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2012 Volume 28 Issue 12
2012, 28(12): 2501-2507
Abstract:
Li1.2Mn0.4+xNixCr0.4-2xO2 (x=0, 0.05, 0.10, 0.15, 0.20) were synthesized by spray-drying process, which was named as SD1 to SD5, respectively. Their crystal structures, element valences and the electrochemical performances were investigated by XRD, XPS, ICP, SEM and TEM. All compounds have a typical feature of a Li-rich layered solid solution material in terms of their crystal structures, and the valences of Ni and Mn are 2.5+ and 4+, respectively. As to the valence of Cr, both +3 and +6 co-exist in the samples from SD1 to SD4. Moreover, the present of amorphous Li2CrO4 gives rise to the strong hygroscopicity, which should be closed related to the poor electrochemical properties. Sample with water-washed treatment could effectively remove the amorphous Li2CrO4, and consequently improved its electrochemical properties. The washed SD4 has a reversible capacity of 237 mA·h·g-1 and the capacity retention is about 99%, when the cell was operated at 50 ℃ in the range of 4.8~2.0 V. If it was operated in the range of 5.0~2.0 V at 50 ℃, the initial discharge capacity increases to 307 mA·h·g-1.
Li1.2Mn0.4+xNixCr0.4-2xO2 (x=0, 0.05, 0.10, 0.15, 0.20) were synthesized by spray-drying process, which was named as SD1 to SD5, respectively. Their crystal structures, element valences and the electrochemical performances were investigated by XRD, XPS, ICP, SEM and TEM. All compounds have a typical feature of a Li-rich layered solid solution material in terms of their crystal structures, and the valences of Ni and Mn are 2.5+ and 4+, respectively. As to the valence of Cr, both +3 and +6 co-exist in the samples from SD1 to SD4. Moreover, the present of amorphous Li2CrO4 gives rise to the strong hygroscopicity, which should be closed related to the poor electrochemical properties. Sample with water-washed treatment could effectively remove the amorphous Li2CrO4, and consequently improved its electrochemical properties. The washed SD4 has a reversible capacity of 237 mA·h·g-1 and the capacity retention is about 99%, when the cell was operated at 50 ℃ in the range of 4.8~2.0 V. If it was operated in the range of 5.0~2.0 V at 50 ℃, the initial discharge capacity increases to 307 mA·h·g-1.
2012, 28(12): 2508-2512
Abstract:
Ruthenium nanoparticles were conveniently immobilized on nitrogen-doped carbon nanotubes (NCNTs) via microwave-assisted ethylene glycol reduction. Ru/NCNTs catalysts presented the excellent catalytic performance and cyclical stability for the aerobic oxidation of benzyl alcohol under atmospheric condition, compared with the catalysts supported on carbon nanotubes (CNTs) and activated carbon (AC). The conversion of benzyl alcohol could rearch 93% and the selectivity of benzaldehyde was higher than 99% at 90 ℃. The doped nitrogen atoms embedded in the NCNTs wall are responsible for the improved catalytic performance.
Ruthenium nanoparticles were conveniently immobilized on nitrogen-doped carbon nanotubes (NCNTs) via microwave-assisted ethylene glycol reduction. Ru/NCNTs catalysts presented the excellent catalytic performance and cyclical stability for the aerobic oxidation of benzyl alcohol under atmospheric condition, compared with the catalysts supported on carbon nanotubes (CNTs) and activated carbon (AC). The conversion of benzyl alcohol could rearch 93% and the selectivity of benzaldehyde was higher than 99% at 90 ℃. The doped nitrogen atoms embedded in the NCNTs wall are responsible for the improved catalytic performance.
2012, 28(12): 2513-2522
Abstract:
A yellow-colored and mesoporous N-F codoped TiO2 photocatalyst (TiONF) with visible-light response was prepared by a hydrolysis-precipitation method using cellulose as the template and TiCl4 as the precursor. The photocatalytic activity was evaluated through the photocatalytic degradation of phenol under ultraviolet (UV), artificial visible (Vis) and solar light irradiation, respectively. The catalysts were characterized by X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), X-ray diffraction (XRD), thermogravimetry-differential scanning calorimetry (TG/DSC), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and N2 adsorption-desorption. The results show that the TiONF obtained by using the cellulose template with suitable N-F doping exhibits higher activity under UV, Vis and solar light irradiation than that obtained without the cellulose template. N-F codoping can increase the amount of surface OH- of TiO2, and retards phase transformation. N-doping can form a new band-gap to extend the light response of TiO2 to visible region, F-doping can promote generation of oxygen vacancies on the surface of TiO2, and can increase surface acidity and Ti3+ of TiO2. The addition of the cellulose template can reduce the average grain size and increase the specific area of TiONF.
A yellow-colored and mesoporous N-F codoped TiO2 photocatalyst (TiONF) with visible-light response was prepared by a hydrolysis-precipitation method using cellulose as the template and TiCl4 as the precursor. The photocatalytic activity was evaluated through the photocatalytic degradation of phenol under ultraviolet (UV), artificial visible (Vis) and solar light irradiation, respectively. The catalysts were characterized by X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), X-ray diffraction (XRD), thermogravimetry-differential scanning calorimetry (TG/DSC), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and N2 adsorption-desorption. The results show that the TiONF obtained by using the cellulose template with suitable N-F doping exhibits higher activity under UV, Vis and solar light irradiation than that obtained without the cellulose template. N-F codoping can increase the amount of surface OH- of TiO2, and retards phase transformation. N-doping can form a new band-gap to extend the light response of TiO2 to visible region, F-doping can promote generation of oxygen vacancies on the surface of TiO2, and can increase surface acidity and Ti3+ of TiO2. The addition of the cellulose template can reduce the average grain size and increase the specific area of TiONF.
2012, 28(12): 2523-2529
Abstract:
Graphite oxide (GO) was prepared from natural graphite by a modified Hummers method. GO was firstly ball milled for 10 h and then exfoliated into graphene oxide by ultrasonication. Finally, graphene was prepared by magnetic mixing reflux method using hydrazine monohydrate as reductant. Graphene is characterized by SEM, AFM, XRD, Raman, FTIR, TEM measurements. The surface morphology and structure of graphene sheets which are prepared by low-energy ball milling assisted oxidization-reduction method and oxidization-reduction method without ball milling are compared and analyzed. The results show that ball milling contributes to the thinning and exfoliation of GO. Otherwise, low-energy ball milling can promote the reduction degree of GO, shorten the reflux reaction time and improve the efficiency of graphene preparation.
