Copper Chloride Hydroxide Research Articles

A novel clinoatacamite route to effectively separate Cu for recycling Ca/Zn/Mn from hazardous smelting waterwork sludge

Cu/Zn/Mn-rich sludge was massively produced in the smelting industries, and legally recycled to reduce its product and to regenerate chemical products. In the past decades, the Cu was commonly recycled as halite from metallic leachate by the classical extraction method, but herein, was effectively purified as copper chloride hydroxide via an advanced hydrothermal route. The results showed that the sludge was carbonate substance comprised of 4.3% Cu, 1.1% Ca, 6.6% Zn and 28.7% Mn, and then completely dissolved as metallic solution by chloride acid. The adsorption of Cu onto the precipitates was investigated via the elution experiment. The results showed that when the solution was directly adjusted to pH 3.5 or 4, the coprecipitation occurred, led to the removal of 90.3–99.5% Cu, 15.5–21.6% Ca, 14.8–18.9% Zn and 11.1–19.1% Mn. But when the solution was hydrothermally treated with the addition of urea, 95% Cu was removed as clinoatacamite, but the loss of Ca/Zn/Mn were only 0.27%, 2.17% and 0.96%, separately. The adsorption of Cu onto clinoatacamite was only 0.02 g/g. In the hydrothermal reaction, the urea was spontaneously decomposed as ammonia and CO2, to consume the newly H+ that generated from the Cu hydrolysis, resulting in continuing the Cu removal at high level. The optimized parameters for Cu removal were at 140 °C for 10 h with the addition of 0.2 g urea. After the Cu removal, Ca/Zn/Mn were rest at high concentration in the treated solution, and stepwise separated as gypsum, gunningite and hausmannite, via the conventional precipitation and extraction routes. The hydrothermal recycling of Cu from metallic solution avoided the conventional multistep of extraction, stripping and evaporation, and showed potential application in the resource utilization of hazardous waste.

Enhanced photocatalytic degradation of methylene blue using carbon dots-modified copper chloride hydroxide nanocomposite

The dye organic pollutants with utilization in chemical industries have been discharged into the environment, causing the water pollution and human disease. Therefore, developing a cheap, reliable and sustainable wastewater cleaning technology is of great importance. Transitional metal is often one of the active photocatalysts for degradation of dye pollution. Among them, Cu has attracted attention due to low price and catalytic activity. In this article, we took Cu sheets as raw materials and used a simple salting-out method to prepare Cu2Cl(OH)3 nanocomposites, which exhibited a photocurrent response under the UV light. At the same time, the structural transformation process from Cu sheet to nanoparticle Cu2Cl(OH)3 was observed over time. The results showed that Cu2Cl(OH)3 displayed significant photocurrent response. In addition, in order to further improve its catalytic performance, Cu2Cl(OH)3 was modified by different concentrations of carbon dots (CDs) and a wide UV light absorption received. Corresponding to it, 1CDs@OHCu was efficient to the photodegradation of methylene blue (MB) within 3 h compared to the mother sample. The physical properties of prepared samples were studied through XRD, UV–vis spectra, SEM, etc. The related kinetic rate of the process of degrading MB was recorded to determine the role of CDs. The intermediates produced during the photo-reaction was monitored via the chemical trapping agent. By analyzing the characteristics and electrochemical features of prepared samples, the catalytic active center was explored. Finally, stability analysis showed that 1CDs@OHCu could be recycled at least 8 times.

Multi-Scale Characterization of Unusual Green and Blue Pigments from the Pharaonic Town of Amara West, Nubia

Pigments from paint palettes and a grindstone excavated from the pharaonic town of Amara West (c. 1300–1050 BCE), which lies between the Second and Third Cataracts of the Nile, were examined using polarized light microscopy, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction, and scanning electron microscopy with energy dispersive X-ray spectroscopy. Most of the pigments were consistent with the typical ancient Egyptian palette, but the greens and some blues were unusual. Two types of green pigment were identified, chlorite (varieties clinochlore and penninite) and copper chloride hydroxide (atacamite type). The former constitutes a type of green earth which has only rarely been identified in pharaonic Egyptian contexts and may be more widespread than is currently reported. The majority of the blue pigment samples were Egyptian blue, but some were found to be a blue earth, the main component of which being sodic amphibole riebeckite. The use of this mineral as a pigment has not previously been reported in any Nile Valley context. These results prompt questions around local and potentially indigenous practices within an ancient colonial context, and highlight avenues for future research.

