The chronological data obtained by a variety of dating methods have confirmed that the sodium enriched metavolcanite series in the area of the Longbohe copper deposit at Jinping, Yunnan Province, was formed during the...The chronological data obtained by a variety of dating methods have confirmed that the sodium enriched metavolcanite series in the area of the Longbohe copper deposit at Jinping, Yunnan Province, was formed during the Proterozoic (its Pb-Pb isochron age=1595±75 Ma), corresponding to the Dahongshan Group sodium enriched metavolcanites. The Sm-Nd isochron age of 1336±46Ma should represent the time at which this series of volcanic rocks experienced spilitization in response to sodium metasomatism, equivalent to the time of sedimentation of the Ailaoshan Group and Yashan Group rocks. The Rb-Sr ages of the volcanic rocks and the Pb-Pb ages of copper ores have recorded the events of strong dynamic metamorphism and of strong reworking-metallogenesis of copper during the Jinningian period. Similarities in forming age, rock assemblage and isotopic characteristics between the sodium enriched metavolcanite series and the Dahongshan Group sodium enriched metavolcanite series have provided new clues to the exploration of the Dahongshan-type copper deposits in this area.展开更多
Platinum-group elements (PGE) in PGE-rich porphyry copper (gold) deposits are mainly Pt and Pd, whereas the concentrations of other PGE (Ru, Rh, Os, Ir) are significantly low. Moreover, Pt and Pd mainly exist in...Platinum-group elements (PGE) in PGE-rich porphyry copper (gold) deposits are mainly Pt and Pd, whereas the concentrations of other PGE (Ru, Rh, Os, Ir) are significantly low. Moreover, Pt and Pd mainly exist in sulfides in the forms of crystal lattice or tiny platinum-group mineral (PGM) inclusions. The present data show that there is a positive relationship between Pt and Pd concentrations and Cu (Au) in porphyry copper (gold) deposits. The comparison of chondrite-normalized PGE distribution patterns between the ore-bearing porphyry intrusions and ore-barren porphyry intrusions in arc setting, 187^Os/188^Os, 87^Sr/86^Sr and S isotopes for porphyry copper (gold) deposits shows that PGEs were mainly derived from the mantle, and fluids from subduction zones devoted trivial PGE to the magma. The porphyry copper (gold) deposits associated with subducted events are most probably enriched in PGE, whereas those related to crustal thickening, lithospheric delamination or underplating rarely concentrate PGE. The osmium isotopic compositions in porphyry copper (gold) deposits reveal that (187^Os/188^Os)i values are highly variable and not lower than those of primitive upper mantle (PUM) and mantle peridotite, however, osmium concentrations are commonly lower than mantle peridotite, suggesting that parental magmas of some porphyry intrusions had experienced crustal contamination during magma evolution. Experimental investigations have proved that PGE exist in the forms of Cl^- and HS^- complexes during transportation and migration of the oreforming fluids. This paper summarizes previous studies including crucial controlling factors and mechanisms for PGE enrichment, and points out that the mantle-derived magmas parental to porphyry intrusions are the prerequisite for PGE enrichment in porphyry copper (gold) deposits. Favorable physical and chemical conditions (including salinity, temperature, pressure, pH, and oxygen fugacity) in hydrothermal fluids crucially control the PGE enrichment, and sulfur concentrations of melts play important roles in this process as well.展开更多
Copper dust with high arsenic content is a hazardous waste that should be treated properly.Herein,the copper dust is oxidized,leached,and separated at room temperature and atmospheric pressure.To separate As and Bi,pa...Copper dust with high arsenic content is a hazardous waste that should be treated properly.Herein,the copper dust is oxidized,leached,and separated at room temperature and atmospheric pressure.To separate As and Bi,part of As(Ⅲ)in copper dust is oxidized to As(V),so that most of the As,Cu,and Zn elements enter the solution and the Bi remains in the leaching residue.Also,the influence of several factors,such as H_(2)SO_(4) dosage,H_(2)O_(2) dosage,liquid-solid ratio,leaching temperature and leaching time,on the leaching percentage of As,Bi,Cu,and Zn is systematically investigated.The optimal conditions are obtained as follows:liquid-solid ratio of 3:1,H_(2)O_(2) dosage of 10 ml/50 g(dust),H_(2)SO_(4) dosage of 4.5 ml/50 g(dust),leaching temperature of 85 C,and leaching time of 3 h.Under these conditions,the leaching percentage of As,Cu,Zn,and Bi is found to be 97.39%,96.11%,97.32%,and 2.40%,respectively.For further recovery of As from the leaching solution,the one-step recycle leaching of the leaching solution is performed to increase the concentration of As in the recycled leaching solution.The concentration of arsenic in the recycling leaching solution is found to be 79.63 g·L^(-1),which is beneficial for the study on further recovery of As_(2)O_(3).展开更多
