High concentrations of copper ions(Cu(Ⅱ)) in water will pose health risks to humans and the ecological environment. Therefore, this study aims to utilize ultrasonic-cured modified municipal solid waste incineration(M...High concentrations of copper ions(Cu(Ⅱ)) in water will pose health risks to humans and the ecological environment. Therefore, this study aims to utilize ultrasonic-cured modified municipal solid waste incineration(MSWI) fly ash for Cu(Ⅱ) adsorption to achieve the purpose of “treating waste by waste.” The effects of p H, adsorption time, initial concentration, and temperature on the modified MSWI fly ash’s adsorption efficiency were systematically studied in this article. The adsorption performance of the modified MSWI fly ash can be enhanced by the ultrasonic modification. At pH = 2, 3 and 4, the adsorption capacity of the modified MSWI fly ash for Cu(Ⅱ) increased by 2.7, 1.9 and 1.2 times, respectively. Furthermore, it was suggested that the adsorption process of the modified MSWI fly ash can be better simulated by the pseudo-second-order kinetic model, with a maximum adsorption capacity calculated by the Langmuir model of 24.196 mg.g-1. Additionally, the adsorption process is spontaneous,endothermic, and chemisorption-dominated from the thermodynamic studies(ΔH and ΔS > 0, ΔG < 0).Finally, the enhanced adsorption performance of the modified MSWI fly ash for Cu(Ⅱ) may be attributed to electrostatic interaction and chelation effects.展开更多
A new binuclear Cu（Ⅱ） complex with nitronyl nitroxide radicals [Cu（NIT3Py）2Cl2]2（NIT3Py = 2-（3＇-pyridinyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been synthesized and structurally characterized b...A new binuclear Cu（Ⅱ） complex with nitronyl nitroxide radicals [Cu（NIT3Py）2Cl2]2（NIT3Py = 2-（3＇-pyridinyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in monoclinic,space group C2/c with a = 38.483（4）,b = 7.2450（8）,c = 27.559（3） ,β = 134.0180（10）°,V = 5525.6（10） 3,C48H64Cl4Cu2N12O8,Mr = 1206.00,Z = 4,Dc = 1.450 g/cm3,μ（MoKα） = 1.025 mm-1,F（000） = 2504,S = 1.066,the final R = 0.0471 and wR = 0.1121 for 3286 observed reflections（I 2σ（I））.The title complex consists of centrosymmetric dinuclear units [Cu（NIT3Py）2Cl2]2,in which the copper ions are square-pyramidally coordinated by two pyridyl nitrogen atoms of two radical ligands and three chlorine anions,two of which bridge the copper ions.The magnetic measurements show ferromagnetic interactions between the copper ions and the radical ligands.展开更多
A new compound （NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-（2＇-chlor-5＇- nitrophenyl）-3-oxide-l-oxyl） 1 and its complex （Cu（NIT-mNO2）（hfac）2） 2 have been synthesized and structurally and magnetically c...A new compound （NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-（2＇-chlor-5＇- nitrophenyl）-3-oxide-l-oxyl） 1 and its complex （Cu（NIT-mNO2）（hfac）2） 2 have been synthesized and structurally and magnetically characterized. Complex 1 crystallizes in monoclinic, space group P211n with a = 10.6798（9）, b = 11.2705（9）, c = 12.9559（10）A, β = 107.3770（10）°, V = 1488.3（2） A^3, C13H15ClN3O4, Mr = 312.73, Z = 4, Dc = 1.396 g/cm^3, g（MoKa） = 0.276 mm^-1, F（000） = 652, the final R = 0.0606 and wR = 0.1773 for 3405 independent reflections with Rint = 0.0203. The nitronyl nitroxide