with moderate to very high diastereoselectivities were observed. A broad range of tosylhydrazone salts derived from aromatic, heteroaromatic, and alpha,beta-unsaturated rated aldehydes was also examined using the same protocol in reactions with benzaldehyde, and again, good yields and high diastereoselectivities were observed in most cases. Thus, a general process for the in situ generation of diazo compounds from tosylhydrazone sodium salts has been established and applied in sulfur-ylide mediated epoxidation reactions. The chiral, camphor-derived, [2.2.1] bicyclic sulfide 7 was employed (at 5-20 mol % loading) to render the above processes asymmetric with a range of carbonyl compounds and tosylhydrazone sodium salts. Benzaldehyde tosylhydrazone sodium salt gave enantioselectivities of 91 ¡À 3% ee and high levels of diastereoselectivity with a range of aldehydes. However, tosylhydrazone salts derived from a range of carbonyl compounds gave more variable selectivities. Although those salts derived from electron-rich or neutral aldehydes gave high enantioselectivities, those derived from electron-deficient or hindered aromatic aldehydes gave somewhat reduced enantioselectivities. Using alpha,beta-unsaturated hydrazones, chiral sulfide 7 gave epoxides with high diastereoselectivities, but only moderate yields were achieved (12-56%) with varying degrees of enantioselectivity. A study of solvent effects showed that, while the impact on enantioselectivity was small, the efficiency of diazo compound generation was influenced, and CH3CN and 1,4-dioxane emerged as the optimum solvents. A general rationalization of the factors that influence both relative and absolute stereochemistry for all of the different substrates is provided. Reversibility in formation of the betaine intermediate is an important issue in the control of diastereoselectivity. Hence, where low diastereocontrol was observed, the results have been rationalized in terms of the factors that contribute to the reduced reversion of the syn betaine back to the original starting materials. The enantioselectivity is governed by ylide conformation, facial selectivity in the ylide reaction, and, again, the degree of reversibility in betaine formation. From experimental evidence and calculations, it has been shown that sulfide 7 gives almost complete control of facial selectivity, and, hence, it is the ylide conformation and degree of reversibility that are responsible for the enantioselectivity observed. A simple test has been developed to ascertain whether the reduced enantioselectivity observed in particular cases is due to poor control in ylide conformation or due to partial reversibility in the formation of the betaine.

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

 

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Crystal structure-selective formation and carrier dynamics of type-II CdS-Cu31S16 heterodimers

Anisotropically phase-segregated CdS-Cu31S16 heterodimers with type-II band alignment were spontaneously formed by selective growth of monoclinic Cu31S16 phases on preformed hexagonal CdS phases. The photo-induced carrier dynamics of the heterodimer was investigated by fluorescence and transient absorption measurements. The Royal Society of Chemistry 2013.

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

 

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Crystal phase-controlled synthesis of Cu2FeSnS4 nanocrystals with a band gap of around 1.5 eV

Cu2FeSnS4 (CFTS) nanocrystals with tunable crystal phase have been synthesized using a solution-based method. As-synthesized CFTS nanocrystals in the shape of oblate spheroid and triangular plate with band gaps of 1.54 ¡À 0.04 and 1.46 ¡À 0.03 eV, respectively, appear attractive as a low-cost substitute for thin film solar cells. The Royal Society of Chemistry 2012.

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

 

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Simultaneous phase and size control in the synthesis of Cu 2SnS3 and Cu2ZnSnS4 nanocrystals

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

 

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Compositionally tunable photoluminescence emission in Cu 2ZnSn(S1-xSex)4 nanocrystals

Inorganic nanostructures: Alloyed Cu2ZnSn(S1-xSe x)4 wurtzite nanocrystals (10nm in size) with a varying composition (x=0-1) were synthesized using a colloidal hot injection route. A photoluminescence (PL) emission study of these nanocrystals shows a compositionally tunable band-gap ranging between 0.9-1.4eV that directly correlates to the sulfur-to-selenium ratio (see picture). Copyright

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

 

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Preparation of Cu Thin Films by the Decomposition of Copper Acetylacetonate on Catalytically Active Substrate Surfaces

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

 

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A Copper-Catalyzed Tandem C?H ortho-Hydroxylation and N?N Bond-Formation Transformation: Expedited Synthesis of 1-(ortho-Hydroxyaryl)-1H-indazoles

A facile, one-pot synthesis of 1H-indazoles featuring a Cu-catalyzed C?H ortho-hydroxylation and N?N bond-formation sequence with the use of pure oxygen as the terminal oxidant was developed. The reaction of readily available 2-arylaminobenzonitriles with various organometallic reagents led to ortho-arylamino N?H ketimine species. Subsequent Cu-catalyzed hydroxylation at the ortho position of the aromatic ring followed by N?N bond formation in DMSO under a pure-oxygen atmosphere afforded a wide variety of 1-(ortho-hydroxyaryl)-1H-indazoles in good to excellent yields. This efficient method does not require the utilization of noble-metal catalysts, elaborate directing groups, or privileged ligands.

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