Electrochemical conversion of nitrate(NO_(3)~-) to ammonia(NH_(3)) can target two birds with one stone well, in NO_(3)^(-)-containing sewage remediation and sustainable NH_(3) production. However, single metalbased ca...Electrochemical conversion of nitrate(NO_(3)~-) to ammonia(NH_(3)) can target two birds with one stone well, in NO_(3)^(-)-containing sewage remediation and sustainable NH_(3) production. However, single metalbased catalysts are difficult to drive high-efficient NO_(3)~- removal due to the multi-electron transfer steps.Herein, we present a tandem catalyst with simple structure, Cu-Co binary metal oxides(Cu-Co-O), by engineering intermediate phases as catalytic active species for NO_(3)~- conversion. Electrochemical evaluation,X-ray photoelectron spectroscopy, and in situ Raman spectra together suggest that the newly-generated Cu-based phases was prone to NO_(3)~- to NO_(2)~- conversion, then NO_(2)~- was reduced to NH_(3) on Co-based species. At an applied potential of -1.1 V vs. saturated calomel electrode, the Cu-Co-O catalyst achieved NO_(3)~- -N removal of 90% and NH_(3) faradaic efficiency of 81% for 120 min in 100 m L of 50 mg/L NO_(3)~- -N,consuming only 0.69 k Wh/mol in a two-electrode system. This study provides a facile and efficient engineering strategy for developing high-performance catalysts for electrocatalytic nitrate conversion.展开更多
According to the chemical and phase composition of the nickel-copper-iron matte containing precious metals and the progress in enrichment of precious metals from the nickel-copper-iron matte containing precious metals...According to the chemical and phase composition of the nickel-copper-iron matte containing precious metals and the progress in enrichment of precious metals from the nickel-copper-iron matte containing precious metals at home and abroad, this paper put forward the process route of enrichment of precious metals and selectively leaching of base metals from the nickel-copper-iron matte by sulfuric acid and sodium hypochlorite. The effects of particle size, leaching temperature, leaching time, amount of sulfuric acid and sodium hypochlorite on the leaching rate of nickel, cobalt, copper and iron are mainly discussed. The results show that raw material particle size has significantly effects on the leaching rate of base metals, high leaching rate of base metals and enrichment of precious metals are obtained with the suitable particle size. Through the experiments, the reasonable experiment parameters and conditions were determined as fellows: particle size of-200 to +250 mesh, leaching temperature 95℃ , leaching time 5 h, sulfuric acid concentration 30%, adding amount of sodium hypochlorite 3 times of matte weight. Under these experiment parameters and conditions, the leaching rate of nickel, cobalt, copper and iron were 97.39%, 96.24%, 98.30% and 99.01%, respectively. The content of nickel, cobalt, copper, iron in the leaching residues was 8.15%, 0.23%, 1.40% and 0.24%, respectively. The content of Pt, Pd, Au, Ag and Rh in the leaching residues was 247 g/t, 521 g/t, 112 g/t, 494 g/t and 24 g/t, respectively. The content of Pt, Pd, Au, Ag and Rh in the leaching solution was <0.0005 g/L, 0.0023 g/L, 0.0007 g/L, <0.0005 g/L and 0.00017 g/L, respectively. This process has advantages as follows: a small investment, simple technology, high enrichment efficiency.展开更多
Bioavailability of heavy metals in soil organic matter depends on its components. Characterization of heavy metal distributions in different fractions of soil organic matter is needed for better understanding of the f...Bioavailability of heavy metals in soil organic matter depends on its components. Characterization of heavy metal distributions in different fractions of soil organic matter is needed for better understanding of the fate of heavy metals. This study investigated the accumulation and partitioning of copper and zinc among different size particulate organic matter (POM) fractions in polluted soils from a former iron ore processing site in western Shaoxing County, Zhejiang Province. Physical fractionations were carried out to separate soil primary particles according to their size and density. Copper and Zn had a heterogeneous distribution among soil particle fractions. Copper and Zn were significantly (p < 0.05) enriched in the POM fractions. > 0.05 mm POM and < 0.05 mm fine soil fractions were mainly responsible for Cu and Zn retention in soils. The POM fraction contained up to 1 322 mg Cu kg-1 and 1 115 mg Zn kg-1 and the fine soil fraction contained up to 422 mg Cu kg-1 and 537 mg Zn kg-1. The total POM fraction was responsible for 15.8%-41.2% and 12.2%-31.7% of the total amount of Cu and Zn, respectively, in the polluted soils. The percentages of Cu and Zn associated with organic matter in < 0.05 mm fine soil fractions for the polluted soils ranged from 14.1% to 24.5%, and 5.4% to 15.8%, respectively. Accumulation of soil organic matter could increase enrichment of Gu (or Zn) in the POM fractions. Also, Cu provided a greater enrichment in the POM fractions than Zn.展开更多