unit （imidazoline ring） is not coplanar with the phenyl ring with the dihedral angle between them of 55.75°. The compound results in a 1-D zig-zag chain structure by intermolecular H-bond interaction. Compound 2 crystallizes in triclinic, space group Pi with a = 10.3699（10）, b = 10.6286（11）, c = 15.1683（15）A, a = 77.5330（10）, ,β = 773080（10）, y = 87.3420（10）＊, V = 1592.5（3） A^3, C23HITCIFI2N3O8Cu, Mr = 790.39, Z = 2, Dc = 1.648 g/cm^3, μ（MoKa） = 0.888 mm^-1, F（000） = 788, the final R = 0.0793 and wR = 0.2153 for 5794 independent reflections with Rint = 0.0196. The Cu（Ⅱ） ion is located at a center of symmetry, and each Cu（Ⅱ） is surrounded by six oxygen atoms at the vertices of a distorted tetragonal octahedron. Four of the six oxygen atoms belong to two hfac ligands and occupy the equatorial coordination sites, while the other two of NIT-mNO2 act as μ-1,5 bridge between the Cu（Ⅱ） ion, thus forming a 1-D chain structure. The magnetic susceptibility data indicate intermolecular antiferromagnetic interactions between compound 1 and intrachain ferromagnetic behaviors.展开更多
A new copper（Ⅱ） complex, [Cu（BMI）4（SO4）]·DMF·2H2O （BMI = benzimidazole）, has been synthesized by the treatment of CuCN with 2-mercaptobenzimidazole in the presence of 1,10-phenanthroline, and charac...A new copper（Ⅱ） complex, [Cu（BMI）4（SO4）]·DMF·2H2O （BMI = benzimidazole）, has been synthesized by the treatment of CuCN with 2-mercaptobenzimidazole in the presence of 1,10-phenanthroline, and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 17.6260（4）, b = 11.1252（3）, c = 18.6573（4）A°, β= 107.9010（10）°, V = 3481.45（14）A°^3, Z = 4, C31H35CuN9O7S, Mr= 741.28, F（000） = 1540, Dc = 1.414 g/cm^3,μ = 0.746 mm^-1, the final R = 0.0649 and wR = 0.1609 for 4382 observed reflections with I 〉 2σ（I）. The Cu（Ⅱ） atom is coordinated by five unidentate ligands （one sulfate and four benzimidazole ligands） generated in situ, displaying a slightly distorted square pyramid geometry.展开更多
A new dinuclear copper complex, [Cu（C9H11N3）Cl2]2（C18H22Cl4Cu2N6）, has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic P1^- space group with a = 7.526（3）, b ...A new dinuclear copper complex, [Cu（C9H11N3）Cl2]2（C18H22Cl4Cu2N6）, has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic P1^- space group with a = 7.526（3）, b = 9.473（4）, c = 9.535（3）A, α = 117.214（10）, β = 108.251（9）, γ = 91.560（6）°, V = 562.3（4）A^3, Z = 1, Mr = 591.30, F（000） = 298, Dc = 1.746 g/cm^3, μ（MoKα） = 2.385 mm^-1, the final R = 0.0577 and wR = 0.1248 for 2188 unique reflections with 1629 observed ones （Ⅰ〉 2σ（Ⅰ））. In the title complex, each copper（Ⅱ） atom is located at the center of a distorted trigonal bipyramid of five coordination atoms （two nitrogen and three chlorine atoms）. Two copper（Ⅱ） atoms were bridged by two chlorine anions （Cl（2） and Cl（2a）） to form a Cu（Ⅱ）-Cu（Ⅱ） binuclear entity with the distance between two copper（Ⅱ） atoms of 3.398 （A）.展开更多