Graphite oxide (GO) was prepared from natural graphite by a modified Hummers method. GO was firstly ball milled for 10 h and then exfoliated into graphene oxide by ultrasonication. Finally, graphene was prepared by magnetic mixing reflux method using hydrazine monohydrate as reductant. Graphene is characterized by SEM, AFM, XRD, Raman, FTIR, TEM measurements. The surface morphology and structure of graphene sheets which are prepared by low-energy ball milling assisted oxidization-reduction method and oxidization-reduction method without ball milling are compared and analyzed. The results show that ball milling contributes to the thinning and exfoliation of GO. Otherwise, low-energy ball milling can promote the reduction degree of GO, shorten the reflux reaction time and improve the efficiency of graphene preparation.
2012, 28(12): 2530-2534
Abstract:
A semi-rigid tetrahedral linker tetrakis[3-(carboxyphenyl)oxamethyl]methane acid (H4L) and its coordination polymer [Cu(H2L)(Py)2]n (Py=pyridyne) were synthesized and characterized by elemental analyses, IR spectroscopy, etc. The single crystal structure show the title complex crystallizes in the monoclinic system with space group C2/c, a=1.943 0(7) nm, b=0.926 4(3) nm, c=2.784 9(9) nm, β=96.763(3)°, V=4.978(3) nm3, Z=4, F(000)=1 724. In the complex each Cu(Ⅱ) atoms is coordinated with two pyridyne and two oxygen atom from two arms of H2L2-, and displays a one-dimensional line topology with the other two arms free. Platon calculation show that the guest accessible volume (1.397 nm3 per unit cell) comprises 28.1% of the unit cell volume. The thermal analysis shows the title compound is trable up to 236.9 ℃. CCDC: 817405.
A semi-rigid tetrahedral linker tetrakis[3-(carboxyphenyl)oxamethyl]methane acid (H4L) and its coordination polymer [Cu(H2L)(Py)2]n (Py=pyridyne) were synthesized and characterized by elemental analyses, IR spectroscopy, etc. The single crystal structure show the title complex crystallizes in the monoclinic system with space group C2/c, a=1.943 0(7) nm, b=0.926 4(3) nm, c=2.784 9(9) nm, β=96.763(3)°, V=4.978(3) nm3, Z=4, F(000)=1 724. In the complex each Cu(Ⅱ) atoms is coordinated with two pyridyne and two oxygen atom from two arms of H2L2-, and displays a one-dimensional line topology with the other two arms free. Platon calculation show that the guest accessible volume (1.397 nm3 per unit cell) comprises 28.1% of the unit cell volume. The thermal analysis shows the title compound is trable up to 236.9 ℃. CCDC: 817405.
2012, 28(12): 2535-2539
Abstract:
Coordination polymer {[Mn2(phen)2(H2pztc)Mn2(phen)2(Hpztc)2 (H2O)2]·4H2O}n (1) has been synthesized by the hydrothermal reaction of MnCl2·4H2O, pyrazine-2,3,5,6-tetracarboxylic acid (H4pztc) and 1,10-phenanthroline (phen), which were further characterized by IR, elemental analysis, X-ray diffraction single-crystal structural analysis and magnetic susceptibility. It belongs to triclinic crystal system, P1 space group with a=0.955 02(19) nm, b=1.323 4(3) nm, c=1.515 7(3) nm, α=68.95(3)°, β=77.33(3)°, γ=81.92(3)°, V=1.740 3(6) nm3, Z=2. The manganese(Ⅱ) ions in the complex are 6-coordinated and 7-coordinated. The Mn(Ⅱ) ions of complex 1 are connected by pztc and phen, resulting in a 1D chain. Variable temperature magnetic susceptibility measurements reveal the existence of antiferromagnetic interactions in the complex 1. CCDC: 694108.
Coordination polymer {[Mn2(phen)2(H2pztc)Mn2(phen)2(Hpztc)2 (H2O)2]·4H2O}n (1) has been synthesized by the hydrothermal reaction of MnCl2·4H2O, pyrazine-2,3,5,6-tetracarboxylic acid (H4pztc) and 1,10-phenanthroline (phen), which were further characterized by IR, elemental analysis, X-ray diffraction single-crystal structural analysis and magnetic susceptibility. It belongs to triclinic crystal system, P1 space group with a=0.955 02(19) nm, b=1.323 4(3) nm, c=1.515 7(3) nm, α=68.95(3)°, β=77.33(3)°, γ=81.92(3)°, V=1.740 3(6) nm3, Z=2. The manganese(Ⅱ) ions in the complex are 6-coordinated and 7-coordinated. The Mn(Ⅱ) ions of complex 1 are connected by pztc and phen, resulting in a 1D chain. Variable temperature magnetic susceptibility measurements reveal the existence of antiferromagnetic interactions in the complex 1. CCDC: 694108.
2012, 28(12): 2540-2547
Abstract:
A dinuclear 3,8-dithiophen substituted 1,10-phenanthroline (dtphen) manganese(Ⅱ) complex and a pair of 3,8-di-3-methylthiophen substituted 1,10-phenanthroline (dmtphen) manganese(Ⅱ) and cobalt(Ⅱ) complexes, formulated as [trans-Mn2Cl4(dtphen)2] (1), [cis-MnCl2(dmtphen)2] (2) and [cis-CoCl2(dmtphen)2] (3), were synthesized and characterized by elemental analysis, FTIR, UV-Vis spectra and X-ray single-crystal structural analysis. The two Mn(Ⅱ) complexes exhibit diverse coordination models in the whole molecular structures. In mononuclear complexe 2 and 3, both dmtphen ligands have similar trans/trans conformation but different dihedral angles ranging from 14.1(1)°~51.5(1)° because of the spatial crowding effects of methyl group. In contrast, the dihedral angles of dtphen ligands in dinuclear complex 1 are only within 2.0(1)°~20.2(1)° and the two side thiophene rings in the dtphen ligand adopt the cis/trans conformation relative to the central phen unit. CCDC: 870021, 1; 870022, 2; 870023, 3.
A dinuclear 3,8-dithiophen substituted 1,10-phenanthroline (dtphen) manganese(Ⅱ) complex and a pair of 3,8-di-3-methylthiophen substituted 1,10-phenanthroline (dmtphen) manganese(Ⅱ) and cobalt(Ⅱ) complexes, formulated as [trans-Mn2Cl4(dtphen)2] (1), [cis-MnCl2(dmtphen)2] (2) and [cis-CoCl2(dmtphen)2] (3), were synthesized and characterized by elemental analysis, FTIR, UV-Vis spectra and X-ray single-crystal structural analysis. The two Mn(Ⅱ) complexes exhibit diverse coordination models in the whole molecular structures. In mononuclear complexe 2 and 3, both dmtphen ligands have similar trans/trans conformation but different dihedral angles ranging from 14.1(1)°~51.5(1)° because of the spatial crowding effects of methyl group. In contrast, the dihedral angles of dtphen ligands in dinuclear complex 1 are only within 2.0(1)°~20.2(1)° and the two side thiophene rings in the dtphen ligand adopt the cis/trans conformation relative to the central phen unit. CCDC: 870021, 1; 870022, 2; 870023, 3.
