The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0....The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.展开更多
Converting carbon dioxide(CO2)into value-added chemicals by CO2 reduction has been considered as a potential way to solve the current energy crisis and environmental problem.Among the methods of CO2 reduction,the elec...Converting carbon dioxide(CO2)into value-added chemicals by CO2 reduction has been considered as a potential way to solve the current energy crisis and environmental problem.Among the methods of CO2 reduction,the electrochemical method has been widely used due to its mild reaction condition and high reaction efficiency.In the electrochemical reduction system,the CO2 electrocatalyst is the most important part.Although many CO2 electrocatalysts have been developed,efficient catalysts with high activity,selectivity and stability are still lacking.Copper sulfide compound,as a low-toxicity and emerging material,has broad prospects in the field of CO2 reduction due to its unique structural and electrochemical properties.Much progress has been achieved with copper sulfide nanocrystalline and the field is rapidly developing.This paper summarizes the preparation,recent progress in development,and factors affecting the electrocatalytic CO2 reduction performance with copper sulfide compound as a catalyst.Prospects for future development are also outlined,with the aim of using copper sulfide compound as a highly active and stable electrocatalyst for CO2 reduction.展开更多
Two new compounds,1（[Cu（IDB_）2]Cl_2·2CH_3CH_2OH·2H_2O（IDB = N,N-di（2-benzimidazolylmethyl）imine]） and 2（[Cu（EDTB）]·2[C_6H_4（OH）COO]·6H_2O（EDTB = N,N,N＇,N＇-tetrakis-[（2-benzimidazoly...Two new compounds,1（[Cu（IDB_）2]Cl_2·2CH_3CH_2OH·2H_2O（IDB = N,N-di（2-benzimidazolylmethyl）imine]） and 2（[Cu（EDTB）]·2[C_6H_4（OH）COO]·6H_2O（EDTB = N,N,N＇,N＇-tetrakis-[（2-benzimidazolyl）methyl]-1,2-ethanediamine]）,have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Crystal 1 belongs to the triclinic system,space group P1 with a = 9.565（2）,b = 9.863（2）,c = 10.252（3） ？,α = 81.915,β = 88.330,γ = 87.347°,V = 956.28（40） ？3,Z = 1,F（000） = 427,D_c = 1.419 g/cm3,Mr = 817.27 and μ（MoKα） = 0.764 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0505,wR = 0.1417; R indices（all data）： R = 0.0591,wR = 0.1525. Crystal 2 is of triclinic system,space group P1 with a = 11.487（3）,b = 13.396（4）,c = 17.977（5） ？,α = 73.899（5）,β = 86.629（5）,γ = 65.018（4）°,V = 2403.8（12） ？3,Z = 2,F（000） = 1072,D3c = 1.417 g/cm,Mr = 1025.54,μ（MoKα） = 0.528 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0769,w R = 0.163 2; R indices（all data）： R = 0.0769,wR = 0.1632. The two compounds exhibit mononuclear structures. The copper（Ⅱ） atom of crystal 1 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand IDB to adopt a distorted octahedral coordination geometry. The copper（Ⅱ） atom of crystal 2 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand EDTB to show a distorted octahedral coordination geometry. Particularly,the two compounds exhibit fluorescent properties at room temperature in ethanol.展开更多
A novel compound Cu（phen）（m-CBA）2 was synthesized with m-chlorobenzoic acid（m-CBA）, 1,10-phenanthroline（phen） and Cu（OAc）2·H2O. It was characterized by IR, UV, elemental analyses and X-ray crystallograp...A novel compound Cu（phen）（m-CBA）2 was synthesized with m-chlorobenzoic acid（m-CBA）, 1,10-phenanthroline（phen） and Cu（OAc）2·H2O. It was characterized by IR, UV, elemental analyses and X-ray crystallography. It crystallizes in the monoclinic crystal system with C2/c space group, a=2.9699（4） nm, b=1.15452（2） nm, c=1.5335（2） nm, β=111.118（2）°, V=4.905 1（1） nm3, Z=8, F（000）=2 328, R1=0.072 8, wR2=0.223 4 [I2σ（I）]. Structure analysis shows that the copper center coordinates with two nitrogen atoms from one 1,10-phenanthroline molecule, two oxygen atoms from two m-chlorobenzoic acid molecules, giving a distorted squared planar coordination geometry. This novel compound shows paramagnetic interactions between copper centers.展开更多
The title compounds 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid（C11H9Cl N2O2, HL）（1） and [Cu（L）2（H2O）]（2） were prepared and structurally characterized by elemental analysis, IR and single-crysta...The title compounds 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid（C11H9Cl N2O2, HL）（1） and [Cu（L）2（H2O）]（2） were prepared and structurally characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compound 1（C11H9Cl N2O2） crystallizes in the monoclinic system, space group P21/n with a = 7.249（3）, b = 20.515（10）, c = 7.249（3）,β= 96.30°, V = 1071.6（9） ？3, Z = 4, Mr = 236.65, Dc = 1.467 g/cm3, F（000） = 488, GOOF = 1.029, μ= 0.341 mm-1, the final R = 0.0736 and w R = 0.1966 for 1500 observed reflections with I 〉 2σ（I）. Compound 2（C22H18Cl2Cu N4O5） crystallizes in the monoclinic system, space group P21/c with a = 7.2931（6）, b = 24.548（2）, c = 13.2726（11）, β= 99.4040（10）°, V = 2344.2（3） ？3, Z = 4, Mr = 552.84, Dc = 1.566 g/cm3, F（000） = 1124, GOOF = 1.050, μ= 1.201 mm-1, the final R = 0.0376 and w R = 0.1000 for 3626 observed reflections with I 〉 2σ（I）. 1 and 2 are connected through hydrogen bonding interactions to generate 2D and 3D supramolecular structures, respectively. Moreover, the preliminary antibacterial activities of 1 and 2 against the gram positive bacteria（S. aureus, C. albicans and B. subtilis） and gram negative bacteria（E. coli and P. aeruginosa） have been tested by using the microdilution method, and the results indicate that 2 is more active than 1 against the tested bacteria.展开更多