Process intensification using liquid emulsion membranes (LEMs) for extraction of copper has been studied in this work. In LEM process the extraction and stripping processes are combined in one stage. The solubility of...Process intensification using liquid emulsion membranes (LEMs) for extraction of copper has been studied in this work. In LEM process the extraction and stripping processes are combined in one stage. The solubility of the solute or the chemical affinity between the solute and carrier reagent in the membrane results in the separation of the solute from the feed mixture. In this work the membrane phase comprised of LIX 664N as the extractant dissolved in kerosene and Span 80 as surfactant. The stripping phase was sulfuric acid with 180 g/l concentration and feed phase had copper concentration of 3.5 g/l. Effect of various process parameters such as batch contact time, speed of agitation, W:O ratio and treat ratio has been experimentally investigated to get better insight of the process. The maximum enrichment of copper in the internal phase obtained was 11.6 times with batch contact time of 10 minutes, agitation speed of 300 rpm and treat ratio of 6:1.展开更多
1 Introduction Sareke glutenite-type copper deposit is the large size copper deposit discovered in recent years,and it is located Sarekebayi intracontinental pull-apart basin in the western margin of the Tarim basin.C...1 Introduction Sareke glutenite-type copper deposit is the large size copper deposit discovered in recent years,and it is located Sarekebayi intracontinental pull-apart basin in the western margin of the Tarim basin.Conglomerate of展开更多
This paper discusses the enrichment and depletion regularities for porphyry coppermolybdenum ore deposits in different regions and varied deposit genetic types in the same area, taking three porphyry copper-molybdenum...This paper discusses the enrichment and depletion regularities for porphyry coppermolybdenum ore deposits in different regions and varied deposit genetic types in the same area, taking three porphyry copper-molybdenum ore deposits (i.e., the Chengmenshan in Jiangxi, Wunugetushan in Inner Mongolia, Baishantang in Gansu) and two copper deposits in Gansu Province (the Huitongshan skarn deposit and Gongpoquan composite deposit) as case studies. The results show that porphyry Cu-Mo deposits or skarn copper deposits include both enrichment of the ore-forming elements and associated elements, and depletion of some lithophile dispersed elements, rare earth elements (REE) and some major elements. And the depleted elements vary with deposits, having generality and their own features. On a deposit scale, the positive anomalies of enriched elements and negative anomalies of depleted elements follow in a sequence to comprise regular anomaly models of spatial structures. The exploration in the Tongchang deposit in Jiangxi and Huitongshan deposit in Gansu suggests that anomaly models play a key role in the identification of mineral occurrences and deposits compared to one single enriched element anomaly. And the anomaly models exert a critical effect on the optimization of prospecting targets and their potential evaluation.展开更多
A new Cu(Ⅱ) complex [Cu(4-cba)(1,10-phen)(H2O)2](NO3) (4-Hcba = 4-cyanobenzoic acid) has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characteriz...A new Cu(Ⅱ) complex [Cu(4-cba)(1,10-phen)(H2O)2](NO3) (4-Hcba = 4-cyanobenzoic acid) has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data: C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420(2), b = 9.1070(2), c = 15.1140(6) A, a = 76.889(9), β = 81.332(11), γ = 74.844( 11)°, V = 1009.89(5) A^3, Z = 2, Dc = 1.605 g/cm^3, F(000) = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ(Ⅰ). The Cu(Ⅱ) atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.展开更多
A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallograph...A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.展开更多
The influence of chloride or sulphur dioxide on the corrosion behavior of copper tube in the air-conditioning system was studied using scanning electron microscope (SEM), energy dispersion spectrometer (EDS) and cycli...The influence of chloride or sulphur dioxide on the corrosion behavior of copper tube in the air-conditioning system was studied using scanning electron microscope (SEM), energy dispersion spectrometer (EDS) and cyclic polarization techniques. The results showed that the corrosion of copper tube are mainly caused by the SO42- and Cl- ions in the circulating water, and the former is mainly responsible for the general corrosion of the copper tube whilst the latter for the pitting corrosion. The different influences of SG42- and Cl- ions on the corrosion type of copper tube may be attributed to that the radius of SO42- ion is much larger than that of Cl- ion. Meanwhile the results also indicated that SO42- inhibits the pitting corrosion caused by Cl- and Cl- inhibits the general corrosion initiated by SO42- due to their competitive adsorption on the copper matrix.展开更多