Preparation and Characterization of CuO Nanoparticles Prepared by Chemical Method

Copper oxide (CuO) nanoparticles were prepared by the sol-gel method, by the reaction of copper chloride and ammonium hydroxide as procurers. Nanopowders are annealing at different temperatures (100 °C, 200 °C, and 600 °C) for 120 min and confirmed the monoclinic phase by X-ray diffraction analysis of the metal oxide with lattice parameters a = 4.694 Å, b = 3.456 Å and c = 5.165Å for annealing temperature 400°C. Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), and UV-Visible Spectroscopy spectrum was used to determine the structure, average crystallize, and morphology. We found increasing in size and energy gap (Eg) from (62.95 nm to 106.84 nm) and from (1.72 eV to 1.49 eV), when annealing temperature increasing from 200 °C to 600 °C, respectively.

Experimental and theoretical studies of cinnamyl alcohol as a novel corrosion inhibitor for copper foils in rolling oil

AbstractCinnamyl alcohol (CA) was added to the rolling oil of copper foils as a novel corrosion inhibitor, and its anticorrosion performance and mechanism were studied using potentiodynamic polarization and electrochemical impedance spectroscopy. Microstructure and chemical composition of the copper electrode surface were analyzed by scanning electron microscopy, energy‐dispersive spectroscopy, and X‐ray photoelectron spectroscopy. The results showed that CA acted as a mixed‐type inhibitor, and the maximum inhibition efficiency of 87.7% was achieved at 2.4 mM. Moreover, a protective film was formed on the copper surface, which attributed to the C–OH groups in the CA molecule. The absorption of CA on the copper surface was physisorption, which conformed to Langmuir adsorption isotherm, with a standard adsorption free energy of −11.38 kJ/mol. In the presence of CA, some flaky corrosion products changed into granular corrosion products. The synergistic effect of the granular corrosion products (copper chloride hydroxide) and the CA film further decreased the corrosion rate.

Synthesis of CuNiSn LDHs as highly efficient Fenton catalysts for degradation of phenol

A series of CuNiSn ternary layered double hydroxides (LDH) were synthesized as catalysts for degradation of phenol via Fenton reaction. At Cu/Ni ratios above 0.2, copper chloride hydroxide co-exists with LDH. Multivalent Cu+/Cu2+, Ni2+/Ni3+ and Sn2+/Sn4+ ions are present in LDH due to the electron transfer between metals in brucite-like sheets. The catalytic activity varies directly with the Cu+ percentage, and the maximum activity is achieved at Cu/Ni/Sn ratio of 1/2/0.75. This catalyst (Cu1Ni2Sn0.75) can mineralize 97.8% phenol under mild conditions and shows good stability. Multivalent Cu, Ni and Sn cations in LDH could construct a closed electron cycle. This allows the rapid regeneration of Cu+ active species through electron transfer within LDH rather than through slow Fenton-like reaction, as what usually happens in conventional Fenton catalysts. In addition, a positive synergistic effect between copper chloride hydroxide and LDH is observed in Cu1Ni2Sn0.75, favoring the formation of Cu+.

Multianalytical approach for the analysis of the Codices Millenarius Maior and Millenarius Minor in Kremsmuenster Abbey, Upper Austria