A new dinuclear copper complex, [Cu（C13HgN2O）Cl]2.（CH3CN）2 （C30H24C12Cu2N6O2）, has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclirile system, space group P1, w...A new dinuclear copper complex, [Cu（C13HgN2O）Cl]2.（CH3CN）2 （C30H24C12Cu2N6O2）, has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclirile system, space group P1, with a = 7.6677（14）, b = 9.2375（17）, c = 11.227（2） ]A, α = 81.338（3）,β = 88.173（4）, γ = 66.199（3）°, V = 718.9（2） ]A^3, Z = 1, Mr = 698.53, F（000） = 354, Dc = 1.613 g/cm^3, μ（MoKa） = 1.705 mm^-1, the final R = 0.0645 and wR = 0.1364 for 2474 unique reflections with 1809 observed ones （I 〉 20（I））. In the title complex, each copper（H） atom is located at the center of a distorted tetrahedron consisting of four coordinate atoms （one nitrogen atom, two oxygen anions, and one chlorine atom）. Two copper（Ⅱ） atoms are bridged by two oxygen anions （O（1） and O（la）） of two phenolates to form a Cu（Ⅱ）-Cu（Ⅱ） binuclear entity, and the distance between two copper（Ⅱ） atoms is 3.0144（15） A.展开更多
Four new Cu（Ⅱ） complexes with two benzotriazole-based ligands, [Cu2（L^1）2（NO3）2]· 2H2O （1）, [Cu2（L^1）2]·2ClO4·2H2O （2）, [Cu2（HL^2）2（NO3）4]·2CH3COCH3 （3） and [Cu（HL^2）2（Cl）]&#...Four new Cu（Ⅱ） complexes with two benzotriazole-based ligands, [Cu2（L^1）2（NO3）2]· 2H2O （1）, [Cu2（L^1）2]·2ClO4·2H2O （2）, [Cu2（HL^2）2（NO3）4]·2CH3COCH3 （3） and [Cu（HL^2）2（Cl）]·Cl·2CH2Cl2 （4）, where HL^1 = 1,3-bis（benzotriazol-2-yl）-2-propanol and HL^2 = 1,3-bis（benzotriazol-1-yl）-2-propanol, were synthesized and structurally characterized by elemental analyses, IR and single-crystal X-ray diffraction analyses. It is revealed that complexes 1～3 have dinuclear structures, while 4 possesses a one-dimensional （1-D） chain structure, which extends in two orthogonal orientations. In 1～4, the coordination numbers of Cu（Ⅱ） centers range from four to six, which may be attributed to the different geometries and coordination abilities of the ligands and anions. The L^1 ligand in complexes 1 and 2 adopts a tridentate di-chelating coordination mode, whereas ligand HL^2 in complexes 3 and 4 has a bidentate bridging coordination mode. The different coordination modes of these two ligands may be explained by the different charges of nitrogen donor atoms in the benzotriazole ring, which has been investigated by density functional theory （DFT） calculations.展开更多
Reaction of the ligand dmpt（dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline）with CuCl2 afforded mixed valent Cu（Ⅰ）/Cu（Ⅱ） discrete tetranuclear complexes[Cu（Ⅱ）Cl2（dmpt）Cu（Ⅰ）Cl]（1）,while the reaction of ...Reaction of the ligand dmpt（dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline）with CuCl2 afforded mixed valent Cu（Ⅰ）/Cu（Ⅱ） discrete tetranuclear complexes[Cu（Ⅱ）Cl2（dmpt）Cu（Ⅰ）Cl]（1）,while the reaction of ligand dppz（dppz = dipyrido[3,2-a：20,30-c]phenazine） with divalent halogen copper salt CuX2（X=Cl,Br） gave one-dimensional chain mixed valent Cu（Ⅰ）/Cu（Ⅱ） complexes [Cu（Ⅱ）Cl2（dppz）Cu（Ⅰ）Cl]n（2） and discrete mixed valent Cu（Ⅰ）/Cu（Ⅱ）complexes [Cu（Ⅱ）Br2（dppz）（DMF）Cu（Ⅰ）Br]（3）. Complex 2 consists of a one-dimensional chain-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-Cl-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-with Cu（Ⅱ） and Cu（Ⅰ） atoms linked together by chloride anion. Complex 3 is a discrete complex,which is the same as complexes 1 and 2 involving two different copper valent Cu（Ⅰ） and Cu（Ⅱ）. The Cu（Ⅰ） ion presents a pseudo-trihedral geometry,while the Cu（Ⅱ） ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover,halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.展开更多
基金supported by the key program of the National Natural Science Foundation of China(52236008).