One novel copper(II)-organic compound,namely Cu[Cu2(PP)2](CBPC)2]·2(H2O)(1,H2CBPC = 1-[(2'-carboxybiphenyl-4-yl)methyl]-2-propylimidazole-4-carboxylic acid,HPP = 3-(2-pyridyl)pyrazole),was designed...One novel copper(II)-organic compound,namely Cu[Cu2(PP)2](CBPC)2]·2(H2O)(1,H2CBPC = 1-[(2'-carboxybiphenyl-4-yl)methyl]-2-propylimidazole-4-carboxylic acid,HPP = 3-(2-pyridyl)pyrazole),was designed and synthesized under hydrothermal conditions.X-ray diffraction analysis reveals that two Cu(II)ions in the quasi-planar dimmer of [Cu2(PP)2] are linked by the carboxylate oxygen atoms on the phenyl ring and the imidazole ring,respectively,yielding one snake-shaped structure.Magnetic measurements reveal that compound 1 shows the strongly antiferromagnetic property.Crystal data of 1:C58H52Cu3N10O10,Mr = 1239.72,monoclinic,P21/c,a = 14.900(7),b = 15.029(7),c = 12.308(6),β = 102.519(9)o,V = 2691(2)3,Z = 2,Dc = 1.530 g/cm3,F(000)= 1274,μ = 1.246 mm-1,R = 0.0416,wR = 0.0780(I 2σ(I))and S = 0.999.展开更多
Two new metal-organic complexes [Cd2(1,4-BDC)(4-pytyp)(H2O)4]·(1,4-BDC)(1) and [Cu2(1,4-BDC)(4-pytyp)2(H2O)2]·(1,4-BDC)·8H2O(2)(4-pytyp = 4'-(4''-pyridyl)-2,2':6',2''-terp...Two new metal-organic complexes [Cd2(1,4-BDC)(4-pytyp)(H2O)4]·(1,4-BDC)(1) and [Cu2(1,4-BDC)(4-pytyp)2(H2O)2]·(1,4-BDC)·8H2O(2)(4-pytyp = 4'-(4''-pyridyl)-2,2':6',2''-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.展开更多
One novel 1-D copper(Ⅱ)-organic compound,namely {[Cu2(PP)2(CBPC)]2·7H2O}n(1,H2CBPC=1-[(2'-carboxybiphenyl-4-yl)methyl]-2-propylimidazole-4-carboxylic acid,HPP=3-(2-pyridyl)pyrazole),was synthesized ...One novel 1-D copper(Ⅱ)-organic compound,namely {[Cu2(PP)2(CBPC)]2·7H2O}n(1,H2CBPC=1-[(2'-carboxybiphenyl-4-yl)methyl]-2-propylimidazole-4-carboxylic acid,HPP=3-(2-pyridyl)pyrazole),was synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that the two Cu(Ⅱ) ions in the distorted dimer [Cu2(PP)2] of 1 are linked by the carboxylate oxygen atoms on the phenyl and imidazole rings,respectively,forming one interesting snake-like chain.Single-crystal X-ray analyses reveal that it crystallizes in monoclinic,space group C2/c with a=30.656(8),b=12.715(3),c=22.405(5),β=122.758(3)°,V=7344(3)3,Z=4,Mr=1681.65,Dc=1.521 g/cm3,F(000)=3464,μ=1.221 mm-1,the final R=0.0453 and wR=0.1023 for 4617 observed reflections with Ⅰ 〉2σ(Ⅰ).展开更多
The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H1...The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?展开更多
A new asymmetric bidentate copper(Ⅱ) complex,CuL 2(HL=2-((E)-(4-bromophenylimino)methyl)-6-bromo-4-chlorophenol),has been synthesized and characterized by elemental analyses and single-crystal X-ray diffrac...A new asymmetric bidentate copper(Ⅱ) complex,CuL 2(HL=2-((E)-(4-bromophenylimino)methyl)-6-bromo-4-chlorophenol),has been synthesized and characterized by elemental analyses and single-crystal X-ray diffraction.The complex crystallizes in the monoclinic space group P2 1 /c with a=11.218(3),b=9.355(3),c=13.449(4),β=108.722(4)°,V=1336.8(6)3,Z=2,Dc=2.008 g/cm 3,μ(MoKα)=7.024 mm-1,F(000)=806,S=0.999,the final R=0.0342 and wR=0.0641for2611observed reflections (I〉2σ(I)).The central copper(Ⅱ) is four-coordinate and bonds to two nitrogen and two oxygen atoms from two Schiff base ligands.The complex is linked into a two-dimensional supramolecular structure by weak intermolecular interactions.In addition,DNA-binding properties of the metal complex were investigated using spectrometric titrations and viscosity measurements.The results show that the complex binds with calf-thymus DNA(CT-DNA),presumably via a partial intercalative mode.The intrinsic binding constant of the Cu(Ⅱ) complex with DNA is 7.335×10 3 M-1.展开更多
A copper(Ⅱ) complex Cu(L)2(NO3)2 constructed by the L (L = N-(4,6-dimethoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea) ligand crystallizes in monoclinic, space group C2/c with a = 16.2416(16), b = 9.1385...A copper(Ⅱ) complex Cu(L)2(NO3)2 constructed by the L (L = N-(4,6-dimethoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea) ligand crystallizes in monoclinic, space group C2/c with a = 16.2416(16), b = 9.1385(7), c = 22.0008(18) A, β = 108.077(2)°, V = 3104.3(5) A^3, Dc = 1.627 g/cm^3, Z = 4, C20H28CuN10O14S2, Mr = 760.18,μ(MoKa) = 0.920 mm^-1, F(000) = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections (I 〉 2σ(I)). X-ray diffraction shows the existence of weak complementary intramolecular N-H...O (DA) hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu(Ⅱ) ion, intermolecular C-H...O hydrogen bonds and weak π...π stacking interactions, leading to the formation of a multi-dimensional supramolecular network.展开更多
