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2014 Volume 30 Issue 2
2014, (2): 229-234
doi: 10.11862/CJIC.2014.011
Abstract:
ZnO nanorod/Mica composite powders were successfully fabricated with chemical liquid deposition (CLD). The composite powder consisting of mica and ZnO nanorod was fabricated via a two-step process: (1) The ZnO colloid particles were absorbed on the surface of sheetlike mica particles via electrostatic interaction, and then heat-treatment was used to attain mica particles with ZnO nanocrystals loaded on the surface; (2) Precursor solution prepared with zinc sulfate heptahydrate, ethanolamine and ammonia was used to load ZnO nanorods on the surface of mica. The resultant composite particles were characterized by XRD, Zeta potential analyzer, scanning electron microscope (SEM) and spectral radiometer. The results showed that the ζ potential of mica in the ethanol/water solution (1:1, V/V) was -37 mV, while the ζ potential of ZnO colloidal particles was 16 mV. Thus the ZnO colloidal particles can be absorbed on the surface of mica particles via electrostatic interaction. As increased deposition density of ZnO nanorod on the surface of mica particles, the emissivity of the particles in 8~14 μm region increased from 0.800 to 0.863. Compared with the rodlike ZnO particles, the aggregation of structural unit had no obvious effect on the infrared emissivity of the particles.
ZnO nanorod/Mica composite powders were successfully fabricated with chemical liquid deposition (CLD). The composite powder consisting of mica and ZnO nanorod was fabricated via a two-step process: (1) The ZnO colloid particles were absorbed on the surface of sheetlike mica particles via electrostatic interaction, and then heat-treatment was used to attain mica particles with ZnO nanocrystals loaded on the surface; (2) Precursor solution prepared with zinc sulfate heptahydrate, ethanolamine and ammonia was used to load ZnO nanorods on the surface of mica. The resultant composite particles were characterized by XRD, Zeta potential analyzer, scanning electron microscope (SEM) and spectral radiometer. The results showed that the ζ potential of mica in the ethanol/water solution (1:1, V/V) was -37 mV, while the ζ potential of ZnO colloidal particles was 16 mV. Thus the ZnO colloidal particles can be absorbed on the surface of mica particles via electrostatic interaction. As increased deposition density of ZnO nanorod on the surface of mica particles, the emissivity of the particles in 8~14 μm region increased from 0.800 to 0.863. Compared with the rodlike ZnO particles, the aggregation of structural unit had no obvious effect on the infrared emissivity of the particles.
2014, (2): 235-241
doi: 10.11862/CJIC.2014.051
Abstract:
The cathode material LiFePO4 with tap density of ca. 1.2 g·cm-3 was synthesized by solvothermal method, using P123 as soft template and ethylene glycol as solvent. The composition, crystal shape, morphology and pore structure of the as-prepared samples were characterized by X-ray diffraction(XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM), Brunauer-Emmett-Teller (BET). The results show that the nest-like LiFePO4 consists of single-crystalline nanoplates with an open three-dimensional porous hierarchical structure. A reasonable formation mechanism is proposed based on time dependent experiments. The main evolving process involves the following steps: nucleation, oriented growth, aggregation and oriented growth. The electrochemical testing results show that the initial discharge specific capacities of nest-like LiFePO4 reach to 132.5 mAh·g-1 at 0.1C.
The cathode material LiFePO4 with tap density of ca. 1.2 g·cm-3 was synthesized by solvothermal method, using P123 as soft template and ethylene glycol as solvent. The composition, crystal shape, morphology and pore structure of the as-prepared samples were characterized by X-ray diffraction(XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM), Brunauer-Emmett-Teller (BET). The results show that the nest-like LiFePO4 consists of single-crystalline nanoplates with an open three-dimensional porous hierarchical structure. A reasonable formation mechanism is proposed based on time dependent experiments. The main evolving process involves the following steps: nucleation, oriented growth, aggregation and oriented growth. The electrochemical testing results show that the initial discharge specific capacities of nest-like LiFePO4 reach to 132.5 mAh·g-1 at 0.1C.
