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Thiocyanate hydrometallurgy for the recovery of gold. Part I: Chemical and thermodynamic considerations

Thiocyanate has been identified and studied as a promising alternative lixiviant for gold in acidic solutions. Eh-pH and ion species distribution diagrams for SCN-H2O, Au-SCN-H2O, Ag-SCN-H2O, Cu-SCN-H2O, and Fe-SCN-H2O systems were constructed to predict the behavior of each metal ion in the thiocyanate system and also to explain the experimental results. Thermodynamic analyses suggest that gold can be leached by thiocyanate under appropriate leaching potentials, forming aurous or auric complexes with thiocyanate, depending on the thiocyanate concentration and leaching potential. According to species distribution diagrams, silver (I) and copper (I) form insoluble salts at moderate thiocyanate concentrations and are soluble at low and high thiocyanate concentrations. Ferric ion forms a series of complexes with thiocyanate. The study of the ferric ion effect indicates that gold can be leached in acid thiocyanate solution with ferric sulfate as the oxidant. Also the presence of excess ferric ion reduces the apparent thiocyanate activity for copper (I) and silver (I) dissolution. The findings of this thermodynamic assessment are useful in the analysis of some of the phenomena encountered in the leaching and recovery of gold from thiocyanate solutions as discussed in subsequent papers.

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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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In-situ synchrotron far infrared spectroscopy of surface films on a copper electrode in aqueous solutions

Far infrared spectra of the surface films formed upon anodic oxidation of copper have been obtained in-situ for the first time in aqueous solution environments using a synchrotron source. The spectroelectrochemical behavior of copper was studied in NaOH and in a dilute solution of KSCN in perchlorate. The oxide film at -0.05 V vs. SCE in 0.1 M NaOH solution has been identified as Cu2O. In the passive region at 0.3 V, CuO and Cu(OH)2 appear to be present on the surface. Vibrational bands observed in 0.025 M KSCN + perchlorate solution are attributed to a multilayer film of copper(I) thiocyanate.

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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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Revealing the Chemistry between Band Gap and Binding Energy for Lead-/Tin-Based Trihalide Perovskite Solar Cell Semiconductors

A relationship between reported experimental band gaps (solid) and DFT-calculated binding energies (gas) is established, for the first time, for each of the four ten-membered lead (or tin) trihalide perovskite solar cell semiconductor series examined in this study, including CH3NH3PbY3, CsPbY3, CH3NH3SnY3 and CsSnY3 (Y=I(3?x)Brx=1?3, I(3?x)Clx=1?3, Br(3?x)Cl x=1?3, and IBrCl). The relationship unequivocally provides a new dimension for the fundamental understanding of the optoelectronic features of solid-state solar cell thin films by using the 0 K gas-phase energetics of the corresponding molecular building blocks.

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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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Resolving a Critical Instability in Perovskite Solar Cells by Designing a Scalable and Printable Carbon Based Electrode-Interface Architecture

Thin-film solar cells based on hybrid organo-halide lead perovskites achieve over 22% power conversion efficiency (PCE). A photovoltaic technology at such high performance is no longer limited by efficiency. Instead, lifetime and reliability become the decisive criteria for commercialization. This requires a standardized and scalable architecture which does fulfill all requirements for larger area solution processing. One of the most highly demanded technologies is a low temperature and printable conductive ink to substitute evaporated metal electrodes for the top contact. Importantly, that electrode technology must have higher environmental stability than, for instance, an evaporated silver (Ag) electrode. Herein, planar and entirely low-temperature-processed perovskite devices with a printed carbon top electrode are demonstrated. The carbon electrode shows superior photostability compared to reference devices with an evaporated Ag top electrode. As hole transport material, poly (3?hexyl thiophene) (P3HT) and copper(I) thiocyanate (CuSCN), two cost-effective and commercially available p-type semiconductors are identified to effectively replace the costlier 2,2?,7,7?-Tetrakis-(N,N-di-4-methoxyphenylamino)-9,9?-spirobifluorene (spiro-MeOTAD). While methylammonium lead iodide (MAPbI3)-based perovskite solar cells (PSCs) with an evaporated Ag electrode degrade within 100 h under simulated sunlight (AM 1.5), fully solution-processed PSCs with printed carbon electrodes preserve more than 80% of their initial PCE after 1000 h of constant illumination.