A metal-organic coordination compound formulated as [Cu（MOPIP）（BDC）]n·0.5n（H2O） 1 （MOPIP - 2-（4-methoxyphenyl）-1H-imidazo[4,5-f][1,10] phenanthroline, BDC = 1,4-benze Nedicarboxylate） has been hydrother...A metal-organic coordination compound formulated as [Cu（MOPIP）（BDC）]n·0.5n（H2O） 1 （MOPIP - 2-（4-methoxyphenyl）-1H-imidazo[4,5-f][1,10] phenanthroline, BDC = 1,4-benze Nedicarboxylate） has been hydrothermally synthesized and structurally characterized by elemental analysis, thermogravimetric analysis, IR spectrum, and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P1^-, with a = 8.872（5）, b = 11.163（6）, c = 12.589（6）A, α = 94.687（7）, β = 99.930（6）, γ = 103.074（7）°, V = 1186.7（12）A^3, C28H19CuN4O5.5, Mr= 563.01, Dc = 1.576 g/cm^3,μ（MoKa） = 0.973 mm^-1, F（000） = 576, Z = 2, the final R = 0.0607 and wR = 0.1618 for 3419 observed reflections （I 〉 2σ（I））.展开更多
The mixed ligand coordination compound of copper with norfloxacin (NFLX) and 1, 10-phen has been synthesized and characterized by means of X-ray single crystal diffraction. The structure features of the coordination ...The mixed ligand coordination compound of copper with norfloxacin (NFLX) and 1, 10-phen has been synthesized and characterized by means of X-ray single crystal diffraction. The structure features of the coordination compound are described. Antibacterial activities of the coordination compound have been tested against different microorganisms. The antitumor activities of the coordination compound on leukemia HL-60 cell line and liver cancer BEL-7402 cell line have been measured, respectively. The results indicated that the coordination compound has strong inhibitory effect on HL-60 and BEL-7402 cell lines.展开更多
The title compound [Cu（C11H29N5）]（ClO4）2 was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The compound crystallizes in the monoclinic system, space group P21/n with...The title compound [Cu（C11H29N5）]（ClO4）2 was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The compound crystallizes in the monoclinic system, space group P21/n with α = 9.405（2）, b = 14.495（3）, c = 14.715（3） A, β= 90.262（3）°, V=2006.1（7） A^3,M,=493.83,Z=4,F）（000）= 1028,Dc= 1.635 g/cm^3, T= 298（2） K,μ= 1.403 mm^-1 and = 0.71073 A. The was refined to R = 0.0508 and wR = 0. 1250 for 2293 observed reflections with I 〉 2σ（I）. The Cu（Ⅱ） atom possesses a five-coordtinate CuN5 environment which shows a slightly distorted square-pyramidal geonetry. Antimicrobial activity study found that the complex is active against Salmonella species, Staphylococcus aureu, Bacillus pumilus and Bacillus coliforms.展开更多
A novel copper（II） coordination polymer of {[Cu3L2（4,4＂-bipy）4]（CIO4）2＂20H20}, （1） was synthesized by the reaction of H2L （C6HsN（CH2COOH）2, phenyliminodiacetic acid）, CuSO4.5H20, NaCIO4.H20 and 4,4＂-bi...A novel copper（II） coordination polymer of {[Cu3L2（4,4＂-bipy）4]（CIO4）2＂20H20}, （1） was synthesized by the reaction of H2L （C6HsN（CH2COOH）2, phenyliminodiacetic acid）, CuSO4.5H20, NaCIO4.H20 and 4,4＂-bipy （4,4＂-bipyridine） in water/methanol, followed by slow evaporating at room temperature. The compound was characterized by elemental analysis （EA）, infrared spectroscopy （IR）, thermogravimetric analysis （TGA） and single-crystal/powder X-ray diffraction. The result of single-crystal X-ray diffraction analysis reveals that 1 crystallizes in the monoclinic crystal system with C2/c space group, a = 2.9974（4）, b = 1.7270（2）, c = 2.0007（3） nm, fl = 128.793（2）°, V= 8.0722（19） nm3, Z = 4, Dc = 1.472 g.cm-3,/a = 0.942 mm-1, F（000） = 3716, R= 0.0487 and wR = 0.1204 （I 〉 20（/））. The basic structural unit of 1 is a trinuclear cluster unit of [Cu3L2]2＋, which is constructed by two #2-L2- ligands bridging and chelating three Cu（Ⅱ） ions. These [Cu3L2]2＋ units are connected with each other by 4,4＂-bipy ligands to generate a 2D cation brickwall-like network of [Cu3L2（4,4＂-bipy）4]n2n＋. These adjacent 2D cation layers are further stacked in a staggered fashion via interlayer stacking interactions to form a 3D supramolecular structure with 1D open square channels, in which the C104- counter anions and lattice water molecules are filled. Furthermore, the magnetic property of 1 was also investigated.展开更多