2014, (2): 242-250
doi: 10.11862/CJIC.2014.048
Abstract:
To solve the main obstacles associated with the charge-discharge process of α-Fe2O3 anode, such as serious volume expansion and low initial coulombic efficiency, 3D porous α-Fe2O3/nitrogen-doped graphene(N-GNS)/carbon nanotubes(CNTs) nanocomposites were synthesized via a facile hydrothermal method. The nanocomposites were characterized by XRD, SEM, TEM and XPS measurements and the results indicated that CNTs were successfully inserted into the interlamination between N-GNS, providing more defects than pristine GNS for α-Fe2O3 nucleating and the lithium ion storage. α-Fe2O3 nanoparticles with an average size of 30~70 nm were uniformly anchored in 3D N-GNS/CNTs carbon matrix and reacted with lithium ion efficiently. The electrochemical test results showed that this 3D composite structure can significantly improve the electrochemical performance of α-Fe2O3/GNS anode.
To solve the main obstacles associated with the charge-discharge process of α-Fe2O3 anode, such as serious volume expansion and low initial coulombic efficiency, 3D porous α-Fe2O3/nitrogen-doped graphene(N-GNS)/carbon nanotubes(CNTs) nanocomposites were synthesized via a facile hydrothermal method. The nanocomposites were characterized by XRD, SEM, TEM and XPS measurements and the results indicated that CNTs were successfully inserted into the interlamination between N-GNS, providing more defects than pristine GNS for α-Fe2O3 nucleating and the lithium ion storage. α-Fe2O3 nanoparticles with an average size of 30~70 nm were uniformly anchored in 3D N-GNS/CNTs carbon matrix and reacted with lithium ion efficiently. The electrochemical test results showed that this 3D composite structure can significantly improve the electrochemical performance of α-Fe2O3/GNS anode.
2014, (2): 251-256
doi: 10.11862/CJIC.2014.020
Abstract:
A (D-π-A) ligand, ferrocene-cyano-carboxylic acid, was synthesized, and it was assembled with organotins, dibutyltin oxide (n-Bu2SnO), to obtain a novel ferrocene organotin coordination compond. They have been characterized by 1H NMR, 119Sn NMR, IR, FT-IR, UV-Vis and elemental analysis. The crystal structure of complex has been determined by X-ray single crystal diffraction. Their electrochemical and two-photon absorption properties were systematically studied using cyclic voltammetry and Z-scan determination method. The results indicated that the complex is more difficult to be oxidized and possess a larger two-photon absorption cross section than its ligand. CCDC: 921958.
A (D-π-A) ligand, ferrocene-cyano-carboxylic acid, was synthesized, and it was assembled with organotins, dibutyltin oxide (n-Bu2SnO), to obtain a novel ferrocene organotin coordination compond. They have been characterized by 1H NMR, 119Sn NMR, IR, FT-IR, UV-Vis and elemental analysis. The crystal structure of complex has been determined by X-ray single crystal diffraction. Their electrochemical and two-photon absorption properties were systematically studied using cyclic voltammetry and Z-scan determination method. The results indicated that the complex is more difficult to be oxidized and possess a larger two-photon absorption cross section than its ligand. CCDC: 921958.
2014, (2): 257-263
doi: 10.11862/CJIC.2014.017
Abstract:
Four metal-organic supramolecular complexes, [Zn(3,5-dnbc)2(2,2'-bipy)(H2O)]·(3,5-Hdnbc) (1), [Cu(3,5-dnbc)2(2,2'-bipy)(H2O)] (2), [Cu(2,2'-bipy)2(3,5-dnbc)](NO3)·2(3,5-Hdnbc) (3), and [Cu(2,2'-bipy)2Cl](3,5-dnbc)·(3,5-Hdnbc) (4) were obtained by the reactions of 3,5-dinitrobenzoic acid and 2,2'-bipyridine as ligands with Zn2+ and Cu2+ ions. The four complexes were characterized by elemental analysis, IR, and the crystal structures were determined by single X-ray diffraction. The complexes of 1 and 2 were characterized by thermal gravimetric analysis. All of the four complexes are mononuclear complexes. In complex 1, Zn2+ is five-coordination in a distorted trigonal bipyramid geometry; in complex 2, Cu2+ is five-coordination in a distorted tetragonal pyramid geometry; in complex 3 and 4, Cu2+ is five-coordination in a distorted trigonal bipyramid geometry. Hydrogen bonding and π-π interactions are observed in these complexes. CCDC: 931926, 1; 931927, 2; 931928, 3; 931929, 4.