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

 

Final Thoughts on Chemistry for Cuprous thiocyanate

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Unusual complexation of Cu(I) by pyrimidine/pyridine-pyrazole derived ligands exploiting the molecular function of 2-mercapto-4,6-dimethylpyrimidine – Syntheses, crystal structures and electrochemistry

Reaction of 2 equiv. amount of copper(II) chloride dihydrate with 2 equiv. of methyl-5-methyl-1-(4,6-dimethyl-2-pyrimidyl)pyrazole-3-carboxylate (DpymPzC) in presence of 1 equiv. of 2-mercapto-4,6-dimethylpyrimidine (DpymtH) at pH ? 6 afforded the tricoordinated copper(I) complex [Cu(DpymPzC)Cl] (1). The same reaction with copper(II) perchlorate hexahydrate, as the metal salt under the same equivalent ratio at pH ? 6 formed the tetracoordinated copper(I) complex [Cu(DpymPzC)2]ClO4 (2). In both the cases, the role of DpymtH is nothing but only to reduce the copper(II) salt in situ finally forming the copper(I) complex. On the other hand, the direct reaction between the copper(I) thiocyanate and DpymPzC in 2:2 equiv. ratio produced a tricoordinated copper(I) complex [Cu(DpymPzC)SCN] (3). In a similar reaction of 2 equiv. amount of copper(II) chloride dihydrate with 2 equiv. amount of ethyl-5-methyl-1-(2-pyridyl)pyrazole-3-carboxylate (PyPzC) in presence of 1 equiv. of DpymtH at pH ? 6, an intense red coloured microcrystalline compound (4) was obtained. In contrast, 1 equiv. of PyPzC and 2 equiv. of DpymtH on reaction with 1 equiv. of copper(II) chloride dihydrate at pH ? 6 produced a novel tetranuclear mixed coordinated [Cu4(DpymtH)4Cl4] complex (5). Here DpymtH plays dual role – a reducing agent for the copper(II) salt followed by a chelating ligand towards copper(I) so formed in situ. Among the above species, 1, 2 and 5 are crystallographically characterized. In 1, the central copper atom is in distorted triangular planar geometry with N2Cl chromophore whereas in 2, the same is in distorted tetrahedral geometry with N4 chromophore. Notably, the extent of distortion from the ideal geometry is more in 2. In 5, which is in chair conformation, out of four copper atoms, two being in S2Cl chromophore are tricoordinated and the remaining two are tetracoordinated with NS2Cl chromophore. The metal centers are bridged through DpymtH in its ‘thione’ form. Interestingly, the chelation (in part) results in formation of the highly stable four-membered two chelate rings around the two tetracoordinated copper atoms in 5. The two copper centers along the long arm of the chair are separated through a distance of 5.190 A while those in the short arm are at a length of 3.629 A. The electronic, IR spectra and electrochemistry of the complexes 1, 2 and 5 have also been investigated.

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

 

Brief introduction of Cuprous thiocyanate

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Synthesis and structural characterization of seven copper(I) complexes with 3-amino-5,6-dimethyl-1,2,4-triazine and triphenylphosphine/triphenylarsine

Seven new copper(I) complexes containing 3-amino-5,6-dimethyl-1,2,4- triazine (ADMT), [Cu(mu-Cl)(ADMT)(PPh3)]2 (1), [Cu(mu-NCS)(ADMT)(PPh3)]2 (2), [Cu(ADMT)(PPh 3)2Cl] (3), [Cu(ADMT)(PPh3)2Br] (4), [Cu(mu-Cl)(ADMT)(AsPh3)]2 (5), [Cu(mu-Br)(ADMT) (AsPh3)]2 (6) and [Cu(ADMT)(AsPh3) 2I] (7) have been synthesized by the reactions of CuX (X = Cl, Br, I, SCN) with triphenylphosphine/triphenylarsine EPh3 (E = P for 1-4; E = As for 5-7) and ADMT in mixed solvents. Complexes 1-7 have been characterized by IR, NMR, luminescence, elemental analyses and X-ray diffraction. In 1, 2, 5 and 6, the intermolecular hydrogen bonds of type I R22(8) are formed by two N-H donors and two N atoms from two ADMT ligands. In 1-7, the intramolecular hydrogen bond of type II R11(6) is formed between one N-H donor from ADMT and one halide ion. In 1, 2, 5 and 6, the halide ions and thiocyanate ions bridge two copper atoms to form the parallelogram Cu2X2, which are further linked to form infinite zigzag chains along a-axis through the hydrogen bond of type I R2 2(8).