文摘The chronological data obtained by a variety of dating methods have confirmed that the sodium enriched metavolcanite series in the area of the Longbohe copper deposit at Jinping, Yunnan Province, was formed during the Proterozoic (its Pb-Pb isochron age=1595±75 Ma), corresponding to the Dahongshan Group sodium enriched metavolcanites. The Sm-Nd isochron age of 1336±46Ma should represent the time at which this series of volcanic rocks experienced spilitization in response to sodium metasomatism, equivalent to the time of sedimentation of the Ailaoshan Group and Yashan Group rocks. The Rb-Sr ages of the volcanic rocks and the Pb-Pb ages of copper ores have recorded the events of strong dynamic metamorphism and of strong reworking-metallogenesis of copper during the Jinningian period. Similarities in forming age, rock assemblage and isotopic characteristics between the sodium enriched metavolcanite series and the Dahongshan Group sodium enriched metavolcanite series have provided new clues to the exploration of the Dahongshan-type copper deposits in this area.
基金supported by the 12th Five-Year Plan project of State Key Laboratory of Ore Deposit Geochemistry,Chinese Academy of Sciences(SKLOG-ZY125-06)the Knowledge Innovation Project,Chinese Academic Sciences(KZCX2-YW-136-1)
文摘Platinum-group elements (PGE) in PGE-rich porphyry copper (gold) deposits are mainly Pt and Pd, whereas the concentrations of other PGE (Ru, Rh, Os, Ir) are significantly low. Moreover, Pt and Pd mainly exist in sulfides in the forms of crystal lattice or tiny platinum-group mineral (PGM) inclusions. The present data show that there is a positive relationship between Pt and Pd concentrations and Cu (Au) in porphyry copper (gold) deposits. The comparison of chondrite-normalized PGE distribution patterns between the ore-bearing porphyry intrusions and ore-barren porphyry intrusions in arc setting, 187^Os/188^Os, 87^Sr/86^Sr and S isotopes for porphyry copper (gold) deposits shows that PGEs were mainly derived from the mantle, and fluids from subduction zones devoted trivial PGE to the magma. The porphyry copper (gold) deposits associated with subducted events are most probably enriched in PGE, whereas those related to crustal thickening, lithospheric delamination or underplating rarely concentrate PGE. The osmium isotopic compositions in porphyry copper (gold) deposits reveal that (187^Os/188^Os)i values are highly variable and not lower than those of primitive upper mantle (PUM) and mantle peridotite, however, osmium concentrations are commonly lower than mantle peridotite, suggesting that parental magmas of some porphyry intrusions had experienced crustal contamination during magma evolution. Experimental investigations have proved that PGE exist in the forms of Cl^- and HS^- complexes during transportation and migration of the oreforming fluids. This paper summarizes previous studies including crucial controlling factors and mechanisms for PGE enrichment, and points out that the mantle-derived magmas parental to porphyry intrusions are the prerequisite for PGE enrichment in porphyry copper (gold) deposits. Favorable physical and chemical conditions (including salinity, temperature, pressure, pH, and oxygen fugacity) in hydrothermal fluids crucially control the PGE enrichment, and sulfur concentrations of melts play important roles in this process as well.
基金This work was financially supported by the Fundamental Research Funds for the Central South University. Postdoctoral Research Foundation of Central South University (140050037).
文摘Copper dust with high arsenic content is a hazardous waste that should be treated properly.Herein,the copper dust is oxidized,leached,and separated at room temperature and atmospheric pressure.To separate As and Bi,part of As(Ⅲ)in copper dust is oxidized to As(V),so that most of the As,Cu,and Zn elements enter the solution and the Bi remains in the leaching residue.Also,the influence of several factors,such as H_(2)SO_(4) dosage,H_(2)O_(2) dosage,liquid-solid ratio,leaching temperature and leaching time,on the leaching percentage of As,Bi,Cu,and Zn is systematically investigated.The optimal conditions are obtained as follows:liquid-solid ratio of 3:1,H_(2)O_(2) dosage of 10 ml/50 g(dust),H_(2)SO_(4) dosage of 4.5 ml/50 g(dust),leaching temperature of 85 C,and leaching time of 3 h.Under these conditions,the leaching percentage of As,Cu,Zn,and Bi is found to be 97.39%,96.11%,97.32%,and 2.40%,respectively.For further recovery of As from the leaching solution,the one-step recycle leaching of the leaching solution is performed to increase the concentration of As in the recycled leaching solution.The concentration of arsenic in the recycling leaching solution is found to be 79.63 g·L^(-1),which is beneficial for the study on further recovery of As_(2)O_(3).