Four metal-organic supramolecular complexes, [Zn(3,5-dnbc)2(2,2'-bipy)(H2O)]·(3,5-Hdnbc) (1), [Cu(3,5-dnbc)2(2,2'-bipy)(H2O)] (2), [Cu(2,2'-bipy)2(3,5-dnbc)](NO3)·2(3,5-Hdnbc) (3), and [Cu(2,2'-bipy)2Cl](3,5-dnbc)·(3,5-Hdnbc) (4) were obtained by the reactions of 3,5-dinitrobenzoic acid and 2,2'-bipyridine as ligands with Zn2+ and Cu2+ ions. The four complexes were characterized by elemental analysis, IR, and the crystal structures were determined by single X-ray diffraction. The complexes of 1 and 2 were characterized by thermal gravimetric analysis. All of the four complexes are mononuclear complexes. In complex 1, Zn2+ is five-coordination in a distorted trigonal bipyramid geometry; in complex 2, Cu2+ is five-coordination in a distorted tetragonal pyramid geometry; in complex 3 and 4, Cu2+ is five-coordination in a distorted trigonal bipyramid geometry. Hydrogen bonding and π-π interactions are observed in these complexes. CCDC: 931926, 1; 931927, 2; 931928, 3; 931929, 4.
2014, (2): 264-270
doi: 10.11862/CJIC.2014.031
Abstract:
Two copper complexes: Cu2(mpz*eaT-EtO)2(N3)2Cl2 (1) and Cu2(mpz*eaT-MeO)2(N3)4 (2) (mpz*eaT-EtO=2-(3,5-dimethyl pyrazole)-4-ethanol-6-diethylamine-1,3,5-triazine, mpz*eaT-MeO=2-(3,5-dimethyl pyrazole)-4-methanol-6-diethylamine-1,3,5-triazine) were synthesized with the tridentate chelate triazine-pyrazole derivative 2,4-di(3,5-dimethyl pyrazole)-6-diethylamine-1,3,5-triazine (bpz*eaT) in the anhydrous ethanol and anhydrous methanol system, respectively. The complexes were characterized by elemental analysis, IR spectroscopy, UV spectrum thermal gravimetric analyses and single crystal X-ray diffraction. The crystal of complex 1 belongs to triclinic system, Space group P1, a=0.994 9(2) nm, b=1.021 6(2) nm, c=1.148 0(2) nm, α=115.11(3)°, β=106.99(3)°, γ=100.39(3)°, V=0.9460(3) nm3, Z=1; The crystal of complex 2 belongs to Monoclinic, Space group P21/c, a=1.546 4(5) nm, b=1.400 8(5) nm, c=0.890 5(3) nm, β=103.227(5)°, V=1.877 9(10) nm3, Z=2. Structural analyses have revealed that the center copper atom is five-coordinated to form distorted pyramidic geometry. CCDC: 935290, 1; 935291, 2.
Two copper complexes: Cu2(mpz*eaT-EtO)2(N3)2Cl2 (1) and Cu2(mpz*eaT-MeO)2(N3)4 (2) (mpz*eaT-EtO=2-(3,5-dimethyl pyrazole)-4-ethanol-6-diethylamine-1,3,5-triazine, mpz*eaT-MeO=2-(3,5-dimethyl pyrazole)-4-methanol-6-diethylamine-1,3,5-triazine) were synthesized with the tridentate chelate triazine-pyrazole derivative 2,4-di(3,5-dimethyl pyrazole)-6-diethylamine-1,3,5-triazine (bpz*eaT) in the anhydrous ethanol and anhydrous methanol system, respectively. The complexes were characterized by elemental analysis, IR spectroscopy, UV spectrum thermal gravimetric analyses and single crystal X-ray diffraction. The crystal of complex 1 belongs to triclinic system, Space group P1, a=0.994 9(2) nm, b=1.021 6(2) nm, c=1.148 0(2) nm, α=115.11(3)°, β=106.99(3)°, γ=100.39(3)°, V=0.9460(3) nm3, Z=1; The crystal of complex 2 belongs to Monoclinic, Space group P21/c, a=1.546 4(5) nm, b=1.400 8(5) nm, c=0.890 5(3) nm, β=103.227(5)°, V=1.877 9(10) nm3, Z=2. Structural analyses have revealed that the center copper atom is five-coordinated to form distorted pyramidic geometry. CCDC: 935290, 1; 935291, 2.