An extensive series of experiments was carried out in order to identify suitable catalysts to boost the reaction rate of wet air oxidation of real textile wastewaters at relatively mild temperature and pressure. Exper...An extensive series of experiments was carried out in order to identify suitable catalysts to boost the reaction rate of wet air oxidation of real textile wastewaters at relatively mild temperature and pressure. Experimental results indicated that all catalysts tested in this investigation had shown an impressive increase in the initial COD and TOC removal rate as well as the COD and TOC removal levels in two hours reaction. Among all the catalysts tested, copper salts were more effective than the rest. Anions of the salt solutions also played a role in the catalytic process with nitrate ions having better effect than sulfate ions. Hence copper nitrates were more effective than copper sulfates. It was also found that a mixture of salts with different metals performed better than either of the component single salt alone.展开更多
Since the discovery of superconductivity of the BiSrCuO system at 20K, the work of synthesizing high Tc superconductors without rare-earths by adding some elements other than rare-earths in the BiSrCuO system has made...Since the discovery of superconductivity of the BiSrCuO system at 20K, the work of synthesizing high Tc superconductors without rare-earths by adding some elements other than rare-earths in the BiSrCuO system has made a lot of progress. Recently, N. Fukushima et al. have synthesized Bi4Sr4RE2Cu4O16+δ (RE = Nd, Eu or Y) by substituting RE for Ca in the Bi4Sr4Ca2Cu4O16+δ superconductor and revealed that it has a crystal structure identical with this superconductor, but it is an insulator. In this paper, the authors report the superconductivity and structure of the BiSrCaEuCuO compound synthesized by adding 5 at% of rare-earth Eu in the BiSrCaCuO system.展开更多
The title compound, [Cu（phen）2（SO4）（H2O）]·0.5C4H4O4·7H2O （phen = 1,10-phe-nan throline and C4H4O4 = fumaric acid）, has been synthesized and characterized by single-crystal X-ray diffraction. The crys...The title compound, [Cu（phen）2（SO4）（H2O）]·0.5C4H4O4·7H2O （phen = 1,10-phe-nan throline and C4H4O4 = fumaric acid）, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 11.4827（2）, b = 11.9086（2）, c = 13.77350（10） A, α = 80.6830（10）, β = 66.6480（10）, γ = 64.048000）°, V = 1554.63（4） A^3, Mr = 722.17, Z = 2, Dc = 1.543 g/cm^3,μ = 0.845 mm^-1, F（000） = 750, R = 0.0349 and wR = 0.0837 for 4754 observed reflections （1 〉 2σ（I））. The compound contains a six-coordinated copper（Ⅱ） center, which is surround by four N atoms of two phen ligands （Cu-N distances in the range of 1.997（2）- 2.225（2） A）, one sulfate O atom （Cu-O = 2.0037（17） A） and one water O atom （Cu-O（Sw） = 2.719（2） A,） in a distorted octahedral geometry. Extensive hydrogen-bonding interactions are involved in water molecules, ligated sulfate anions and fumaric acid molecules. In addition, π-π interactions via aromatic nitrogen-containing ligands are also discussed. The combination of non-covalent interactions leads to the formation of a 3-D network structure.展开更多
The new compound, （H3O）2[Cu3Cl3（H2O）3（NC9H12.5O6）2] 1, has been synthesized by the hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction. The crystal is of hexagonal, space g...The new compound, （H3O）2[Cu3Cl3（H2O）3（NC9H12.5O6）2] 1, has been synthesized by the hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction. The crystal is of hexagonal, space group P6 3/m with a = 10.6975（13）, c = 14.881 （3） A, V = 1474.8（4） A^3, C18H31Cl3Cu3N2O15·2（H3O）, Mr = 850.47, Z = 2, Dx = 1.915 g/cm^3, μ= 2.495 mm^-1, F（000） = 866, R = 0.0517 and wR = 0.0900 for 537 observed reflections （1 〉 2a（Ⅰ））. This compound contains two oxonium ions and one [Cu3Cl3（H2O）3（H0.5ntp）2]^2- anion （ntp = nitrilotripropanoato）, in which two tridentate ntp ligands connected by three copper（Ⅱ） ions enclose a cage-like unit. Each copper（Ⅱ） ion is coordinated by one water molecule, one chloride ligand and two carboxylate oxygen atoms from two ntp ligands assume a slightly distorted square-planar geometry. There are O-H…Cl hydrogen bonding interactions between unligated oxonium ions and ligated chlorine atoms of the units resulting in two-dimensional sheets and wheel-like three-dimensional interpenetrating frameworks.展开更多