基金supported by National Natural Science Foundation of China (Nos.52131003 and 42007180)Special Research Assistant Program of Chinese Academy of Science, Natural Science Foundation of Chongqing (No.cstc2020jcyj-msxm X0775)+1 种基金Scientific Research Instrument Development Project of Chinese Academy of Sciences (No.YJKYYQ20200044)Outstanding Scientist of Chongqing Talent Program (No.CQYC20210101288)。
文摘Electrochemical conversion of nitrate(NO_(3)~-) to ammonia(NH_(3)) can target two birds with one stone well, in NO_(3)^(-)-containing sewage remediation and sustainable NH_(3) production. However, single metalbased catalysts are difficult to drive high-efficient NO_(3)~- removal due to the multi-electron transfer steps.Herein, we present a tandem catalyst with simple structure, Cu-Co binary metal oxides(Cu-Co-O), by engineering intermediate phases as catalytic active species for NO_(3)~- conversion. Electrochemical evaluation,X-ray photoelectron spectroscopy, and in situ Raman spectra together suggest that the newly-generated Cu-based phases was prone to NO_(3)~- to NO_(2)~- conversion, then NO_(2)~- was reduced to NH_(3) on Co-based species. At an applied potential of -1.1 V vs. saturated calomel electrode, the Cu-Co-O catalyst achieved NO_(3)~- -N removal of 90% and NH_(3) faradaic efficiency of 81% for 120 min in 100 m L of 50 mg/L NO_(3)~- -N,consuming only 0.69 k Wh/mol in a two-electrode system. This study provides a facile and efficient engineering strategy for developing high-performance catalysts for electrocatalytic nitrate conversion.
基金The National Basic Research Program (973 Plan)of China (2012CB724201)
文摘According to the chemical and phase composition of the nickel-copper-iron matte containing precious metals and the progress in enrichment of precious metals from the nickel-copper-iron matte containing precious metals at home and abroad, this paper put forward the process route of enrichment of precious metals and selectively leaching of base metals from the nickel-copper-iron matte by sulfuric acid and sodium hypochlorite. The effects of particle size, leaching temperature, leaching time, amount of sulfuric acid and sodium hypochlorite on the leaching rate of nickel, cobalt, copper and iron are mainly discussed. The results show that raw material particle size has significantly effects on the leaching rate of base metals, high leaching rate of base metals and enrichment of precious metals are obtained with the suitable particle size. Through the experiments, the reasonable experiment parameters and conditions were determined as fellows: particle size of-200 to +250 mesh, leaching temperature 95℃ , leaching time 5 h, sulfuric acid concentration 30%, adding amount of sodium hypochlorite 3 times of matte weight. Under these experiment parameters and conditions, the leaching rate of nickel, cobalt, copper and iron were 97.39%, 96.24%, 98.30% and 99.01%, respectively. The content of nickel, cobalt, copper, iron in the leaching residues was 8.15%, 0.23%, 1.40% and 0.24%, respectively. The content of Pt, Pd, Au, Ag and Rh in the leaching residues was 247 g/t, 521 g/t, 112 g/t, 494 g/t and 24 g/t, respectively. The content of Pt, Pd, Au, Ag and Rh in the leaching solution was <0.0005 g/L, 0.0023 g/L, 0.0007 g/L, <0.0005 g/L and 0.00017 g/L, respectively. This process has advantages as follows: a small investment, simple technology, high enrichment efficiency.
基金Project supported by the Natural Science Foundation of Zhejiang Province (No. M403038).
文摘Bioavailability of heavy metals in soil organic matter depends on its components. Characterization of heavy metal distributions in different fractions of soil organic matter is needed for better understanding of the fate of heavy metals. This study investigated the accumulation and partitioning of copper and zinc among different size particulate organic matter (POM) fractions in polluted soils from a former iron ore processing site in western Shaoxing County, Zhejiang Province. Physical fractionations were carried out to separate soil primary particles according to their size and density. Copper and Zn had a heterogeneous distribution among soil particle fractions. Copper and Zn were significantly (p < 0.05) enriched in the POM fractions. > 0.05 mm POM and < 0.05 mm fine soil fractions were mainly responsible for Cu and Zn retention in soils. The POM fraction contained up to 1 322 mg Cu kg-1 and 1 115 mg Zn kg-1 and the fine soil fraction contained up to 422 mg Cu kg-1 and 537 mg Zn kg-1. The total POM fraction was responsible for 15.8%-41.2% and 12.2%-31.7% of the total amount of Cu and Zn, respectively, in the polluted soils. The percentages of Cu and Zn associated with organic matter in < 0.05 mm fine soil fractions for the polluted soils ranged from 14.1% to 24.5%, and 5.4% to 15.8%, respectively. Accumulation of soil organic matter could increase enrichment of Gu (or Zn) in the POM fractions. Also, Cu provided a greater enrichment in the POM fractions than Zn.