2014, (2): 271-276
doi: 10.11862/CJIC.2014.025
Abstract:
A multi-step method was adopted to prepare a magnetic Pt/Fe3O4-MCNT catalyst by loading as-prepared Fe3O4 and Pt nanoparticles onto multi-walled carbon nanotubes (MCNT). The structure and magnetic properties of the prepared Pt/Fe3O4-MCNT catalyst were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), superconducting quantum interference device (SQUID), and thermogravimetry-differential thermal analysis (TG-DTA). The results reveal that the as-prepared Fe3O4 and Pt nanoparticles are well dispersed on the MCNT. Additionally, the magnetic measurements show that both fresh and recycled magnetic Pt/Fe3O4-MCNT catalysts display excellent superparamagnetic properties at room temperature. The selective hydrogenation of cinnamaldehyde to cinnamyl alcohol was performed on the magnetic Pt/Fe3O4-MCNT catalyst, showing a superior activity in the hydrogenation of the C=O bond. A selectivity of 96% to cinnamyl alcohol can be achieved at a cinnamaldehyde conversion of about 50%. The reason of the good selectivity probably ascribes to the high dispersion of the uniformed Pt particles on the MCNT. Additionally, the catalyst can be easily recovered from the reaction medium under the external magnetic field and maintain its catalytic properties after used for several recycles.
A multi-step method was adopted to prepare a magnetic Pt/Fe3O4-MCNT catalyst by loading as-prepared Fe3O4 and Pt nanoparticles onto multi-walled carbon nanotubes (MCNT). The structure and magnetic properties of the prepared Pt/Fe3O4-MCNT catalyst were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), superconducting quantum interference device (SQUID), and thermogravimetry-differential thermal analysis (TG-DTA). The results reveal that the as-prepared Fe3O4 and Pt nanoparticles are well dispersed on the MCNT. Additionally, the magnetic measurements show that both fresh and recycled magnetic Pt/Fe3O4-MCNT catalysts display excellent superparamagnetic properties at room temperature. The selective hydrogenation of cinnamaldehyde to cinnamyl alcohol was performed on the magnetic Pt/Fe3O4-MCNT catalyst, showing a superior activity in the hydrogenation of the C=O bond. A selectivity of 96% to cinnamyl alcohol can be achieved at a cinnamaldehyde conversion of about 50%. The reason of the good selectivity probably ascribes to the high dispersion of the uniformed Pt particles on the MCNT. Additionally, the catalyst can be easily recovered from the reaction medium under the external magnetic field and maintain its catalytic properties after used for several recycles.
2014, (2): 277-283
doi: 10.11862/CJIC.2014.021
Abstract:
Nickel-based catalysts were prepared with different metal promoters by incipient impregnation method, and the catalytic performance of CO methanation were studied in slurry-bed reactor. XRD, H2-TPR, and HR-TEM were used to characterize the catalysts, the results show that additives of Zr, Co, Ce, Zn, La improved the dispersion of Nickel species on support, and decreased the particle size of Ni and reduced the reduction temperature of catalyst, while the additive of Mg increased the reduction temperature. The catalytic results show that additives of Zr, Co, Ce, Zn, La improved the catalytic performance of CO methanation in slurry-bed reactor, especially the catalyst with La additive. Further investigation shows that when the loading of La reached 8%, the catalyst exhibited the best catalytic performance, with the conversion of CO of 96.3%, the selectivity and space-time yield (STY) of CH4 of 87.1% and 179.6 g·kg-1·h-1, respectively. While the catalyst doped with Mg additivie decreased the catalytic performance.