2012, 28(12): 2548-2557
Abstract:
The in vitro bioactive behaviors of hydrated tricalcium silicate(Ca3SiO5, C3S) paste were studied. The results show that dry hydrated C3S paste contains about 23.97wt% Ca(OH)2, and the dissolution of Ca(OH)2 results in increased pH value of simulated body fluid (SBF). Apatite particles are firstly induced to deposit on hydrated C3S paste surface. Then, hydrated C3S paste surface is co-deposited with CaCO3 and apatite particles. HCO3- is the principal buffer system of SBF, and the carbonation of Ca(OH)2 and deposition of CaCO3 mainly contribute to the decreasing of pH value. As a result of lower ion exchanges, hydrated C3S paste surface is finally deposited with apatite. The deposition of apatite contributes to the further decreasing of pH value. The in vitro bioactivity and further biocompatibility evaluations of C3S and C3S devised materials must be improved by considering the concentration and behavior of HCO3- in living body.
The in vitro bioactive behaviors of hydrated tricalcium silicate(Ca3SiO5, C3S) paste were studied. The results show that dry hydrated C3S paste contains about 23.97wt% Ca(OH)2, and the dissolution of Ca(OH)2 results in increased pH value of simulated body fluid (SBF). Apatite particles are firstly induced to deposit on hydrated C3S paste surface. Then, hydrated C3S paste surface is co-deposited with CaCO3 and apatite particles. HCO3- is the principal buffer system of SBF, and the carbonation of Ca(OH)2 and deposition of CaCO3 mainly contribute to the decreasing of pH value. As a result of lower ion exchanges, hydrated C3S paste surface is finally deposited with apatite. The deposition of apatite contributes to the further decreasing of pH value. The in vitro bioactivity and further biocompatibility evaluations of C3S and C3S devised materials must be improved by considering the concentration and behavior of HCO3- in living body.
2012, 28(12): 2558-2564
Abstract:
Two lanthanideⅢ metal-organic complexes, [Eu(DICNQ)2(NO3)3]·(CH3CN)2 (1) and [Tb(DICNQ)(NO3)3]2 (2), were prepared from Eu(NO3)3·6H2O and Tb(NO3)3·6H2O with 6,7-dicyanodipyridoquinoxaline (DICNQ) by solvothermal reactions, respectively, and characterized by single-crystal X-ray diffraction analyses. Compound 1 crystallizes in the monoclinic noncentrosymmetric space group Cc, with a=1.157 7(6) nm, b=3.193 4(2) nm, c=1.106 6(6) nm, β=97.633(2)°, V=4.055(4) nm3, Z=4, Mr=984.63, Dc=1.613 g·cm-3, μ=1.623 mm-1, F(000)=1 952, S=1.035 and T=293(2) K. The final R=0.033 5 and wR=0.078 1 for 6 467 observed reflections with I>2σ(I). Compound 2 crystallizes in the triclinic centrosymmetric space group P1, with a=0.871 1(3) nm, b=0.890 8(3) nm, c=1.544 9(5) nm, α=80.852(9)°, β=84.217(9)°, γ=65.475(7)°, V=1.076 0(6) nm3, Z=1, Mr=1 254.44, Dc=1.936 g·cm-3, μ=3.356 mm-1, F(000)=604, S=1.026 and T=293(2) K. The final R=0.036 8 and wR=0.095 6 for 3 697 observed reflections with I>2σ(I). Compound 1 is built upon isolated neutral molecules, which are connected by C-H…O hydrogen-bonding interactions, while compound 2 forms a packing structure by π…π stacking interactions as well as intermolcular C-H…N and intramolecular C-H…O hydrogen-bonding interactions. CCDC: 857317, 1; 857318, 2.
Two lanthanideⅢ metal-organic complexes, [Eu(DICNQ)2(NO3)3]·(CH3CN)2 (1) and [Tb(DICNQ)(NO3)3]2 (2), were prepared from Eu(NO3)3·6H2O and Tb(NO3)3·6H2O with 6,7-dicyanodipyridoquinoxaline (DICNQ) by solvothermal reactions, respectively, and characterized by single-crystal X-ray diffraction analyses. Compound 1 crystallizes in the monoclinic noncentrosymmetric space group Cc, with a=1.157 7(6) nm, b=3.193 4(2) nm, c=1.106 6(6) nm, β=97.633(2)°, V=4.055(4) nm3, Z=4, Mr=984.63, Dc=1.613 g·cm-3, μ=1.623 mm-1, F(000)=1 952, S=1.035 and T=293(2) K. The final R=0.033 5 and wR=0.078 1 for 6 467 observed reflections with I>2σ(I). Compound 2 crystallizes in the triclinic centrosymmetric space group P1, with a=0.871 1(3) nm, b=0.890 8(3) nm, c=1.544 9(5) nm, α=80.852(9)°, β=84.217(9)°, γ=65.475(7)°, V=1.076 0(6) nm3, Z=1, Mr=1 254.44, Dc=1.936 g·cm-3, μ=3.356 mm-1, F(000)=604, S=1.026 and T=293(2) K. The final R=0.036 8 and wR=0.095 6 for 3 697 observed reflections with I>2σ(I). Compound 1 is built upon isolated neutral molecules, which are connected by C-H…O hydrogen-bonding interactions, while compound 2 forms a packing structure by π…π stacking interactions as well as intermolcular C-H…N and intramolecular C-H…O hydrogen-bonding interactions. CCDC: 857317, 1; 857318, 2.
2012, 28(12): 2565-2572
Abstract:
Organic xerogel was rapidly prepared via a lysine-catalyzed gelation process with resorcinol and formaldehyde as the precursors. After carbonization and a subsequent activation with KOH, carbon xerogels with high microporosity and high-specific-surface area could be obtained. The hydrogen storage properties of the porous carbon xerogels were studied. The relationship of the maximum hydrogen storage capacity with specific surfacearea, micropore volume and pore size distribution was investigated. The results show that moderately KOH-activated carbon xerogel (ACX-5) with high surface area of 2 204 m2·g-1 and large total-pore volume of 1.09 cm3·g-1 exhibits the largest hydrogen storage capacity of 4.3wt% at 77 K and under 1.1 MPa hydrogen pressure.