文摘High concentrations of copper ions(Cu(Ⅱ)) in water will pose health risks to humans and the ecological environment. Therefore, this study aims to utilize ultrasonic-cured modified municipal solid waste incineration(MSWI) fly ash for Cu(Ⅱ) adsorption to achieve the purpose of “treating waste by waste.” The effects of p H, adsorption time, initial concentration, and temperature on the modified MSWI fly ash’s adsorption efficiency were systematically studied in this article. The adsorption performance of the modified MSWI fly ash can be enhanced by the ultrasonic modification. At pH = 2, 3 and 4, the adsorption capacity of the modified MSWI fly ash for Cu(Ⅱ) increased by 2.7, 1.9 and 1.2 times, respectively. Furthermore, it was suggested that the adsorption process of the modified MSWI fly ash can be better simulated by the pseudo-second-order kinetic model, with a maximum adsorption capacity calculated by the Langmuir model of 24.196 mg.g-1. Additionally, the adsorption process is spontaneous,endothermic, and chemisorption-dominated from the thermodynamic studies(ΔH and ΔS > 0, ΔG < 0).Finally, the enhanced adsorption performance of the modified MSWI fly ash for Cu(Ⅱ) may be attributed to electrostatic interaction and chelation effects.
基金supported by the National Natural Science Foundation of China (No. 20901059)the Technological Development Foundation Project of Tianjin Educational Committee (No. 20080503)
文摘A new binuclear Cu（Ⅱ） complex with nitronyl nitroxide radicals [Cu（NIT3Py）2Cl2]2（NIT3Py = 2-（3＇-pyridinyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in monoclinic,space group C2/c with a = 38.483（4）,b = 7.2450（8）,c = 27.559（3） ,β = 134.0180（10）°,V = 5525.6（10） 3,C48H64Cl4Cu2N12O8,Mr = 1206.00,Z = 4,Dc = 1.450 g/cm3,μ（MoKα） = 1.025 mm-1,F（000） = 2504,S = 1.066,the final R = 0.0471 and wR = 0.1121 for 3286 observed reflections（I 2σ（I））.The title complex consists of centrosymmetric dinuclear units [Cu（NIT3Py）2Cl2]2,in which the copper ions are square-pyramidally coordinated by two pyridyl nitrogen atoms of two radical ligands and three chlorine anions,two of which bridge the copper ions.The magnetic measurements show ferromagnetic interactions between the copper ions and the radical ligands.