文摘Process intensification using liquid emulsion membranes (LEMs) for extraction of copper has been studied in this work. In LEM process the extraction and stripping processes are combined in one stage. The solubility of the solute or the chemical affinity between the solute and carrier reagent in the membrane results in the separation of the solute from the feed mixture. In this work the membrane phase comprised of LIX 664N as the extractant dissolved in kerosene and Span 80 as surfactant. The stripping phase was sulfuric acid with 180 g/l concentration and feed phase had copper concentration of 3.5 g/l. Effect of various process parameters such as batch contact time, speed of agitation, W:O ratio and treat ratio has been experimentally investigated to get better insight of the process. The maximum enrichment of copper in the internal phase obtained was 11.6 times with batch contact time of 10 minutes, agitation speed of 300 rpm and treat ratio of 6:1.
基金supported by the metallogenic regularities and prediction of glutenite type Cu-Pb-Zn deposit in Tarim west margin(201511016-1)the special mapping techniques and its application demonstration in Sareke overall-exploration area in Xinjiang(12120114081501)
文摘1 Introduction Sareke glutenite-type copper deposit is the large size copper deposit discovered in recent years,and it is located Sarekebayi intracontinental pull-apart basin in the western margin of the Tarim basin.Conglomerate of
基金financially supported by the research special fund of public service sector from the Ministry of Land and Resources (No. 201111008)
文摘This paper discusses the enrichment and depletion regularities for porphyry coppermolybdenum ore deposits in different regions and varied deposit genetic types in the same area, taking three porphyry copper-molybdenum ore deposits (i.e., the Chengmenshan in Jiangxi, Wunugetushan in Inner Mongolia, Baishantang in Gansu) and two copper deposits in Gansu Province (the Huitongshan skarn deposit and Gongpoquan composite deposit) as case studies. The results show that porphyry Cu-Mo deposits or skarn copper deposits include both enrichment of the ore-forming elements and associated elements, and depletion of some lithophile dispersed elements, rare earth elements (REE) and some major elements. And the depleted elements vary with deposits, having generality and their own features. On a deposit scale, the positive anomalies of enriched elements and negative anomalies of depleted elements follow in a sequence to comprise regular anomaly models of spatial structures. The exploration in the Tongchang deposit in Jiangxi and Huitongshan deposit in Gansu suggests that anomaly models play a key role in the identification of mineral occurrences and deposits compared to one single enriched element anomaly. And the anomaly models exert a critical effect on the optimization of prospecting targets and their potential evaluation.
基金This work was supported by the NSF for Distinguished Young Scientist of China (20425104) and the NSF of Fujian Province (A0420002, 2005I017)
文摘A new Cu(Ⅱ) complex [Cu(4-cba)(1,10-phen)(H2O)2](NO3) (4-Hcba = 4-cyanobenzoic acid) has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data: C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420(2), b = 9.1070(2), c = 15.1140(6) A, a = 76.889(9), β = 81.332(11), γ = 74.844( 11)°, V = 1009.89(5) A^3, Z = 2, Dc = 1.605 g/cm^3, F(000) = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ(Ⅰ). The Cu(Ⅱ) atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.
基金Supported by the National Natural Science Foundation of China(No.21607051)Institute Foundation of Siping City(No.2017057)the Science and Technology Research Projects of the Education Committee of Jilin Province(No.JJKH20180779KJ)
文摘A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.
文摘The influence of chloride or sulphur dioxide on the corrosion behavior of copper tube in the air-conditioning system was studied using scanning electron microscope (SEM), energy dispersion spectrometer (EDS) and cyclic polarization techniques. The results showed that the corrosion of copper tube are mainly caused by the SO42- and Cl- ions in the circulating water, and the former is mainly responsible for the general corrosion of the copper tube whilst the latter for the pitting corrosion. The different influences of SG42- and Cl- ions on the corrosion type of copper tube may be attributed to that the radius of SO42- ion is much larger than that of Cl- ion. Meanwhile the results also indicated that SO42- inhibits the pitting corrosion caused by Cl- and Cl- inhibits the general corrosion initiated by SO42- due to their competitive adsorption on the copper matrix.