Organic xerogel was rapidly prepared via a lysine-catalyzed gelation process with resorcinol and formaldehyde as the precursors. After carbonization and a subsequent activation with KOH, carbon xerogels with high microporosity and high-specific-surface area could be obtained. The hydrogen storage properties of the porous carbon xerogels were studied. The relationship of the maximum hydrogen storage capacity with specific surfacearea, micropore volume and pore size distribution was investigated. The results show that moderately KOH-activated carbon xerogel (ACX-5) with high surface area of 2 204 m2·g-1 and large total-pore volume of 1.09 cm3·g-1 exhibits the largest hydrogen storage capacity of 4.3wt% at 77 K and under 1.1 MPa hydrogen pressure.
Effect of Mn Source on 5 V LiNi0.5Mn1.5O4 Positive Electrode Materials Prepared by Combustion Method
2012, 28(12): 2573-2580
Abstract:
Sub-micrometric LiNi0.5Mn1.5O4 cathode materials were prepared by sucrose combustion method with two different Mn sources. The effect of manganese acetate and manganese nitrate on the crystal structure, morphology, particle size and electrical performance of the prepared samples was evaluated by X-ray diffraction (XRD),scanning electron microscopy (SEM), particle size analysis, cyclic voltammetry (CV),galvanostatic charge-discharge test and electrochemical impedance spectroscopy (EIS). XRD analysis shows that the structure of both samples is a typical cubic spinel with Fd3m space group. The particle size and the distribution of the LiNi0.5Mn1.5O4 powder are strongly influenced by Mn source. The materials prepared by manganese acetate have smaller particle size and narrower particle size distribution, which can facilitate Li ions extraction and insertion. Furthermore, the sample LiNi0.5Mn1.5O4 prepared by manganese acetate has better electrochemical performances. An initial specific capacity of 144.5 mAh·g-1 at 1C in the voltage range of 3.6~5.2 V, 96% of the initial capacity after 100 cycles is maintained, and capacities of 136.3, 132.0, 124.7 and 96.6 mAh·g-1 are achieved at the rate of 3C, 5C, 10C and 20C, respectively.
Sub-micrometric LiNi0.5Mn1.5O4 cathode materials were prepared by sucrose combustion method with two different Mn sources. The effect of manganese acetate and manganese nitrate on the crystal structure, morphology, particle size and electrical performance of the prepared samples was evaluated by X-ray diffraction (XRD),scanning electron microscopy (SEM), particle size analysis, cyclic voltammetry (CV),galvanostatic charge-discharge test and electrochemical impedance spectroscopy (EIS). XRD analysis shows that the structure of both samples is a typical cubic spinel with Fd3m space group. The particle size and the distribution of the LiNi0.5Mn1.5O4 powder are strongly influenced by Mn source. The materials prepared by manganese acetate have smaller particle size and narrower particle size distribution, which can facilitate Li ions extraction and insertion. Furthermore, the sample LiNi0.5Mn1.5O4 prepared by manganese acetate has better electrochemical performances. An initial specific capacity of 144.5 mAh·g-1 at 1C in the voltage range of 3.6~5.2 V, 96% of the initial capacity after 100 cycles is maintained, and capacities of 136.3, 132.0, 124.7 and 96.6 mAh·g-1 are achieved at the rate of 3C, 5C, 10C and 20C, respectively.
2012, 28(12): 2581-2586
Abstract:
A complex of Zinc(Ⅱ), [Zn(atma)2]n in which the Hatma=[5-amino-1,3,4-thiadiazol-2-yl]thioglycolic acid has been synthesized and structurally characterized. The structure of the complex was determined by IR, TGA, elemental analysis and single crystal X-ray diffraction. In crystal, the title compound self-assembled from 2D layers to 3D surpramolecular framework by π-π interaction, hydrogen bonding and intercalation of groups. The cyclic voltammetry behaviors of the complex on glass carbon electrode showed a typical irreversible process. The antibacterial assays indicate that the complex shows better activities than ligand. CCDC: 805509.
A complex of Zinc(Ⅱ), [Zn(atma)2]n in which the Hatma=[5-amino-1,3,4-thiadiazol-2-yl]thioglycolic acid has been synthesized and structurally characterized. The structure of the complex was determined by IR, TGA, elemental analysis and single crystal X-ray diffraction. In crystal, the title compound self-assembled from 2D layers to 3D surpramolecular framework by π-π interaction, hydrogen bonding and intercalation of groups. The cyclic voltammetry behaviors of the complex on glass carbon electrode showed a typical irreversible process. The antibacterial assays indicate that the complex shows better activities than ligand. CCDC: 805509.
2012, 28(12): 2587-2592
Abstract:
The effect of directional electric field on the band gap of NiPc-COF was studied based on Density Functional Theory (DFT) calculations. The results indicate that electric field along [100] can effectively affect the electronic structure of NiPc-COF and result in the band gap of 0.22 eV at the electric field (EF) of 3.09 V·nm-1. Furthermore, both electronic structure and frontier orbits, coupled with Mülliken charge population, reveal that the polarization of charge density along [100] direction leads to the split of some degenerate orbits resulting in the decrease of band gap.
The effect of directional electric field on the band gap of NiPc-COF was studied based on Density Functional Theory (DFT) calculations. The results indicate that electric field along [100] can effectively affect the electronic structure of NiPc-COF and result in the band gap of 0.22 eV at the electric field (EF) of 3.09 V·nm-1. Furthermore, both electronic structure and frontier orbits, coupled with Mülliken charge population, reveal that the polarization of charge density along [100] direction leads to the split of some degenerate orbits resulting in the decrease of band gap.
2012, 28(12): 2593-2596
Abstract:
Two new complexes [CuL4Cl2] (1) and [AgL2]NO3 (2) (L=diniconazole) were synthesized by solvothermal condition and structurally characterized by element analysis, IR and single crystal X-ray diffraction. Complex 1 is the Triclinic system, space group P1 with a=0.882 3(7) nm, b=1.370 5(10) nm, c=1.516 4(11) nm, α=91.507(11)°, β=97.356(9)°, γ=107.683(9)°. Complex 2 belongs to the Monoclinic system, space group P21/c with a=1.229 2(3) nm, b=1.272 1(3) nm, c=2.431 7(5) nm, α=90°, β=98.694(3)°, γ=90°. 1 and 2 are linked into a one dimensional chain by intermolecular hydrogen bonds. CCDC: 805738, 1; 818240, 2.
Two new complexes [CuL4Cl2] (1) and [AgL2]NO3 (2) (L=diniconazole) were synthesized by solvothermal condition and structurally characterized by element analysis, IR and single crystal X-ray diffraction. Complex 1 is the Triclinic system, space group P1 with a=0.882 3(7) nm, b=1.370 5(10) nm, c=1.516 4(11) nm, α=91.507(11)°, β=97.356(9)°, γ=107.683(9)°. Complex 2 belongs to the Monoclinic system, space group P21/c with a=1.229 2(3) nm, b=1.272 1(3) nm, c=2.431 7(5) nm, α=90°, β=98.694(3)°, γ=90°. 1 and 2 are linked into a one dimensional chain by intermolecular hydrogen bonds. CCDC: 805738, 1; 818240, 2.