基金the National Natural Science Foundation of China (No. 20471026)Natural Science Foundation of Henan Province (No. 0311021200) the Foundation of Education Committee of Henan Province (2006150017)
文摘A new compound （NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-（2＇-chlor-5＇- nitrophenyl）-3-oxide-l-oxyl） 1 and its complex （Cu（NIT-mNO2）（hfac）2） 2 have been synthesized and structurally and magnetically characterized. Complex 1 crystallizes in monoclinic, space group P211n with a = 10.6798（9）, b = 11.2705（9）, c = 12.9559（10）A, β = 107.3770（10）°, V = 1488.3（2） A^3, C13H15ClN3O4, Mr = 312.73, Z = 4, Dc = 1.396 g/cm^3, g（MoKa） = 0.276 mm^-1, F（000） = 652, the final R = 0.0606 and wR = 0.1773 for 3405 independent reflections with Rint = 0.0203. The nitronyl nitroxide unit （imidazoline ring） is not coplanar with the phenyl ring with the dihedral angle between them of 55.75°. The compound results in a 1-D zig-zag chain structure by intermolecular H-bond interaction. Compound 2 crystallizes in triclinic, space group Pi with a = 10.3699（10）, b = 10.6286（11）, c = 15.1683（15）A, a = 77.5330（10）, ,β = 773080（10）, y = 87.3420（10）＊, V = 1592.5（3） A^3, C23HITCIFI2N3O8Cu, Mr = 790.39, Z = 2, Dc = 1.648 g/cm^3, μ（MoKa） = 0.888 mm^-1, F（000） = 788, the final R = 0.0793 and wR = 0.2153 for 5794 independent reflections with Rint = 0.0196. The Cu（Ⅱ） ion is located at a center of symmetry, and each Cu（Ⅱ） is surrounded by six oxygen atoms at the vertices of a distorted tetragonal octahedron. Four of the six oxygen atoms belong to two hfac ligands and occupy the equatorial coordination sites, while the other two of NIT-mNO2 act as μ-1,5 bridge between the Cu（Ⅱ） ion, thus forming a 1-D chain structure. The magnetic susceptibility data indicate intermolecular antiferromagnetic interactions between compound 1 and intrachain ferromagnetic behaviors.
基金This work was supported by the NNSF of China (Nos. 20471061 and 30170229) and the Science & Technology Innovation Foundation for the Young Scholar of Fujian Province (No. 2005J059)
文摘A new copper（Ⅱ） complex, [Cu（BMI）4（SO4）]·DMF·2H2O （BMI = benzimidazole）, has been synthesized by the treatment of CuCN with 2-mercaptobenzimidazole in the presence of 1,10-phenanthroline, and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 17.6260（4）, b = 11.1252（3）, c = 18.6573（4）A°, β= 107.9010（10）°, V = 3481.45（14）A°^3, Z = 4, C31H35CuN9O7S, Mr= 741.28, F（000） = 1540, Dc = 1.414 g/cm^3,μ = 0.746 mm^-1, the final R = 0.0649 and wR = 0.1609 for 4382 observed reflections with I 〉 2σ（I）. The Cu（Ⅱ） atom is coordinated by five unidentate ligands （one sulfate and four benzimidazole ligands） generated in situ, displaying a slightly distorted square pyramid geometry.
基金This work was supported by the National Natural Science Foundation of China (No. 20571058)the Natural Science Foundation of Hubei Province (No. 2005ABA022) the Science and Technology Tackle Key Foundation of Hubei Province (No. 2005AA401C54)
文摘A new dinuclear copper complex, [Cu（C9H11N3）Cl2]2（C18H22Cl4Cu2N6）, has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic P1^- space group with a = 7.526（3）, b = 9.473（4）, c = 9.535（3）A, α = 117.214（10）, β = 108.251（9）, γ = 91.560（6）°, V = 562.3（4）A^3, Z = 1, Mr = 591.30, F（000） = 298, Dc = 1.746 g/cm^3, μ（MoKα） = 2.385 mm^-1, the final R = 0.0577 and wR = 0.1248 for 2188 unique reflections with 1629 observed ones （Ⅰ〉 2σ（Ⅰ））. In the title complex, each copper（Ⅱ） atom is located at the center of a distorted trigonal bipyramid of five coordination atoms （two nitrogen and three chlorine atoms）. Two copper（Ⅱ） atoms were bridged by two chlorine anions （Cl（2） and Cl（2a）） to form a Cu（Ⅱ）-Cu（Ⅱ） binuclear entity with the distance between two copper（Ⅱ） atoms of 3.398 （A）.