Nickel-based catalysts were prepared with different metal promoters by incipient impregnation method, and the catalytic performance of CO methanation were studied in slurry-bed reactor. XRD, H2-TPR, and HR-TEM were used to characterize the catalysts, the results show that additives of Zr, Co, Ce, Zn, La improved the dispersion of Nickel species on support, and decreased the particle size of Ni and reduced the reduction temperature of catalyst, while the additive of Mg increased the reduction temperature. The catalytic results show that additives of Zr, Co, Ce, Zn, La improved the catalytic performance of CO methanation in slurry-bed reactor, especially the catalyst with La additive. Further investigation shows that when the loading of La reached 8%, the catalyst exhibited the best catalytic performance, with the conversion of CO of 96.3%, the selectivity and space-time yield (STY) of CH4 of 87.1% and 179.6 g·kg-1·h-1, respectively. While the catalyst doped with Mg additivie decreased the catalytic performance.
2014, (2): 284-292
doi: 10.11862/CJIC.2014.024
Abstract:
In this paper, NbS2-xSex nanoparticles were synthesized by solid state reaction. The effect of Se doped amount, reaction temperature and reaction time on evolution rules of crystal form and morphology of the production of Nb2-xSex nanomaterials were discussed, phase and microstructure of as-synthesized samples were examined by means of XRD, SEM, TEM and HRTEM. The results show that the morphology of NbS2-xSex nanobelt(nanoclintheriform) turned into nanoflake after Se was doped, meanwhile diffraction peaks were broadened, peak intensity become weaker, grains were refined. What's more, the doping amount, reaction temperature and reaction time play a greater impact on the morphology of the production. The morphology of NbS1.9Se0.1 which was doped by 5at% Se at 750 ℃ for 2h was fine. The results of UMT-2 tribology experiment show that the doped NbS2-xSex has excellent friction performance when NbS2-xSex was used as additive in liquid paraffin oil. Furthermore the NbS1.9Se0.1 that doped 5at% Se, at 750 ℃ for 2 h, has the best friction performance and the friction mechanism was also explained at the same time.
In this paper, NbS2-xSex nanoparticles were synthesized by solid state reaction. The effect of Se doped amount, reaction temperature and reaction time on evolution rules of crystal form and morphology of the production of Nb2-xSex nanomaterials were discussed, phase and microstructure of as-synthesized samples were examined by means of XRD, SEM, TEM and HRTEM. The results show that the morphology of NbS2-xSex nanobelt(nanoclintheriform) turned into nanoflake after Se was doped, meanwhile diffraction peaks were broadened, peak intensity become weaker, grains were refined. What's more, the doping amount, reaction temperature and reaction time play a greater impact on the morphology of the production. The morphology of NbS1.9Se0.1 which was doped by 5at% Se at 750 ℃ for 2h was fine. The results of UMT-2 tribology experiment show that the doped NbS2-xSex has excellent friction performance when NbS2-xSex was used as additive in liquid paraffin oil. Furthermore the NbS1.9Se0.1 that doped 5at% Se, at 750 ℃ for 2 h, has the best friction performance and the friction mechanism was also explained at the same time.
2014, (2): 293-302
doi: 10.11862/CJIC.2014.033
Abstract:
ZnOand doped ZnOnano-powder with M2+(M=Cu, Cd, Ag and Fe ) were synthesized by citrate sol-gel method. The composition,structures and morphology of the samples were characterized by means of modern testing techniques. The antibacterial activities of the samples against Staphylococcus aureus, Escherichia coli and Candida albicans were carried out using inhibition zone, minimum inhibitory concentration and minimal bactericidal concentrations methods in the sunlight. Results showed that the antibacterial activity of samples doped with Cu, Cd and Ag enhanced obviously compared to ZnO, which may be because that the lattice and charge defects produced by M2+ ions replaced Zn2+ prevented the photogenerated holes and electrons from recombining and enhanced the photocatalytic activity and antibacterial activity.