The title compound {Cu2(pdc)2(4,4?-bipy)(H2O)3H2O}2 1 (H2pdc = pyridine-2,6- dicarboxylic acid, also known as dipicolinic acid; 4,4?-bipy = 4,4?-bipyridine) has been synthesized by the hydrothermal reaction and its st...The title compound {Cu2(pdc)2(4,4?-bipy)(H2O)3H2O}2 1 (H2pdc = pyridine-2,6- dicarboxylic acid, also known as dipicolinic acid; 4,4?-bipy = 4,4?-bipyridine) has been synthesized by the hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pi with a = 7.2278(3), b = 10.6259(4), c = 17.7614(6) ? a = 79.5990(10), = 83.6300(10), ? = 71.8280(10)o, V = 1272.60(8) ?, C48H44Cu4N8O24, Mr = 1371.07, Z = 1, Dc = 1.789 g/cm3, = 1.747 mm-1, F(000) = 696, R = 0.0397 and wR = 0.1137 for 3938 observed reflections (I > 2s(I)). There are two kinds of Cu coordination environments, and each central copper(II) atom is five-coordinated in a distorted square-based pyramidal coordination geo- metry. Four copper(II) atoms are linked by four pdc and two 4,4?-bipy ligands to form an annular rectangle structure. Extensive hydrogen-bonding interactions involving carboxylate O atoms as well as coordinated and free water molecules lead to the formation of a three-dimensional network struc- ture.展开更多
Chiral coordination polymers have attracted intense interest mainly due to their potential applications. Hence, two new chiral copper（Ⅱ） coordination polymers { [Cu（tsgluO）（H2O）]2·3H2O}n （1） and [Cu（tsg...Chiral coordination polymers have attracted intense interest mainly due to their potential applications. Hence, two new chiral copper（Ⅱ） coordination polymers { [Cu（tsgluO）（H2O）]2·3H2O}n （1） and [Cu（tsgluO）（2,2＇-bipy）], （2） （H2tsglu=（＋）-N-tosyl-1-glutamic acid; 2,2＇-bipy=2,2＇-bipyridine） were synthesized in the absence or presence of 2,2＇-bipy ligand and structurally characterized. A single crystal X-ray diffraction study revealed that compound 1 consists of a paddle-wheel dicopper（Ⅱ） core, which links other equivalents via four tsgluO2- ligands to form a 1D double chain. Such a chain is further interconnected through weak π-π stacking and hydrogen bonding interactions to form a 3D H-bonded supramolecular structure with 1D channels hosting lattice water molecules. Whereas, compound 2, containing the coordinating 2,2＇-bipy, gives rise to a ladder-like 1D double chain. Antiferromagnetic interactions were observed in 1 and 2.展开更多
An organic-inorganic compound [Cu（2,2＇-bpy）2][{Cu（2,2＇-bpy）2}2W12O40（H2）]·4H2O （Mr = 4048.00） was prepared from the hydrothermal reaction of Na2WO4.2H2O, CuC12·2H20, 2,2＇-bipyridine （2,2＇-bpy） ...An organic-inorganic compound [Cu（2,2＇-bpy）2][{Cu（2,2＇-bpy）2}2W12O40（H2）]·4H2O （Mr = 4048.00） was prepared from the hydrothermal reaction of Na2WO4.2H2O, CuC12·2H20, 2,2＇-bipyridine （2,2＇-bpy） and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196（8）, b = 20.4212（8）, c = 21.8129（9）A, β = 96.992（3）^o, V= 8365.0（6）A3, Dc= 3.214 g/cm^3, Z = 4μ（MoKct） = 17.269mm^-1 and F（000） = 7324. Of the 119837 total reflections, 17315 were unique （Rint = 0.0489）. The final R = 0.0385 and wR = 0.0770 for 11142 observed reflections with I 〉 2a（I）. Single-crystal X-ray diffraction reveals that the structure is composed of [（Cu（2,2＇-bpy）2}2W12040（H2）]^2- anions, discrete [Cu（2,2＇-bpy）2]^2＋ cations and lattice water molecules, and the anion is made up of a {W12O40（H2）}^6- α-Keggin core decorated with two [Cu（2,2＇-bpy）2}^2＋ groups through bridging oxygen atoms.展开更多
Three solvent-dependent chiral copper（II） compounds, {[Cu2（bzgluO）2（HzO）2]-4HzO}n （1）, {[Cu2（bzgluO）2-（DMSO）2].H2O}, （2） and [Cuz（bzgluO）2（DMF）2], （3） （H2bzgluO=N-benzoyl-L-glutamic acid） have be...Three solvent-dependent chiral copper（II） compounds, {[Cu2（bzgluO）2（HzO）2]-4HzO}n （1）, {[Cu2（bzgluO）2-（DMSO）2].H2O}, （2） and [Cuz（bzgluO）2（DMF）2], （3） （H2bzgluO=N-benzoyl-L-glutamic acid） have been synthe-sized under ambient temperature conditions and characterized by elemental analysis, IR spectra, UV spectra, ther- mogravimetric analysis, powder X-ray diffraction （PXRD） and single-crystal X-ray diffraction. Compounds 1 and 2 both crystallize in the orthorhombic space group P212121. Compound 3 crystallizes in the tetragonal space group P43. Compound 1 exhibits a ladder-like 1D chain structure, which is extended by hydrogen-bonding interactions to form a 3D supramolecular network. Compounds 2 and 3 both give a diamond-like 3D structure. Besides, there are hydrogen-bonding interactions in 2. The structural difference indicates that the solvent system plays a crucial role in modulating structures of coordination compounds. Circular dichroism （CD） and the magnetic properties of the compounds have also been investigated.展开更多
A sealed-off CuBr vapour laser with the maximal average output laser power of 20 W was fabricated and investigated. The corresponding efficiency is 1.2% and the specific average output laser power is 123 mW/cm^3 in an...A sealed-off CuBr vapour laser with the maximal average output laser power of 20 W was fabricated and investigated. The corresponding efficiency is 1.2% and the specific average output laser power is 123 mW/cm^3 in an active volume of 163 cm^3. The lifetime of the laser is more than 300 hours operating at 12 - 15 W.展开更多
基金supported by the National Natural Science Foundation of China(21173100 and 21320102001)~~
文摘The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.