Two precious Carolingian manuscripts kept in the library of Kremsmuenster Abbey in Upper Austria were subject of investigation. The well-known Codices Millenarius Maior (Inv. No. CC Cim 1, Fig. 1a) and Millenarius Minor (Inv. No. CC Cim 2, Fig. 1b) were studied within the framework of the Centre of Image and Material Analysis in Cultural Heritage (CIMA) in Vienna. The manuscripts are especially famous for their precious and colorful miniatures of a very early medieval period. The aim of the work was the material identification (colors and inks) used for the make-up of the two codices in order to gain a better understanding of their evolution and their provenance. The instrumentation available in the CIMA laboratories allowed performing in situ measurements using non-destructive and non-invasive analytical methods. The investigations comprised a combination of three complementary methods: X-ray fluorescence analysis (XRF), Fourier transform infrared spectrometry in the reflection mode (rFTIR) and Raman spectrometry. In addition to the identification of the pigments and inks also a detailed characterization of the parchment concerning its manufacturing process was achieved by that combination. The identification of calcium carbonates on the surface of the parchment is an indicator for the liming or whitening of the animal skin, whereas the polishing process of the parchment surface with pumice stone, left traces of silicates, detected by rFTIR. The combination of XRF and Raman spectrometry enabled the characterization of black/brown inks in the text revealing the usage of iron gall inks. For the red inks applied for text and initials vermilion and red lead were applied in both codices. Furthermore, the pigment palette used for the illumination included: lead white, orpiment/realgar, red lead, vermilion and red iron oxides as well as azurite and indigo, together with the rather rare copper chloride hydroxide. Furthermore, in both gospels the application of metal leaves as well as powders made of silver–copper and gold–copper alloys could be determined by XRF on several folios.

Vondechenite, a new hydrous calcium copper chloride hydroxide, from the Bellerberg, East-Eifel volcanic area, Germany

Vondechenite, a new hydrous calcium copper chloride hydroxide, from the Bellerberg, East-Eifel volcanic area, Germany

Catalytic removal of organic template from TEA-β zeolite by copper ions

The simultaneous decomposition of organic template and incorporation of copper ions into the zeolite were investigated during the heating mixture of copper chloride hydroxide and TEA-β zeolite under static air atmosphere. Detailed characterizations of the samples during calcination and subsequent copper removal treatment were performed with the aid of TG/MS, IR, XRD, pyridine-IR, XPS, 27Al and 29Si MAS-NMR. It was evidenced that the zeolite detemplation process facilitated the copper ions reduction and migration, inducing the solid ion exchange of copper species with TEA-β zeolite at lower temperature. These reduced copper ions migrated into the zeolite to occupy BrØnsted acid sites, and acted as catalysts to accelerate the oxidative decomposition of organic molecules significantly. The result showed that the virtually complete removal of organic template and incorporation of copper ions were obtained in one step by calcination at 350 °C for 3 h, and these ingoing copper species could be easily removed by re-exchanging with ammonium solution. After detemplation and copper removal, the purified H-β zeolite could still retain a well-defined structure and BrØnsted acid sites, showing a higher catalytic activity on the alkylation of benzene with ethylene compared with the conventionally prepared H-β zeolite.

Characterization of the Corrosion Product Films Formed on the As-Cast and Friction-Stir Processed Ni-Al Bronze in a 3.5 wt% NaCl Solution

An as-cast Ni-Al bronze (NAB) was subjected to friction-stir processing (FSP). The friction-stir processed NAB (FSPed NAB) exhibited better corrosion resistance in a 3.5 wt% sodium chloride solution. The corrosion product films formed on the as-cast and FSPed NAB were characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), and electron probe micro-analysis (EPMA). Uncorroded phases were retained in the films. The interfaces between these phases and their surrounding corrosion products allowed the chloride ions in and reduced the film protectiveness. For the as-cast NAB, the un-corroded phases were large in size or continuous in structure, resulting in continuous interfaces. Therefore, the film on the as-cast NAB exhibited relatively inferior protectiveness. The films on the as-cast and FSPed NAB were similar in composition with mainly copper chloride hydroxide Cu2(OH)3Cl in the outer layer, and Al2O3 and Cu2O with the incorporation of Fe and Ni in the inner layer. Stability of the fi...

Solution Transformation of the Products of AC Electrochemical Metal Oxidation

Electrochemical oxidation of copper and aluminium using alternating current of industrial frequency results in the formation of non-equilibrium products. Their transformations during the ageing in sodium chloride solutions of different concentrations have been considered. According to X-Ray diffraction confirmed by TG/DSC/DTG analysis, irrespective of solution concentration, the ageing products consist of aluminium oxyhydroxide (boehmite, AlOOH), copper-aluminium carbonate hydroxide hydrate (Cu–Al/LDH) and copper chloride hydroxide (Cu2(OH)3Cl). The increase of the solution concentration leads to Cu2(OH)3Cl formation and makes difficulties for metal oxide carbonization to Cu–Al/LDH. Ageing in highly diluted solution contributes not only to Cu–Al/LDH formation but also boehmite hydration that is verified by IR-spectra. The pore structure characteristics have been also discussed. They do not significantly depend on phase composition and vary in ranges of 161.2–172.6 m2/g (specific surface areas), 0.459–0.535 cm2/g (total pore volumes). Pore size distributions reveal that a pore structure is predominantly formed by pore with the sizes from 3 to 22nm; 3.6nm is the size of pores with the largest pore volume.