2012, 28(12): 2597-2604
Abstract:
La-doped SrTiO3 catalysts with different La contents were prepared by a sol-gel method, and characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-Vis diffuse reflectance spectra (UV-Vis DRS), and low temperature nitrogen adsorption. The photocatalytic activities were evaluated by photo-degradation of methyl orange (MO). The results show that La-doped SrTiO3 keeps a perovskite structure and the absorption edge of 0.5% La-SrTiO3 sample is obviously red-shifted. There is no big difference between pure SrTiO3 and 0.5% La-SrTiO3 samples in particle size and morphologies. With the increase of La content, the photocatalytic activities of La-SrTiO3 samples under UV and visible light irradiation first increase, reaching a maximums around La content of 0.5%, and then decrease with further increasing La. Compared with pure SrTiO3, the 0.5% La-SrTiO3 sample obviously exhibits much higher UV and visible light photocatalytic activity. The enhanced photocatalytic activity can be mainly attributed to the increase of BET surface area, the enhancement in adsorption performance, the stronger absorption in 250~650 nm light region and the lower band-gap energy level.
La-doped SrTiO3 catalysts with different La contents were prepared by a sol-gel method, and characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-Vis diffuse reflectance spectra (UV-Vis DRS), and low temperature nitrogen adsorption. The photocatalytic activities were evaluated by photo-degradation of methyl orange (MO). The results show that La-doped SrTiO3 keeps a perovskite structure and the absorption edge of 0.5% La-SrTiO3 sample is obviously red-shifted. There is no big difference between pure SrTiO3 and 0.5% La-SrTiO3 samples in particle size and morphologies. With the increase of La content, the photocatalytic activities of La-SrTiO3 samples under UV and visible light irradiation first increase, reaching a maximums around La content of 0.5%, and then decrease with further increasing La. Compared with pure SrTiO3, the 0.5% La-SrTiO3 sample obviously exhibits much higher UV and visible light photocatalytic activity. The enhanced photocatalytic activity can be mainly attributed to the increase of BET surface area, the enhancement in adsorption performance, the stronger absorption in 250~650 nm light region and the lower band-gap energy level.
2012, 28(12): 2605-2611
Abstract:
The thermodynamics of NH4+-Mg2+-PO43--H+-H2O system was investigated based on the construction of predominance diagrams. The lgCT,Mg-lgCT,P and lgCT,P-pH diagrams were constructed at an arbitrary Mg/P molar ratio with consideration of the ion strength influence(CT,Mg: total concentration of magnesium; CT,P: total concentration of phosphorus; CT,N: total concentration of nitrogen). The thermodynamic stable zones of struvite (MgNH4PO4·6H2O), bobierrite (Mg3(PO4)2·8H2O), newberyite (MgHPO4·3H2O), and magnesium hydroxide (Mg(OH)2) were determined. The results show that struvite and bobierrite are the dominating phases in a wide range of pH value. Struvite and newberyite coexist with solute phase at low pH value and high total concentration of phosphorus while struvite and magnesium hydroxide are more stable at the alkaline condition. The minimum total concentration of nitrogen appears at pH value of 9.08~9.52 while struvite and bobierrite coexist with the solute phase. The predominance diagrams could be used to predict the precipitation-dissolution equilibrium of struvite for ammonia nitrogen removal and recovery from wastewater.
The thermodynamics of NH4+-Mg2+-PO43--H+-H2O system was investigated based on the construction of predominance diagrams. The lgCT,Mg-lgCT,P and lgCT,P-pH diagrams were constructed at an arbitrary Mg/P molar ratio with consideration of the ion strength influence(CT,Mg: total concentration of magnesium; CT,P: total concentration of phosphorus; CT,N: total concentration of nitrogen). The thermodynamic stable zones of struvite (MgNH4PO4·6H2O), bobierrite (Mg3(PO4)2·8H2O), newberyite (MgHPO4·3H2O), and magnesium hydroxide (Mg(OH)2) were determined. The results show that struvite and bobierrite are the dominating phases in a wide range of pH value. Struvite and newberyite coexist with solute phase at low pH value and high total concentration of phosphorus while struvite and magnesium hydroxide are more stable at the alkaline condition. The minimum total concentration of nitrogen appears at pH value of 9.08~9.52 while struvite and bobierrite coexist with the solute phase. The predominance diagrams could be used to predict the precipitation-dissolution equilibrium of struvite for ammonia nitrogen removal and recovery from wastewater.
2012, 28(12): 2612-2616
Abstract:
Niobium nitride (NbN) nanoparticles have been synthesized by using a solid state reaction method in an autoclave at 350 ℃. According to the X-ray powder diffraction pattern, the NbN product can be index as cubic Fm3m space group. High-resolution electron microscopy and scanning electron microscope investigations show that the NbN particles obtained have diameters ranging from 30 to 300 nm. TGA curves indicate that the sample has good stability before 540 °C in air. The NbN sample combined with Li sheet was assembled into a coin cell. Its first charge specific capacity can reach 314 mAh·g-1. After 50 cycles, its capacity remains 228 mAh·g-1, showing a good cycling stability.
Niobium nitride (NbN) nanoparticles have been synthesized by using a solid state reaction method in an autoclave at 350 ℃. According to the X-ray powder diffraction pattern, the NbN product can be index as cubic Fm3m space group. High-resolution electron microscopy and scanning electron microscope investigations show that the NbN particles obtained have diameters ranging from 30 to 300 nm. TGA curves indicate that the sample has good stability before 540 °C in air. The NbN sample combined with Li sheet was assembled into a coin cell. Its first charge specific capacity can reach 314 mAh·g-1. After 50 cycles, its capacity remains 228 mAh·g-1, showing a good cycling stability.
2012, 28(12): 2617-2625
Abstract:
The effect of plating time and brightening additives (composed of saccharin, butynediol and sodium dodecyl sulfate) on the properties of gold deposits plated from a non-cyanide bath with 5, 5′-dimethylhydantoin (DMH) as the complexing agent was investigated by using scanning electron microscopy (SEM) and linear sweep voltammetry measurements. The results indicate that surface morphologies of gold electrodeposits are not markedly affected and do not change significantly with increasing deposition time, and brightening additives increase the cathodic polarization of bath and refine the grains of electrodeposits. The gold deposition rate in basic bath containing HAuCl4, DMH, K3PO4, KH2PO4 is 0.3 μm·min-1, and the high deposition rate is not influenced by the introduction of brightening additives. The properties of electrodeposits were evaluated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that the gold electrodeposits have a preferential orientation along (111) direction and are composed of pure Au0 state. The electrochemical behavior of Au(Ⅲ) in the bath onto glassy carbon electrode (GCE) at 45 ℃ was studied by cyclic voltammetry and standard rotating disk. The results indicate that the electrodeposition of metallic Au in the bath is an irreversible process and is controlled by the diffusion of Au (Ⅲ) onto GCE. The stability of the DMH-gold bath is also discussed.