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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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Assembly of novel 2D and 3D heterometallic SbIII-CuI polymers based on antimony(III) thiolates as metallothiolato ligands

A new type of neutral heterometallic SbIII-CuI thiolate coordination polymer has been synthesized under solvothermal conditions by using antimony(III) thiolates as metalloligands and CuSCN as the source of the second metal ion. Reaction of [Sb(edt)Cl] (1) (edt = ethane-1,2-dithiolate) with 1 equivalent of CuSCN affords [{Sb2(edt) 2(mu3-S)CuCl(CuSCN)}n] (2), which features a 2D layer consisted of -CuSCNCuSCN-chains and {Sb2(edt) 2(mu3-S)CuCl} units. During the reaction, 1 was converted into a sulfur-bridged dimer Sb(edt)2S, which behaves simultaneously as a bridging and chelating ligand through all of its sulfur atoms to connect four Cu+ ions in the framework structure of 2. Replacement of Cl- in 1 with pymt-gives a new antimony(III) thiolate formulated as [Sb(edt)-(pymt)] (3) (pymt = 2-pyrimidinethiol), which was further treated with CuSCN to afford coordination polymers [{[Sb(edt)(pymt)] 2(CuSCN)3}n] (4) and [{[Sb(edt)(pymt)]-(CuSCN) 2}n] (5). In the assemblies of 4 and 5, the structure of 3 remains intact and the whole compound serves as a multidentate ligand through Sedt and Npymt atoms to Cu+ ions. Complex 4 also contains -CuSCNCuSCN- chains, which are linked by tridentate {Sb(edt)(pymt)} fragments to form a 2D polymer. Complex 5 is a 3D architecture with {Sb(edt)(pymt)} units acting as bidentate bridging ligand to link the (CuSCN)n layers and {(CuSCN)2}n columns. Complexes 2-5 showed optical transitions with band gaps of 2.66 to 3.41 eV, and their optical properties were studied by DFT calculations. Wiley-VCH Verlag GmbH & Co. KGaA, 2009.

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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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Novel benzotriazoles anti-inflammatory compounds

The present invention relates to novel benzotriazoles of the formula I 1wherein Het is an optionally substituted 5-membered heterocycle containing one to two heteroatoms selected from nitrogen, sulfur and oxygen wherein at least one of said heteroatoms atoms must be nitrogen; R2 is selected from the group consisting of hydrogen, (C1-C6)alkyl or other suitable substituents; R3 is selected from the group consisting of hydrogen, (C1-C6)alkyl or other suitable substituents; s is an integer from 0-5; to intermediates for their preparation, to pharmaceutical compositions containing them and to their medicinal use. The compounds of the present invention are potent inhibitors of MAP kinases, preferably p38 kinase. They are useful in the treatment of inflammation, osteoarthritis, rheumatoid arthritis, cancer, repurfusion or ischemia in stroke or heart attack, autoimmune diseases and other disorders.

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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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X-RAY FLUORESCENT SPECTROSCOPY STUDY OF THE CHARGE STATE OF HETEROATOMS IN ORGANIC COMPOUNDS OF THIRD ROW ELEMENTS. 7. THIOCYANATES AND ISOTHIOCYANATES

We propose an x-ray spectral criterion as a characteristic of organic and inorganic thiocyanates and iosthiocyanates.We establish the lack of interaction between the level of the unshared electron pair of sulfur and the ?CN-orbitals in thiocyanates.

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

 

Discovery of Cuprous thiocyanate

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Improved CuSCN-ZnO diode performance with spray deposited CuSCN

P-type copper(I) thiocyanate (beta-CuSCN) was deposited using a pneumatic micro-spray gun from a saturated solution in propyl sulphide. An as-produced 6 mum CuSCN film exhibited a hole mobility of 70 cm 2/V¡¤s and conductivity of 0.02 S¡¤m-1. A zinc oxide (ZnO) nanorod array was filled with CuSCN, demonstrating the capability of the process for filling nanostructured materials. This produced a diode with a n-type ZnO and p-type CuSCN junction. The best performing diodes exhibited rectifications of 3550 at ¡À 3 V. The electronic characteristics exhibited by the diode were attributed to a compact grain structure of the beta-CuSCN giving increased carrier mobility and an absence of cracks preventing electrical shorts between electrode contacts that are typically associated with beta-CuSCN films.

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