基金the National Postdoctoral Program for Innovative Talents of China,Postdoctoral Science Foundation of China(Grant No.2018M640759)Natural Science Foundation of China(Grant No.21872174 and U1932148)+4 种基金Project of Innovation-Driven Plan in Central South University(Grant No.20180018050001)State Key Laboratory of Powder Metallurgy,International Science and Technology Cooperation Program(Grant No.2017YFE0127800)Hunan Provincial Science and Technology Program(2017XK2026)Shenzhen Science and Technology Innovation Project(Grant No.JCYJ20180307151313532)Thousand Youth Talents Plan of China and Hundred Youth Talents Program of Hunan.
文摘Converting carbon dioxide(CO2)into value-added chemicals by CO2 reduction has been considered as a potential way to solve the current energy crisis and environmental problem.Among the methods of CO2 reduction,the electrochemical method has been widely used due to its mild reaction condition and high reaction efficiency.In the electrochemical reduction system,the CO2 electrocatalyst is the most important part.Although many CO2 electrocatalysts have been developed,efficient catalysts with high activity,selectivity and stability are still lacking.Copper sulfide compound,as a low-toxicity and emerging material,has broad prospects in the field of CO2 reduction due to its unique structural and electrochemical properties.Much progress has been achieved with copper sulfide nanocrystalline and the field is rapidly developing.This paper summarizes the preparation,recent progress in development,and factors affecting the electrocatalytic CO2 reduction performance with copper sulfide compound as a catalyst.Prospects for future development are also outlined,with the aim of using copper sulfide compound as a highly active and stable electrocatalyst for CO2 reduction.
基金supported by Research Fund for the Doctor Program of Hubei University of Technology(No.BSQD12139)Ministry of Science and Technology Small and Medium-sized Enterprise Venture Funds(No.12C26214204453)+1 种基金Natural Foundation of Hubei Province(No.2010CDA020)the Key Foundation of Industry-University-Research Cooperation of Education Department,Hubei Province(No.CXY2009A010)
文摘Two new compounds,1（[Cu（IDB_）2]Cl_2·2CH_3CH_2OH·2H_2O（IDB = N,N-di（2-benzimidazolylmethyl）imine]） and 2（[Cu（EDTB）]·2[C_6H_4（OH）COO]·6H_2O（EDTB = N,N,N＇,N＇-tetrakis-[（2-benzimidazolyl）methyl]-1,2-ethanediamine]）,have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction. Crystal 1 belongs to the triclinic system,space group P1 with a = 9.565（2）,b = 9.863（2）,c = 10.252（3） ？,α = 81.915,β = 88.330,γ = 87.347°,V = 956.28（40） ？3,Z = 1,F（000） = 427,D_c = 1.419 g/cm3,Mr = 817.27 and μ（MoKα） = 0.764 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0505,wR = 0.1417; R indices（all data）： R = 0.0591,wR = 0.1525. Crystal 2 is of triclinic system,space group P1 with a = 11.487（3）,b = 13.396（4）,c = 17.977（5） ？,α = 73.899（5）,β = 86.629（5）,γ = 65.018（4）°,V = 2403.8（12） ？3,Z = 2,F（000） = 1072,D3c = 1.417 g/cm,Mr = 1025.54,μ（MoKα） = 0.528 mm^（-1）. The final R indices（I 〉 2σ（I））： R = 0.0769,w R = 0.163 2; R indices（all data）： R = 0.0769,wR = 0.1632. The two compounds exhibit mononuclear structures. The copper（Ⅱ） atom of crystal 1 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand IDB to adopt a distorted octahedral coordination geometry. The copper（Ⅱ） atom of crystal 2 is six-coordinated by four nitrogen atoms of benzimidazole groups and two amine nitrogen atoms from the ligand EDTB to show a distorted octahedral coordination geometry. Particularly,the two compounds exhibit fluorescent properties at room temperature in ethanol.
基金Project (21001118) supported by the National Natural Science Foundation of China
文摘A novel compound Cu（phen）（m-CBA）2 was synthesized with m-chlorobenzoic acid（m-CBA）, 1,10-phenanthroline（phen） and Cu（OAc）2·H2O. It was characterized by IR, UV, elemental analyses and X-ray crystallography. It crystallizes in the monoclinic crystal system with C2/c space group, a=2.9699（4） nm, b=1.15452（2） nm, c=1.5335（2） nm, β=111.118（2）°, V=4.905 1（1） nm3, Z=8, F（000）=2 328, R1=0.072 8, wR2=0.223 4 [I2σ（I）]. Structure analysis shows that the copper center coordinates with two nitrogen atoms from one 1,10-phenanthroline molecule, two oxygen atoms from two m-chlorobenzoic acid molecules, giving a distorted squared planar coordination geometry. This novel compound shows paramagnetic interactions between copper centers.