The effect of plating time and brightening additives (composed of saccharin, butynediol and sodium dodecyl sulfate) on the properties of gold deposits plated from a non-cyanide bath with 5, 5′-dimethylhydantoin (DMH) as the complexing agent was investigated by using scanning electron microscopy (SEM) and linear sweep voltammetry measurements. The results indicate that surface morphologies of gold electrodeposits are not markedly affected and do not change significantly with increasing deposition time, and brightening additives increase the cathodic polarization of bath and refine the grains of electrodeposits. The gold deposition rate in basic bath containing HAuCl4, DMH, K3PO4, KH2PO4 is 0.3 μm·min-1, and the high deposition rate is not influenced by the introduction of brightening additives. The properties of electrodeposits were evaluated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that the gold electrodeposits have a preferential orientation along (111) direction and are composed of pure Au0 state. The electrochemical behavior of Au(Ⅲ) in the bath onto glassy carbon electrode (GCE) at 45 ℃ was studied by cyclic voltammetry and standard rotating disk. The results indicate that the electrodeposition of metallic Au in the bath is an irreversible process and is controlled by the diffusion of Au (Ⅲ) onto GCE. The stability of the DMH-gold bath is also discussed.
2012, 28(12): 2626-2632
Abstract:
This report describes a facile preparation and electrochemical properties of Mn2O3 sub-micron powder via thermal decomposition of an isonicotinic acid manganese complex. An isonicotinic acid manganese complex of [Mn(INA)2(H2O)4]n (INA=isonicotinic acid) was synthesized by liquid diffusion method using an aqueous solution of manganese acetate and isonicotinic acid as the raw material. Mn2O3 sub-micron powder was then prepared by solid-state thermolysis of the as-synthesized INA-Mn complex at higher temperature under atmospheric pressure. The obtained products were characterized by FTIR, TG-DTA, XRD, TEM and FESEM. As an electrode material for supercapacitors, the prepared Mn2O3 electrode shows a strong cycle stability in 0.5 mol·g-1 Na2SO4 electrolyte and a specific capacitance of 88 F·g-1 at a current density of 0.5 A·g-1 vs. the saturated calomel electrode (SCE).
This report describes a facile preparation and electrochemical properties of Mn2O3 sub-micron powder via thermal decomposition of an isonicotinic acid manganese complex. An isonicotinic acid manganese complex of [Mn(INA)2(H2O)4]n (INA=isonicotinic acid) was synthesized by liquid diffusion method using an aqueous solution of manganese acetate and isonicotinic acid as the raw material. Mn2O3 sub-micron powder was then prepared by solid-state thermolysis of the as-synthesized INA-Mn complex at higher temperature under atmospheric pressure. The obtained products were characterized by FTIR, TG-DTA, XRD, TEM and FESEM. As an electrode material for supercapacitors, the prepared Mn2O3 electrode shows a strong cycle stability in 0.5 mol·g-1 Na2SO4 electrolyte and a specific capacitance of 88 F·g-1 at a current density of 0.5 A·g-1 vs. the saturated calomel electrode (SCE).
2012, 28(12): 2633-2637
Abstract:
A new zinc(Ⅱ) coordination polymer [Zn(bbmb)(Pht)]n (bbmb=4,4′-bis(benzimidazol-1-ylmethy1)biphenyl, H2Pht=phthalic acid) has been prepared by hydrothermal method and structurally characterized by elemental analysis, IR, PXRD, TGA and single-crystal X-ray diffraction. The title compound crystallizes in monoclinic, space group P21/c with a=1.085 28(10) nm, b=2.286 7(2) nm, c=1.218 53(12) nm, β=102.589(3)°, V=2.951 3(5) nm3, Z=4, and exhibits a 2D network. Fluorescence spectrum studies reveals that the zinc(Ⅱ) complex exhibits strong fluorescence absorption at 416 nm (λmax) in the solid state at room temperature. CCDC: 880548.
A new zinc(Ⅱ) coordination polymer [Zn(bbmb)(Pht)]n (bbmb=4,4′-bis(benzimidazol-1-ylmethy1)biphenyl, H2Pht=phthalic acid) has been prepared by hydrothermal method and structurally characterized by elemental analysis, IR, PXRD, TGA and single-crystal X-ray diffraction. The title compound crystallizes in monoclinic, space group P21/c with a=1.085 28(10) nm, b=2.286 7(2) nm, c=1.218 53(12) nm, β=102.589(3)°, V=2.951 3(5) nm3, Z=4, and exhibits a 2D network. Fluorescence spectrum studies reveals that the zinc(Ⅱ) complex exhibits strong fluorescence absorption at 416 nm (λmax) in the solid state at room temperature. CCDC: 880548.
2012, 28(12): 2638-2642
Abstract:
A coordination complex [Mn(ADB)(phen)(H2O)2] (1) (ADB=azobenzen-4,4′-dicarboxylic acid ion, phen=1,10-phenanthroline) have been synthesized by hydrothermal reaction and characterized by elemental analysis, IR spectra, thermal analysis and electrochemical property, and the crystal structures were determined by single crystal X ray diffraction. Single-crystal X ray diffraction analyses indicate that complex belongs to triclinic system and the space group is P1, the parameters of the crystal cell for the complex are a=0.762 00(13) nm, b=0.915 30(15) nm, c=1.826 2(2) nm, α=88.467(3)°, β=84.145(2)°, γ=77.542(2)°. The manganese centre is six-coordinated, with a distorted octahedral geometry. The Mn(Ⅱ) center is connected to form a 1D zigzag chain structure bridged by azobenzen-4,4′-dicarboxylic acid ligand, further extended into a 3D supramolecular structure through π-π stacking and hydrogen bonding interactions. Magnetic property of 1 is investigated and exhibited antiferromagnetic interactions. CCDC: 847696.