ZnOand doped ZnOnano-powder with M2+(M=Cu, Cd, Ag and Fe ) were synthesized by citrate sol-gel method. The composition,structures and morphology of the samples were characterized by means of modern testing techniques. The antibacterial activities of the samples against Staphylococcus aureus, Escherichia coli and Candida albicans were carried out using inhibition zone, minimum inhibitory concentration and minimal bactericidal concentrations methods in the sunlight. Results showed that the antibacterial activity of samples doped with Cu, Cd and Ag enhanced obviously compared to ZnO, which may be because that the lattice and charge defects produced by M2+ ions replaced Zn2+ prevented the photogenerated holes and electrons from recombining and enhanced the photocatalytic activity and antibacterial activity.
2014, (2): 303-309
doi: 10.11862/CJIC.2014.016
Abstract:
Magnetic fluorescence composite microspheres were fabricated through a layer-by-layer electrostatic self-assembly method. Polyelectrolyte layers were firstly assembled onto the CaCO3 hollow microspheres by the sequential deposition of the PSSand PAHpolyelectrolyte. And then Fe3O4 nanoparticles and CdSe quantum dots were simultaneously assembled onto the hollow microspheres. Furthermore, the resulting magnetic fluorescence composite microspheres were utilized as a chemosensor for the detection of Cu2+ and Pb2+ in aqueous solutions. The results showed that the composite microspheres exhibited strong fluorescence and magnetism, high sensitivity and selectivity towards Cu2+ and Pb2+. Most importantly, it is easy to separate and recycle the composite microspheres from the detection solution using a commercial magnet, thus avoiding secondary contamination and promoting the practical applications of quantum dots.
Magnetic fluorescence composite microspheres were fabricated through a layer-by-layer electrostatic self-assembly method. Polyelectrolyte layers were firstly assembled onto the CaCO3 hollow microspheres by the sequential deposition of the PSSand PAHpolyelectrolyte. And then Fe3O4 nanoparticles and CdSe quantum dots were simultaneously assembled onto the hollow microspheres. Furthermore, the resulting magnetic fluorescence composite microspheres were utilized as a chemosensor for the detection of Cu2+ and Pb2+ in aqueous solutions. The results showed that the composite microspheres exhibited strong fluorescence and magnetism, high sensitivity and selectivity towards Cu2+ and Pb2+. Most importantly, it is easy to separate and recycle the composite microspheres from the detection solution using a commercial magnet, thus avoiding secondary contamination and promoting the practical applications of quantum dots.
2014, (2): 310-316
doi: 10.11862/CJIC.2014.063
Abstract:
The proton conductors La1-xSrxNbO4-σ (0≤x≤0.02) are synthesized by solid-state reaction and their properties are characterized. XRDanalysis shows that all composition samples are monoclinic structure; with an increase in Sr doped amount, cell volume becomes big; La1-xSrxNbO4-σ samples display excellent chemical stability in boiling water and carbon dioxide atmosphere. SEManalysis shows that after the La1-xSrxNbO4-σ powders are sintered at 1500 ℃ for 8 h in air, dense samples with uniform crystalline size are obtained; The Sr doping inhibits crack formation and excessive growth of crystal grain; with an increase in Sr doped amount, crystal grain size becomes small. ACimpedance spectroscopy analysis indicates that conductivities of LaNbO4 are changed by Sr doping and among all samples, La0.995Sr0.005NbO4-σ is of the highest conductivity; the conductivities of the La1-xSrxNbO4-σ samples in humid 5% H2-Ar atmosphere are much higher than that those in dry air; conductivity of La0.995Sr0.005NbO4-σ is 0.003 S·cm-1 in humid 5% H2-Ar atmosphere at 800 ℃ and its conducting activation energy is 0.44 eV.