基金Supported by the National Natural Science Foundation of China(No.20662007)the Bureau of Education of Jiangxi Province(No.GJJ09064)Jiangxi Science and Technology Support Program(20112BBF60009)
文摘The title compounds 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid（C11H9Cl N2O2, HL）（1） and [Cu（L）2（H2O）]（2） were prepared and structurally characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compound 1（C11H9Cl N2O2） crystallizes in the monoclinic system, space group P21/n with a = 7.249（3）, b = 20.515（10）, c = 7.249（3）,β= 96.30°, V = 1071.6（9） ？3, Z = 4, Mr = 236.65, Dc = 1.467 g/cm3, F（000） = 488, GOOF = 1.029, μ= 0.341 mm-1, the final R = 0.0736 and w R = 0.1966 for 1500 observed reflections with I 〉 2σ（I）. Compound 2（C22H18Cl2Cu N4O5） crystallizes in the monoclinic system, space group P21/c with a = 7.2931（6）, b = 24.548（2）, c = 13.2726（11）, β= 99.4040（10）°, V = 2344.2（3） ？3, Z = 4, Mr = 552.84, Dc = 1.566 g/cm3, F（000） = 1124, GOOF = 1.050, μ= 1.201 mm-1, the final R = 0.0376 and w R = 0.1000 for 3626 observed reflections with I 〉 2σ（I）. 1 and 2 are connected through hydrogen bonding interactions to generate 2D and 3D supramolecular structures, respectively. Moreover, the preliminary antibacterial activities of 1 and 2 against the gram positive bacteria（S. aureus, C. albicans and B. subtilis） and gram negative bacteria（E. coli and P. aeruginosa） have been tested by using the microdilution method, and the results indicate that 2 is more active than 1 against the tested bacteria.
基金the Natural Science Foundation of Jilin Province(No.2005103)
文摘A metal-organic coordination compound formulated as [Cu（MOPIP）（BDC）]n·0.5n（H2O） 1 （MOPIP - 2-（4-methoxyphenyl）-1H-imidazo[4,5-f][1,10] phenanthroline, BDC = 1,4-benze Nedicarboxylate） has been hydrothermally synthesized and structurally characterized by elemental analysis, thermogravimetric analysis, IR spectrum, and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P1^-, with a = 8.872（5）, b = 11.163（6）, c = 12.589（6）A, α = 94.687（7）, β = 99.930（6）, γ = 103.074（7）°, V = 1186.7（12）A^3, C28H19CuN4O5.5, Mr= 563.01, Dc = 1.576 g/cm^3,μ（MoKa） = 0.973 mm^-1, F（000） = 576, Z = 2, the final R = 0.0607 and wR = 0.1618 for 3419 observed reflections （I 〉 2σ（I））.
基金funded by the National Natural Science Foundation of China(No.50073019)
文摘The mixed ligand coordination compound of copper with norfloxacin (NFLX) and 1, 10-phen has been synthesized and characterized by means of X-ray single crystal diffraction. The structure features of the coordination compound are described. Antibacterial activities of the coordination compound have been tested against different microorganisms. The antitumor activities of the coordination compound on leukemia HL-60 cell line and liver cancer BEL-7402 cell line have been measured, respectively. The results indicated that the coordination compound has strong inhibitory effect on HL-60 and BEL-7402 cell lines.
基金The project was supported by the Natural Science Foundation of Jiangsu Province (No. BK2005045) and Key Marine Biotechnology Lab. of HHIT
文摘The title compound [Cu（C11H29N5）]（ClO4）2 was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The compound crystallizes in the monoclinic system, space group P21/n with α = 9.405（2）, b = 14.495（3）, c = 14.715（3） A, β= 90.262（3）°, V=2006.1（7） A^3,M,=493.83,Z=4,F）（000）= 1028,Dc= 1.635 g/cm^3, T= 298（2） K,μ= 1.403 mm^-1 and = 0.71073 A. The was refined to R = 0.0508 and wR = 0. 1250 for 2293 observed reflections with I 〉 2σ（I）. The Cu（Ⅱ） atom possesses a five-coordtinate CuN5 environment which shows a slightly distorted square-pyramidal geonetry. Antimicrobial activity study found that the complex is active against Salmonella species, Staphylococcus aureu, Bacillus pumilus and Bacillus coliforms.