The influence of support in the synthesis of dimethyl carbonate by Cu-based catalysts

The effects of various anions containing copper based catalysts were studied in regard to the preparation of dimethyl carbonate (DMC) through oxidative carbonylation of methanol under a liquid phase system. A copper compound providing the strong withdrawing power of halides as anion yielded excellent results with respect to the conversion of methanol and selectivity to DMC.However, copper homogenous catalysts suffer from separation of the catalyst after reaction. Thus, the development of a new reaction system using various supports including Y-zeolite was attempted. The conversion of methanol and selectivity to DMC were affected by the properties of the supports. In particular, Y-zeolite showed the best yield among various supports.The influence of various promoters was examined with the aim of increasing the yield of DMC from methanol. The yield of DMC was increased with the addition of alkali metal in the order Li+<Na+<K+, but with selectivity in the order of Li+>Na+>K+, respectively.Various analyses were conducted in order to elucidate these results. From a XRD analysis, the existence of crystal forms of copper chloride hydroxide of Cu/Na/Y-zeolite (dry) was observed. We confirmed the presence of peaks of CuO in Cu/Na/Y-zeolite (550°C). The CO-TPD analysis revealed that CO desorption is an important step to determine the formation of DMC. The addition of NaOH as a co-catalyst resulted in a lower desorption temperature of carbon monoxide in Cu catalyst. Also, XPS analysis results showed that Cu+ on the calcined Cu/Na/Y-zeolite catalyst was formed by the reduction of Cu2+. XANES results provided the difference of reactivity according to the state of the copper catalyst. Activity of this reaction in terms of DMC yields, obtained in the order of CuCl2>Cu/Na/Y-zeolite (dry)>Cu/Na/Y-zeolite (550°C)>Cu(OH)2 was in accordance with the maximum peak of the low photon energy position.

An investigation into the cause of corrosion on indoor bronze sculpture

Corrosion noted on a number of nineteenth and twentieth century indoor bronze sculptures in the collection of the National Gallery of Canada was the cause for a major condition survey of its Canadian, American, and European bronzes. The results led to a comprehensive study, which included material analysis. This article outlines the steps undertaken to determine the extent and type of corrosion, its possible cause(s), and potential remediation. The survey included 136 bronzes, of which 40 were selected for an in-depth study. Indoor air quality tests of the current building, housing the collection since 1988, were carried out. The dossiers and database records of the selected sculptures were reviewed to investigate their condition, treatment, and storage history. The metal, patina, and corrosion products were subjected to analysis. More areas of corrosion were generally associated with predominantly green patinas and chloride-containing compounds identified in either patina or corrosion samples. The most frequently identified compounds in the patina samples were atacamite, a copper(II) chloride hydroxide, and cuprite, a copper(I) oxide. The most frequently identified compounds in the corrosion samples were atacamite and rouaite, a copper(II) hydroxide nitrate. The analysis determined that the current environment is not contributing to the surface alterations of the sculptures; however, past storage conditions, chemical residues from artificial patination, and likely casting residues are the main causes of the current condition.

Synthesis of a Low-Density Copper Oxide Monolithic Aerogel Using Inorganic Salt Precursor

Copper oxide monolithic aerogel was prepared by sol–gel method using inorganic salt as precursor, ethanol as the solvent, and propylene oxide as the gelation agent. Calcination of the as-prepared aerogels at different temperatures induced a phase change which resulted in the formation of a mesoporous copper oxide aerogels. Field emission scanning electron microscopy (FESEM), Highresolution transmission electron microscopy (HRTEM), and Brunauer-Emmett-Teller(BET) methods were used to characterize the as-prepared aerogels. The combined results indicated that the as-prepared CuO aerogel has high porosity, high surface area, and low density. The X-ray diffraction (XRD) patterns show that the as-prepared CuO aerogel is highly crystalline and is identified to be predominantly copper chloride hydroxide, Cu2Cl(OH)3。