A coordination complex [Mn(ADB)(phen)(H2O)2] (1) (ADB=azobenzen-4,4′-dicarboxylic acid ion, phen=1,10-phenanthroline) have been synthesized by hydrothermal reaction and characterized by elemental analysis, IR spectra, thermal analysis and electrochemical property, and the crystal structures were determined by single crystal X ray diffraction. Single-crystal X ray diffraction analyses indicate that complex belongs to triclinic system and the space group is P1, the parameters of the crystal cell for the complex are a=0.762 00(13) nm, b=0.915 30(15) nm, c=1.826 2(2) nm, α=88.467(3)°, β=84.145(2)°, γ=77.542(2)°. The manganese centre is six-coordinated, with a distorted octahedral geometry. The Mn(Ⅱ) center is connected to form a 1D zigzag chain structure bridged by azobenzen-4,4′-dicarboxylic acid ligand, further extended into a 3D supramolecular structure through π-π stacking and hydrogen bonding interactions. Magnetic property of 1 is investigated and exhibited antiferromagnetic interactions. CCDC: 847696.
2012, 28(12): 2643-2649
Abstract:
Ba1.03Ce0.9-xZrxTm0.1O3-α(x=0.2, 0.4) solid electrolytes with nonstoichiometric composition were prepared by high temperature solid-state reaction. Phase composition and fracture morphologies of the two materials were characterized by using XRD and SEM, respectively. Chemical stability against carbon dioxide and water steam at 900 ℃ was tested. Ionic conduction was studied by using gas concentration cell and ac impedance spectroscopy methods, and the performances of the hydrogen-air fuel cells using the two materials as solid electrolytes were evaluated in the temperature range of 500~900 ℃. The results indicate that the material with x of 0.2 is a single-phase perovskite-type orthorhombic system, and the material with x of 0.4 is a single-phase perovskite-type cubic system. They both have high density and good chemical stability. In wet hydrogen, Ba1.03Ce0.7Zr0.2Tm0.1O3-α shows a pure ionic conduction, but Ba1.03Ce0.5Zr0.4Tm0.1O3-α shows a mixed conduction of ion and electron from 500 to 900 ℃. The two materials both show a mixed conduction of proton, oxide ion and electronic hole in wet air, and a mixed conduction of proton, oxide ion and electron in hydrogen-air fuel cell. The fuel cells using the two materials as solid electrolytes can both work stably. The ionic conduction and performance of the hydrogen-air fuel cell of Ba1.03Ce0.7Zr0.2Tm0.1O3-α are superior to those of Ba1.03Ce0.5Zr0.4Tm0.1O3-α under the same experimental conditions.
Ba1.03Ce0.9-xZrxTm0.1O3-α(x=0.2, 0.4) solid electrolytes with nonstoichiometric composition were prepared by high temperature solid-state reaction. Phase composition and fracture morphologies of the two materials were characterized by using XRD and SEM, respectively. Chemical stability against carbon dioxide and water steam at 900 ℃ was tested. Ionic conduction was studied by using gas concentration cell and ac impedance spectroscopy methods, and the performances of the hydrogen-air fuel cells using the two materials as solid electrolytes were evaluated in the temperature range of 500~900 ℃. The results indicate that the material with x of 0.2 is a single-phase perovskite-type orthorhombic system, and the material with x of 0.4 is a single-phase perovskite-type cubic system. They both have high density and good chemical stability. In wet hydrogen, Ba1.03Ce0.7Zr0.2Tm0.1O3-α shows a pure ionic conduction, but Ba1.03Ce0.5Zr0.4Tm0.1O3-α shows a mixed conduction of ion and electron from 500 to 900 ℃. The two materials both show a mixed conduction of proton, oxide ion and electronic hole in wet air, and a mixed conduction of proton, oxide ion and electron in hydrogen-air fuel cell. The fuel cells using the two materials as solid electrolytes can both work stably. The ionic conduction and performance of the hydrogen-air fuel cell of Ba1.03Ce0.7Zr0.2Tm0.1O3-α are superior to those of Ba1.03Ce0.5Zr0.4Tm0.1O3-α under the same experimental conditions.
2012, 28(12): 2650-2654
Abstract:
Employing N-acetylsalicylhydrazide (H3ashz), imidazole (imdz) as mixed ligands, a new trinuclear nickel(Ⅱ) compound [Ni3(ashz)2(imdz)2]·2DMF has been synthesized and characterized by elemental analysis, IR and X-ray diffraction structural analysis. Crystal data: monoclinic, space group P21/n with a=1.028 0(2) nm, b=1.499 2(3) nm, c=1.523 1(5) nm, β=114.16(2)°, V=2.140 1(9) nm3, Z=2, Dc=1.516 g·cm-3, μ=1.372 mm-1, F(000)= 1 012. In the title complex, two μ2-bridged ashz3- ligands bound to three nickel centers in a linear array. The three nickel atoms are directly linked together by two trans diazine (N-N) bridges, with the neighboring nickel atomic separations of 0.462(1) nm. CCDC: 902486.
Employing N-acetylsalicylhydrazide (H3ashz), imidazole (imdz) as mixed ligands, a new trinuclear nickel(Ⅱ) compound [Ni3(ashz)2(imdz)2]·2DMF has been synthesized and characterized by elemental analysis, IR and X-ray diffraction structural analysis. Crystal data: monoclinic, space group P21/n with a=1.028 0(2) nm, b=1.499 2(3) nm, c=1.523 1(5) nm, β=114.16(2)°, V=2.140 1(9) nm3, Z=2, Dc=1.516 g·cm-3, μ=1.372 mm-1, F(000)= 1 012. In the title complex, two μ2-bridged ashz3- ligands bound to three nickel centers in a linear array. The three nickel atoms are directly linked together by two trans diazine (N-N) bridges, with the neighboring nickel atomic separations of 0.462(1) nm. CCDC: 902486.
2012, 28(12): 2655-2659
Abstract:
A coordination polymer, namely [Cd(3-CPOA)(phen)]n (1) has been constructed hydrothermally using 3-H2CPOA (3-H2CPOA=3-carboxyphenoxyacetatic acid), phen (phen=1,10-phenanthroline) and Cd(OAc)2·2H2O. The complex crystallizes in the monoclinic system, space group C2 with a=1.575 3(7) nm, b=1.035 4(5) nm, c=1.133 9(5) nm, β=97.806(4)°, V=1.832 3(15) nm3, Dc=1.764 g·cm-3, Z=4, R=0.020 4 and wR=0.039 7 (I>2σ(I)). Two Cd(Ⅱ) atoms, two CPOA2- ligands and two phen ligands form a [Cd2(CPOA)2(phen)2] ring. The rings are connected by the coordination interactions of CPOA2- ligands and Cd(Ⅱ) ions to generate a 1D double-chain, which are further extended into a 3D metal-organic supramolecular framework by C-H…O hydrogen bond interactions. Luminescent studies show that complex 1 displays strong blue emission at room temperature. CCDC: 853932.