基金supported by the National Natural Science Foundation of China(No.21071099)
文摘A novel copper（II） coordination polymer of {[Cu3L2（4,4＂-bipy）4]（CIO4）2＂20H20}, （1） was synthesized by the reaction of H2L （C6HsN（CH2COOH）2, phenyliminodiacetic acid）, CuSO4.5H20, NaCIO4.H20 and 4,4＂-bipy （4,4＂-bipyridine） in water/methanol, followed by slow evaporating at room temperature. The compound was characterized by elemental analysis （EA）, infrared spectroscopy （IR）, thermogravimetric analysis （TGA） and single-crystal/powder X-ray diffraction. The result of single-crystal X-ray diffraction analysis reveals that 1 crystallizes in the monoclinic crystal system with C2/c space group, a = 2.9974（4）, b = 1.7270（2）, c = 2.0007（3） nm, fl = 128.793（2）°, V= 8.0722（19） nm3, Z = 4, Dc = 1.472 g.cm-3,/a = 0.942 mm-1, F（000） = 3716, R= 0.0487 and wR = 0.1204 （I 〉 20（/））. The basic structural unit of 1 is a trinuclear cluster unit of [Cu3L2]2＋, which is constructed by two #2-L2- ligands bridging and chelating three Cu（Ⅱ） ions. These [Cu3L2]2＋ units are connected with each other by 4,4＂-bipy ligands to generate a 2D cation brickwall-like network of [Cu3L2（4,4＂-bipy）4]n2n＋. These adjacent 2D cation layers are further stacked in a staggered fashion via interlayer stacking interactions to form a 3D supramolecular structure with 1D open square channels, in which the C104- counter anions and lattice water molecules are filled. Furthermore, the magnetic property of 1 was also investigated.
文摘An extensive series of experiments was carried out in order to identify suitable catalysts to boost the reaction rate of wet air oxidation of real textile wastewaters at relatively mild temperature and pressure. Experimental results indicated that all catalysts tested in this investigation had shown an impressive increase in the initial COD and TOC removal rate as well as the COD and TOC removal levels in two hours reaction. Among all the catalysts tested, copper salts were more effective than the rest. Anions of the salt solutions also played a role in the catalytic process with nitrate ions having better effect than sulfate ions. Hence copper nitrates were more effective than copper sulfates. It was also found that a mixture of salts with different metals performed better than either of the component single salt alone.
文摘Since the discovery of superconductivity of the BiSrCuO system at 20K, the work of synthesizing high Tc superconductors without rare-earths by adding some elements other than rare-earths in the BiSrCuO system has made a lot of progress. Recently, N. Fukushima et al. have synthesized Bi4Sr4RE2Cu4O16+δ (RE = Nd, Eu or Y) by substituting RE for Ca in the Bi4Sr4Ca2Cu4O16+δ superconductor and revealed that it has a crystal structure identical with this superconductor, but it is an insulator. In this paper, the authors report the superconductivity and structure of the BiSrCaEuCuO compound synthesized by adding 5 at% of rare-earth Eu in the BiSrCaCuO system.
文摘The title compound, [Cu（phen）2（SO4）（H2O）]·0.5C4H4O4·7H2O （phen = 1,10-phe-nan throline and C4H4O4 = fumaric acid）, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 11.4827（2）, b = 11.9086（2）, c = 13.77350（10） A, α = 80.6830（10）, β = 66.6480（10）, γ = 64.048000）°, V = 1554.63（4） A^3, Mr = 722.17, Z = 2, Dc = 1.543 g/cm^3,μ = 0.845 mm^-1, F（000） = 750, R = 0.0349 and wR = 0.0837 for 4754 observed reflections （1 〉 2σ（I））. The compound contains a six-coordinated copper（Ⅱ） center, which is surround by four N atoms of two phen ligands （Cu-N distances in the range of 1.997（2）- 2.225（2） A）, one sulfate O atom （Cu-O = 2.0037（17） A） and one water O atom （Cu-O（Sw） = 2.719（2） A,） in a distorted octahedral geometry. Extensive hydrogen-bonding interactions are involved in water molecules, ligated sulfate anions and fumaric acid molecules. In addition, π-π interactions via aromatic nitrogen-containing ligands are also discussed. The combination of non-covalent interactions leads to the formation of a 3-D network structure.
基金This work was financially supported by the NNSF of China (No. 20173063), the State Key Basic Research and Development Plan of China (001CB108906) and the NSF of Fujian Province (E0020001)
文摘The new compound, （H3O）2[Cu3Cl3（H2O）3（NC9H12.5O6）2] 1, has been synthesized by the hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction. The crystal is of hexagonal, space group P6 3/m with a = 10.6975（13）, c = 14.881 （3） A, V = 1474.8（4） A^3, C18H31Cl3Cu3N2O15·2（H3O）, Mr = 850.47, Z = 2, Dx = 1.915 g/cm^3, μ= 2.495 mm^-1, F（000） = 866, R = 0.0517 and wR = 0.0900 for 537 observed reflections （1 〉 2a（Ⅰ））. This compound contains two oxonium ions and one [Cu3Cl3（H2O）3（H0.5ntp）2]^2- anion （ntp = nitrilotripropanoato）, in which two tridentate ntp ligands connected by three copper（Ⅱ） ions enclose a cage-like unit. Each copper（Ⅱ） ion is coordinated by one water molecule, one chloride ligand and two carboxylate oxygen atoms from two ntp ligands assume a slightly distorted square-planar geometry. There are O-H…Cl hydrogen bonding interactions between unligated oxonium ions and ligated chlorine atoms of the units resulting in two-dimensional sheets and wheel-like three-dimensional interpenetrating frameworks.