基金supported by Financial support from the Natural Science Foundation of Shandong (BR2010BQ023) and Qilu Normal University
文摘One novel copper(II)-organic compound,namely Cu[Cu2(PP)2](CBPC)2]·2(H2O)(1,H2CBPC = 1-[(2'-carboxybiphenyl-4-yl)methyl]-2-propylimidazole-4-carboxylic acid,HPP = 3-(2-pyridyl)pyrazole),was designed and synthesized under hydrothermal conditions.X-ray diffraction analysis reveals that two Cu(II)ions in the quasi-planar dimmer of [Cu2(PP)2] are linked by the carboxylate oxygen atoms on the phenyl ring and the imidazole ring,respectively,yielding one snake-shaped structure.Magnetic measurements reveal that compound 1 shows the strongly antiferromagnetic property.Crystal data of 1:C58H52Cu3N10O10,Mr = 1239.72,monoclinic,P21/c,a = 14.900(7),b = 15.029(7),c = 12.308(6),β = 102.519(9)o,V = 2691(2)3,Z = 2,Dc = 1.530 g/cm3,F(000)= 1274,μ = 1.246 mm-1,R = 0.0416,wR = 0.0780(I 2σ(I))and S = 0.999.
基金Supported by the Program for New Century Excellent Talents in University(NCET-10-0176)the Natural Science Foundation of Jilin Province(No.20130521019JH)the fund of Jilin Provincial Education Department of China(No.2014154)
文摘Two new metal-organic complexes [Cd2(1,4-BDC)(4-pytyp)(H2O)4]·(1,4-BDC)(1) and [Cu2(1,4-BDC)(4-pytyp)2(H2O)2]·(1,4-BDC)·8H2O(2)(4-pytyp = 4'-(4''-pyridyl)-2,2':6',2''-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.
基金supported by the Chinese Academy of Sciences (KJCX2-YW-M05,KJCX2-YW-319)the Natural Science Foundation of Fujian Province (2007HZ0001-1,2009HZ0004-1)
文摘One novel 1-D copper(Ⅱ)-organic compound,namely {[Cu2(PP)2(CBPC)]2·7H2O}n(1,H2CBPC=1-[(2'-carboxybiphenyl-4-yl)methyl]-2-propylimidazole-4-carboxylic acid,HPP=3-(2-pyridyl)pyrazole),was synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that the two Cu(Ⅱ) ions in the distorted dimer [Cu2(PP)2] of 1 are linked by the carboxylate oxygen atoms on the phenyl and imidazole rings,respectively,forming one interesting snake-like chain.Single-crystal X-ray analyses reveal that it crystallizes in monoclinic,space group C2/c with a=30.656(8),b=12.715(3),c=22.405(5),β=122.758(3)°,V=7344(3)3,Z=4,Mr=1681.65,Dc=1.521 g/cm3,F(000)=3464,μ=1.221 mm-1,the final R=0.0453 and wR=0.1023 for 4617 observed reflections with Ⅰ 〉2σ(Ⅰ).
基金This work was supported by the foundation of Natural Science Research of Jiangsu Education Department (02KJB150007)
文摘The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?
文摘A new asymmetric bidentate copper(Ⅱ) complex,CuL 2(HL=2-((E)-(4-bromophenylimino)methyl)-6-bromo-4-chlorophenol),has been synthesized and characterized by elemental analyses and single-crystal X-ray diffraction.The complex crystallizes in the monoclinic space group P2 1 /c with a=11.218(3),b=9.355(3),c=13.449(4),β=108.722(4)°,V=1336.8(6)3,Z=2,Dc=2.008 g/cm 3,μ(MoKα)=7.024 mm-1,F(000)=806,S=0.999,the final R=0.0342 and wR=0.0641for2611observed reflections (I〉2σ(I)).The central copper(Ⅱ) is four-coordinate and bonds to two nitrogen and two oxygen atoms from two Schiff base ligands.The complex is linked into a two-dimensional supramolecular structure by weak intermolecular interactions.In addition,DNA-binding properties of the metal complex were investigated using spectrometric titrations and viscosity measurements.The results show that the complex binds with calf-thymus DNA(CT-DNA),presumably via a partial intercalative mode.The intrinsic binding constant of the Cu(Ⅱ) complex with DNA is 7.335×10 3 M-1.
基金the National Natural Science Foundation of China (No.20571060)Education Committee of Shaanxi Province (05JK294)Xi'an Scientific and Technical Plan Project (No. YF07106)
文摘A copper(Ⅱ) complex Cu(L)2(NO3)2 constructed by the L (L = N-(4,6-dimethoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea) ligand crystallizes in monoclinic, space group C2/c with a = 16.2416(16), b = 9.1385(7), c = 22.0008(18) A, β = 108.077(2)°, V = 3104.3(5) A^3, Dc = 1.627 g/cm^3, Z = 4, C20H28CuN10O14S2, Mr = 760.18,μ(MoKa) = 0.920 mm^-1, F(000) = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections (I 〉 2σ(I)). X-ray diffraction shows the existence of weak complementary intramolecular N-H...O (DA) hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu(Ⅱ) ion, intermolecular C-H...O hydrogen bonds and weak π...π stacking interactions, leading to the formation of a multi-dimensional supramolecular network.