Formation of paratacamite nanomaterials via the conversion of aged and oxidized copper nanoparticles in hydrochloric acidic media

Nanoparticles and nanostructured aggregates of paratacamite are prepared in acidic solutions through the conversion of copper-based nanoparticles. Aged and oxidized copper nanoparticles with an average primary particle size of ∼15 nm, when combined with hydrochloric acid solutions in the range of 0.025 to 0.1 M, show interesting behavior yielding both a change in nanoparticle primary size, as measured by an electrospray scanning mobility particle sizer, and in chemical composition to produce a copper chloride hydroxide mineral identified as paratacamite (γ-Cu2(OH)3Cl) by powder X-ray diffraction of the dehydrated solid sample. Taken together, these data suggest that paratacamite nanoparticles in solution can aggregate to yield microporous paratacamite materials. Microporous paratacamite was characterized by several techniques including X-ray diffraction, transmission electron microscopy, energy dispersive X-ray analysis, electron energy loss spectroscopy, X-ray photoelectron spectroscopy and surface area measurements. Oxidation of these copper-based nanoparticles with molecular oxygen and the role of the oxidized layer in the formation of paratacamite have been investigated. Comparison to microscale copper particles showed there is unique oxidation behavior of nanoscale copper particles that results in unique reaction chemistry of oxidized nanoscale copper particles with hydrochloric acid solutions to form paratacamite. This study provides a new route for the formation of paratacamite nanomaterials that can be used in a wide range of chemically interesting applications including hydrogen storage materials and as a heterogeneous catalyst for the synthesis of green solvents such as dimethyl and diethyl carbonates. Additionally, this study suggests a potentially new pathway for the degradation of art objects and ancient artifacts as well as other cultural heritage materials containing small copper particles that has not been previously considered.

AMMINEITE, CuCl2(NH3)2, A NEW SPECIES CONTAINING AN AMMINE COMPLEX: MINERAL DATA AND CRYSTAL STRUCTURE

Ammineite, CuCl 2 (NH 3 ) 2 , the first mineral containing an ammine complex, was discovered at Calleta Pabellon de Pica, Tarapaca region, Chile. The mineral is named for the first described ammine complex as naturally occurring crystals. Ammineite occurs as hypidiomorphic mm-sized blue crystals and also as powdery masses, associated with halite, atacamite, salammoniac and darapskite. The Mohs hardness is 1, the streak is light blue, the luster is vitreous, and the calculated density is 2.38 g/cm 3 at 100 K and 2.31 g/cm 3 at 293 K. The mineral is biaxial positive, with α 1.676(2), β 1.715(2), γ 1.785(2), 2 V calc 76° (for λ 589 nm). The pleochroism for β and γ is dark blue, and for α, light blue; the optical orientation is X = c , Y = b and Z = a . The crystal structure has been solved by direct methods and refined to an R 1 value of 2.4% on the basis of 231 unique observed reflections at 100 K. Ammineite is orthorhombic, space group Cmcm , a 7.688(1), b 10.645(2), c 5.736(1) A, V 469.4(2) A 3 from single-crystal XRD data at 100 K, and a 7.790(1), b 10.643(1), c 5.838(1) A, V 484.1(1) A 3 , from powder XRD data at 293 K, Z = 4. The strongest six X-ray powder-diffraction lines [ d in A( I )( hkl )] are: 6.285(69)(110), 4.278(55)(111), 3.898(56)(200), 2.920(100) (002), 2.763(36)(221) and 2.660(90)(040,112). The chemical composition of ammineite, Cu 37.60, Cl 41.67, N 16.54, H 3.32 wt.%, was determined from both the results of electron microprobe (for Cu and Cl) and elemental analyzer (for N and H). The empirical formula gives Cu 1.00 Cl 1.99 N 1.99 H 5.57 or, ideally, CuCl 2 (NH 3 ) 2 . The basic structural unit, the trans-diammine-dichloridocopper( II) complex, is layered parallel to (001) and connected to the parallel layered complexes up and down nearly perpendicular by two long Cu–Cl bonds. The resulting polyhedron is a [4 + 2]-distorted Cu 2+ N 2 Cl 4 octahedron. The distorted octahedra are connected by shared edges to form zigzag chains running along [001]. The chains are linked by hydrogen bonding between the equatorial NH 3 groups and the equatorial Cl atoms of the adjacent chains. Heating experiments with synthetic CuCl 2 (NH 3 ) 2 in air show that trans-diammine-dichlorido-copper(II) is stable up to 120°C. After 75 hours and heating to 200°C, the sample in air consists of copper chloride hydroxide hydrate and the synthetic analogue of eriochalcite, CuCl 2 ·2H 2 O, whereas the sample of CuCl 2 (NH 3 ) 2 sealed in a glass tube was unchanged after 75 hours at 200°C.