基金This work was financially supported by the NNSFC (No. 20173063) the State Key Basic Research and Development Plan of China (001CB108906) and the NSF of Fujian Province (E0020001)
文摘The title compound {Cu2(pdc)2(4,4?-bipy)(H2O)3H2O}2 1 (H2pdc = pyridine-2,6- dicarboxylic acid, also known as dipicolinic acid; 4,4?-bipy = 4,4?-bipyridine) has been synthesized by the hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pi with a = 7.2278(3), b = 10.6259(4), c = 17.7614(6) ? a = 79.5990(10), = 83.6300(10), ? = 71.8280(10)o, V = 1272.60(8) ?, C48H44Cu4N8O24, Mr = 1371.07, Z = 1, Dc = 1.789 g/cm3, = 1.747 mm-1, F(000) = 696, R = 0.0397 and wR = 0.1137 for 3938 observed reflections (I > 2s(I)). There are two kinds of Cu coordination environments, and each central copper(II) atom is five-coordinated in a distorted square-based pyramidal coordination geo- metry. Four copper(II) atoms are linked by four pdc and two 4,4?-bipy ligands to form an annular rectangle structure. Extensive hydrogen-bonding interactions involving carboxylate O atoms as well as coordinated and free water molecules lead to the formation of a three-dimensional network struc- ture.
基金Project supported by the Natural Science Foundation of China （Nos. 20601007, 20773034）, the Natural Science Foundation of Hebei Education Department （No. H2006002）, the Natural Science Foundation of Hebei Province （No. B2008000143）, and the Doctoral Foundation of Hebei Normal University （No. 103261）~
文摘Chiral coordination polymers have attracted intense interest mainly due to their potential applications. Hence, two new chiral copper（Ⅱ） coordination polymers { [Cu（tsgluO）（H2O）]2·3H2O}n （1） and [Cu（tsgluO）（2,2＇-bipy）], （2） （H2tsglu=（＋）-N-tosyl-1-glutamic acid; 2,2＇-bipy=2,2＇-bipyridine） were synthesized in the absence or presence of 2,2＇-bipy ligand and structurally characterized. A single crystal X-ray diffraction study revealed that compound 1 consists of a paddle-wheel dicopper（Ⅱ） core, which links other equivalents via four tsgluO2- ligands to form a 1D double chain. Such a chain is further interconnected through weak π-π stacking and hydrogen bonding interactions to form a 3D H-bonded supramolecular structure with 1D channels hosting lattice water molecules. Whereas, compound 2, containing the coordinating 2,2＇-bipy, gives rise to a ladder-like 1D double chain. Antiferromagnetic interactions were observed in 1 and 2.
基金This work was supported by the Natural Science Foundation of Fujian Province (No. E0420001) and NCETFJ.
文摘An organic-inorganic compound [Cu（2,2＇-bpy）2][{Cu（2,2＇-bpy）2}2W12O40（H2）]·4H2O （Mr = 4048.00） was prepared from the hydrothermal reaction of Na2WO4.2H2O, CuC12·2H20, 2,2＇-bipyridine （2,2＇-bpy） and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196（8）, b = 20.4212（8）, c = 21.8129（9）A, β = 96.992（3）^o, V= 8365.0（6）A3, Dc= 3.214 g/cm^3, Z = 4μ（MoKct） = 17.269mm^-1 and F（000） = 7324. Of the 119837 total reflections, 17315 were unique （Rint = 0.0489）. The final R = 0.0385 and wR = 0.0770 for 11142 observed reflections with I 〉 2a（I）. Single-crystal X-ray diffraction reveals that the structure is composed of [（Cu（2,2＇-bpy）2}2W12040（H2）]^2- anions, discrete [Cu（2,2＇-bpy）2]^2＋ cations and lattice water molecules, and the anion is made up of a {W12O40（H2）}^6- α-Keggin core decorated with two [Cu（2,2＇-bpy）2}^2＋ groups through bridging oxygen atoms.
文摘Three solvent-dependent chiral copper（II） compounds, {[Cu2（bzgluO）2（HzO）2]-4HzO}n （1）, {[Cu2（bzgluO）2-（DMSO）2].H2O}, （2） and [Cuz（bzgluO）2（DMF）2], （3） （H2bzgluO=N-benzoyl-L-glutamic acid） have been synthe-sized under ambient temperature conditions and characterized by elemental analysis, IR spectra, UV spectra, ther- mogravimetric analysis, powder X-ray diffraction （PXRD） and single-crystal X-ray diffraction. Compounds 1 and 2 both crystallize in the orthorhombic space group P212121. Compound 3 crystallizes in the tetragonal space group P43. Compound 1 exhibits a ladder-like 1D chain structure, which is extended by hydrogen-bonding interactions to form a 3D supramolecular network. Compounds 2 and 3 both give a diamond-like 3D structure. Besides, there are hydrogen-bonding interactions in 2. The structural difference indicates that the solvent system plays a crucial role in modulating structures of coordination compounds. Circular dichroism （CD） and the magnetic properties of the compounds have also been investigated.
基金This work was supported by the National Natural Science Foundation of China (No.1037408 and 10574111)
文摘A sealed-off CuBr vapour laser with the maximal average output laser power of 20 W was fabricated and investigated. The corresponding efficiency is 1.2% and the specific average output laser power is 123 mW/cm^3 in an active volume of 163 cm^3. The lifetime of the laser is more than 300 hours operating at 12 - 15 W.