A coordination polymer, namely [Cd(3-CPOA)(phen)]n (1) has been constructed hydrothermally using 3-H2CPOA (3-H2CPOA=3-carboxyphenoxyacetatic acid), phen (phen=1,10-phenanthroline) and Cd(OAc)2·2H2O. The complex crystallizes in the monoclinic system, space group C2 with a=1.575 3(7) nm, b=1.035 4(5) nm, c=1.133 9(5) nm, β=97.806(4)°, V=1.832 3(15) nm3, Dc=1.764 g·cm-3, Z=4, R=0.020 4 and wR=0.039 7 (I>2σ(I)). Two Cd(Ⅱ) atoms, two CPOA2- ligands and two phen ligands form a [Cd2(CPOA)2(phen)2] ring. The rings are connected by the coordination interactions of CPOA2- ligands and Cd(Ⅱ) ions to generate a 1D double-chain, which are further extended into a 3D metal-organic supramolecular framework by C-H…O hydrogen bond interactions. Luminescent studies show that complex 1 displays strong blue emission at room temperature. CCDC: 853932.
2012, 28(12): 2660-2666
Abstract:
By employing KBF4 or K2SiF6 as fluoride source, a facile glycine-assisted hydrothermal route has been developed to synthesize a series of well-dispersed CaF2∶Ln3+(Ln=Eu, Tb) microcrystals with a variety of morphologies, such as cubes, hollow polyhedra and hollow spheres. X-ray diffraction (XRD), Fourier transform IR (FTIR), scanning electron microscopy (SEM) and photoluminescence (PL) were used to characterize the purity, crystalline phase, morphologies and the photoluminescence properties of the samples. The XRD results show that all the as-prepared CaF2 have cubic structure and high crystallinity. The SEM results indicate that, in the presence of glycine, the as-prepared CaF2 microcrystals present morphologies of highly dispersed hollow polyhedra and hollow spheres obtained from KBF4 and K2SiF6, respectively. Meanwhile, the CaF2 hollow spheres were assembled from numerous nanocubes. In the synthetic process, glycine, fluoride source and reaction time play crucial role in confining the growth of the different morphological CaF2 microcrystals. The growth mechanism for products with diverse microstructures have been proposed based on the experimental results.
By employing KBF4 or K2SiF6 as fluoride source, a facile glycine-assisted hydrothermal route has been developed to synthesize a series of well-dispersed CaF2∶Ln3+(Ln=Eu, Tb) microcrystals with a variety of morphologies, such as cubes, hollow polyhedra and hollow spheres. X-ray diffraction (XRD), Fourier transform IR (FTIR), scanning electron microscopy (SEM) and photoluminescence (PL) were used to characterize the purity, crystalline phase, morphologies and the photoluminescence properties of the samples. The XRD results show that all the as-prepared CaF2 have cubic structure and high crystallinity. The SEM results indicate that, in the presence of glycine, the as-prepared CaF2 microcrystals present morphologies of highly dispersed hollow polyhedra and hollow spheres obtained from KBF4 and K2SiF6, respectively. Meanwhile, the CaF2 hollow spheres were assembled from numerous nanocubes. In the synthetic process, glycine, fluoride source and reaction time play crucial role in confining the growth of the different morphological CaF2 microcrystals. The growth mechanism for products with diverse microstructures have been proposed based on the experimental results.
2012, 28(12): 2667-2673
Abstract:
The copper(Ⅱ) complex [Cu(H2O)(Gly)(PZTA)]ClO4 (Gly=glycinate) was prepared by the reaction of 6-(pyrazin-2′-yl)-1,3,5-triazine-2,4-diamine (PZTA) and glycine (Gly) with copper(Ⅱ) perchlorate, and characterized by elemental analysis, infrared radiation, UV-Vis, and molar conductance. Its crystal structure was determined by single crystal X-ray diffraction method. The complex crystallizes in the monoclinic system, space group C2/c, with cell parameters: a=2.189 6(3) nm, b=1.308 3(2) nm, c=1.465 4(4) nm, β=131.467(3)°, cell volume: V=3.145 6(9) nm3, number of molecules inside the cell: Z=8, final R indices (I>2σ(I)): R1=0.037 4, wR2=0.100 9. The interaction of the complex to DNA was studied by UV spectroscopy, EtBr fluoescent probe and viscosity measurement. The results indicate that the complex could interact with DNA by partial intercalative mode. CCDC: 848150.
The copper(Ⅱ) complex [Cu(H2O)(Gly)(PZTA)]ClO4 (Gly=glycinate) was prepared by the reaction of 6-(pyrazin-2′-yl)-1,3,5-triazine-2,4-diamine (PZTA) and glycine (Gly) with copper(Ⅱ) perchlorate, and characterized by elemental analysis, infrared radiation, UV-Vis, and molar conductance. Its crystal structure was determined by single crystal X-ray diffraction method. The complex crystallizes in the monoclinic system, space group C2/c, with cell parameters: a=2.189 6(3) nm, b=1.308 3(2) nm, c=1.465 4(4) nm, β=131.467(3)°, cell volume: V=3.145 6(9) nm3, number of molecules inside the cell: Z=8, final R indices (I>2σ(I)): R1=0.037 4, wR2=0.100 9. The interaction of the complex to DNA was studied by UV spectroscopy, EtBr fluoescent probe and viscosity measurement. The results indicate that the complex could interact with DNA by partial intercalative mode. CCDC: 848150.
2012, 28(12): 2674-2680
Abstract:
The two 1D coordination polymers [Zn(L)2(TP)]n (1) and [Cu(L)2(TP)]n (2) (L=1-butylbenzimidazole, TP=terephthalate ion) have been prepared via the reaction of 1-butylbenzimidazole, terephthalic acid and Zn(NO3)2·6H2O or Cu(NO3)2·3H2O, respectively. The structures of these complexes were characterized by X-ray diffraction analysis. In the crystal packings of coordination polymers 1 and 2, 2D supramolecular layers are formed through C-H…O or O-H…O hydrogen bonds, respectively. The fluorescence emission spectra of L, 1 and 2 are described. CCDC: 899947, 1; 899948, 2.
The two 1D coordination polymers [Zn(L)2(TP)]n (1) and [Cu(L)2(TP)]n (2) (L=1-butylbenzimidazole, TP=terephthalate ion) have been prepared via the reaction of 1-butylbenzimidazole, terephthalic acid and Zn(NO3)2·6H2O or Cu(NO3)2·3H2O, respectively. The structures of these complexes were characterized by X-ray diffraction analysis. In the crystal packings of coordination polymers 1 and 2, 2D supramolecular layers are formed through C-H…O or O-H…O hydrogen bonds, respectively. The fluorescence emission spectra of L, 1 and 2 are described. CCDC: 899947, 1; 899948, 2.