Study on the formation and role of copper chloride hydroxide in the oxidative carbonylation of methanol to dimethyl carbonate

The synthesis of dimethyl carbonate by oxidative carbonylation of methanol over CuCl/SiO2-TiO2 catalysts has been investigated in a slurry reaction system. The γ-Cu2(OH)3Cl crystals were detected by X-ray diffraction on the catalysts after reaction. It was revealed that γ-Cu2(OH)3Cl was formed by CuCl reacting with O2 and by-product water. The catalytic tests showed that γ-Cu2(OH)3Cl was largely inactive for this reaction, may be attributed to its high stability that resisted the Cu+/Cu2+ redox cycle.

Deterioro de aleaciones de cobre por acción humana

Results are presented from several samples taken from leaves of the Pardon Portico of Mosque-Cathedral of Cordoba, where an alteration on their surface was detected. Metal samples analyzed using X-ray microanalysis and powder xray diffraction were predominantly constituted by copper with some amounts of zinc attributed to brass, whereas other samples were also constituted by copper, tin and lead attributed to bronze. Surface samples were analyzed using the same techniques. In addition Fourier transform infrared spectroscopy was also used.The main compound identified in all the surface of the leaves is copper chloride hydroxide (atacamite). Lead chlorides have also been found. These data show that the sudden alteration that appears may be attributed to the use of some cleaning product containing chloride. Other compounds detected in the surface were gypsum, quartz and oxalates coming from environmental contamination.

Effect of treatment temperature on the crystal structure of activated carbon supported CuCl2–PdCl2 catalysts in the oxidative carbonylation of ethanol to diethyl carbonate

Diethyl carbonate (DEC) was prepared via oxidative carbonylation of ethanol over a heterogeneous Wacker-type catalyst supported by activated carbon (AC). The active species of copper chloride hydroxide crystals has a great effect on the catalytic performance and chemical adsorption capacities. Cu(OH)Cl crystal is the most active catalyst for the diethyl carbonate synthesis. In situ XRD technique was used to analyze the effect of treatment temperature on the crystal structures of catalyst in the oxidative carbonylation of ethanol to diethyl carbonate. Cu(OH)Cl was easily formed at 523K, which showed the best catalytic activities. γ-Cu2(OH)3Cl was formed at 573K, which showed lower catalytic activities in the synthesis of DEC. CuO was formed at the treatment temperature of 673K, which increased the yield of by-products—acetaldehyde and ethyl acetate. The catalytic performance of three catalysts of CuCl2–PdCl2–KCl–NaOH/AC prepared at the different treatment temperatures above indicated the same trend which could be ascribed to the in situ effects on the catalysts under the reaction conditions.

A study of the uptake of copper ions by nanostructured calcium silicate

Presented is a study of the removal of copper ions from dilute aqueous solutions by nanostructured calcium silicate. Two different copper sources, copper nitrate and copper chloride, at various concentrations ranging from 10 to 5000 mg kg −1 copper have been investigated. The uptake of copper ions from aqueous solutions at concentrations below 500 mg kg −1 is 97% and higher within 30 min at silicate loadings of 1 g kg −1. The formation of crystals of copper hydroxide nitrate, Cu 2(OH) 3NO 3, and copper chloride hydroxide, Cu 2(OH) 3Cl, on the surface of the silicate have been observed. Reaction rates and possible mechanisms characterising the uptake have been investigated and discussed.