基金This work was supported by the National Natural Science Foundation of China (No. 20571058)the Natural Science Foundation of Hubei Province (No. 2005ABA022) the Science and Technology Tackle Key Foundation of Hubei Province (No. 2005AA401C54)
文摘A new dinuclear copper complex, [Cu（C13HgN2O）Cl]2.（CH3CN）2 （C30H24C12Cu2N6O2）, has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclirile system, space group P1, with a = 7.6677（14）, b = 9.2375（17）, c = 11.227（2） ]A, α = 81.338（3）,β = 88.173（4）, γ = 66.199（3）°, V = 718.9（2） ]A^3, Z = 1, Mr = 698.53, F（000） = 354, Dc = 1.613 g/cm^3, μ（MoKa） = 1.705 mm^-1, the final R = 0.0645 and wR = 0.1364 for 2474 unique reflections with 1809 observed ones （I 〉 20（I））. In the title complex, each copper（H） atom is located at the center of a distorted tetrahedron consisting of four coordinate atoms （one nitrogen atom, two oxygen anions, and one chlorine atom）. Two copper（Ⅱ） atoms are bridged by two oxygen anions （O（1） and O（la）） of two phenolates to form a Cu（Ⅱ）-Cu（Ⅱ） binuclear entity, and the distance between two copper（Ⅱ） atoms is 3.0144（15） A.
基金supported by the National Natural Science Foundation of China (Nos. 50673043 and 20801029) 863 Project of the Ministry of Science and Technology of China (No. 2006AA020502)
文摘Four new Cu（Ⅱ） complexes with two benzotriazole-based ligands, [Cu2（L^1）2（NO3）2]· 2H2O （1）, [Cu2（L^1）2]·2ClO4·2H2O （2）, [Cu2（HL^2）2（NO3）4]·2CH3COCH3 （3） and [Cu（HL^2）2（Cl）]·Cl·2CH2Cl2 （4）, where HL^1 = 1,3-bis（benzotriazol-2-yl）-2-propanol and HL^2 = 1,3-bis（benzotriazol-1-yl）-2-propanol, were synthesized and structurally characterized by elemental analyses, IR and single-crystal X-ray diffraction analyses. It is revealed that complexes 1～3 have dinuclear structures, while 4 possesses a one-dimensional （1-D） chain structure, which extends in two orthogonal orientations. In 1～4, the coordination numbers of Cu（Ⅱ） centers range from four to six, which may be attributed to the different geometries and coordination abilities of the ligands and anions. The L^1 ligand in complexes 1 and 2 adopts a tridentate di-chelating coordination mode, whereas ligand HL^2 in complexes 3 and 4 has a bidentate bridging coordination mode. The different coordination modes of these two ligands may be explained by the different charges of nitrogen donor atoms in the benzotriazole ring, which has been investigated by density functional theory （DFT） calculations.
基金Supported by the Science and Technology Planning Project of Shengli College China University of Petroleum(No.13070316)
文摘Reaction of the ligand dmpt（dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline）with CuCl2 afforded mixed valent Cu（Ⅰ）/Cu（Ⅱ） discrete tetranuclear complexes[Cu（Ⅱ）Cl2（dmpt）Cu（Ⅰ）Cl]（1）,while the reaction of ligand dppz（dppz = dipyrido[3,2-a：20,30-c]phenazine） with divalent halogen copper salt CuX2（X=Cl,Br） gave one-dimensional chain mixed valent Cu（Ⅰ）/Cu（Ⅱ） complexes [Cu（Ⅱ）Cl2（dppz）Cu（Ⅰ）Cl]n（2） and discrete mixed valent Cu（Ⅰ）/Cu（Ⅱ）complexes [Cu（Ⅱ）Br2（dppz）（DMF）Cu（Ⅰ）Br]（3）. Complex 2 consists of a one-dimensional chain-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-Cl-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-with Cu（Ⅱ） and Cu（Ⅰ） atoms linked together by chloride anion. Complex 3 is a discrete complex,which is the same as complexes 1 and 2 involving two different copper valent Cu（Ⅰ） and Cu（Ⅱ）. The Cu（Ⅰ） ion presents a pseudo-trihedral geometry,while the Cu（Ⅱ） ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover,halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.