The proton conductors La1-xSrxNbO4-σ (0≤x≤0.02) are synthesized by solid-state reaction and their properties are characterized. XRDanalysis shows that all composition samples are monoclinic structure; with an increase in Sr doped amount, cell volume becomes big; La1-xSrxNbO4-σ samples display excellent chemical stability in boiling water and carbon dioxide atmosphere. SEManalysis shows that after the La1-xSrxNbO4-σ powders are sintered at 1500 ℃ for 8 h in air, dense samples with uniform crystalline size are obtained; The Sr doping inhibits crack formation and excessive growth of crystal grain; with an increase in Sr doped amount, crystal grain size becomes small. ACimpedance spectroscopy analysis indicates that conductivities of LaNbO4 are changed by Sr doping and among all samples, La0.995Sr0.005NbO4-σ is of the highest conductivity; the conductivities of the La1-xSrxNbO4-σ samples in humid 5% H2-Ar atmosphere are much higher than that those in dry air; conductivity of La0.995Sr0.005NbO4-σ is 0.003 S·cm-1 in humid 5% H2-Ar atmosphere at 800 ℃ and its conducting activation energy is 0.44 eV.
2014, (2): 317-322
doi: 10.11862/CJIC.2014.008
Abstract:
Two water-soluble derivatives of heptaplatin, cis-[(4R,5R)-4,5-bis(aminomethyl)-2-R-1,3-dioxolane](3-hydroxy-1,1-cyclobutanedicarboxylato) platinum(Ⅱ) (R=ethyl and methyl), were synthesized and characterized by elemental analysis, FAB+-MS and FT-IRalong with 13C NMR. They were evaluated for the cytotoxicity against three human cancer cell lines and for the antitumor activity in the murine S180 model. The results show that despite their cytotoxic potency slightly lower than that of heptaplatin, the derivatives exhibits higher antitumor activity and are worthy of further research.
Two water-soluble derivatives of heptaplatin, cis-[(4R,5R)-4,5-bis(aminomethyl)-2-R-1,3-dioxolane](3-hydroxy-1,1-cyclobutanedicarboxylato) platinum(Ⅱ) (R=ethyl and methyl), were synthesized and characterized by elemental analysis, FAB+-MS and FT-IRalong with 13C NMR. They were evaluated for the cytotoxicity against three human cancer cell lines and for the antitumor activity in the murine S180 model. The results show that despite their cytotoxic potency slightly lower than that of heptaplatin, the derivatives exhibits higher antitumor activity and are worthy of further research.
2014, (2): 323-330
doi: 10.11862/CJIC.2014.002
Abstract:
To obtain high performance membranes of polymer-silver salt complexes for the separation of aromatic/aliphatic hydrocarbons, a novel preparation method of AgCl/polymer hybrid membranes has been reported. AgCl nanoparticles were first synthesized in a water-in-oil (W/O) microemulsion, AgCl/polymer hybrid membranes are subsequently prepared via microemulsion in-situ polymerization. In the preparation of AgCl/polymer hybrid membranes, the composition of the microemulsion could not only affect the morphology of AgCl nanoparticles, but also regulate the performance of the hybrid membranes. In this paper, AgCl nanoparticles were synthesized in W/Omicroemulsion using the ionic liquid 1-dodecyl-3-methyl imidazoium chloride (C12mimCl) as the surfactant and methyl methacrylate-styrene (MMA-St) mixture as the oil phase. Aqueous AgNO3 solution was added to the microemulsion as the source of Ag+ ions. Then, AgCl/poly(MMA-co-St) hybrid membranes were prepared by microemulsion in situ polymerization. The influence of the ratio of St to MMAin the oil phase and molar ratio of water to surfactant (ω) on the morphology of AgCl nanoparticles in the microemulsion were characterized by UV-visible spectroscopy (UV-Vis) and transmission electron microscopy (TEM). The scanning electron microscopy (SEM) and the swelling-sorption experiments of the hybrid membranes were employed to explore the relationship between the composition of the microemulsion and the membrane performance. The results showed that the increase in the ratio of St to MMAin the oil phase depressed the polarity of the oil phase, which led to the formation of more AgCl nanoparticles with good dispersion in the hybrid membrane. And these increased significantly the equilibrium swelling-sorption degree in benzene (A∞,b) and the swelling-sorption selectivity of benzene to cyclohexane (αs,b/c) of AgCl/poly(MMA-co-St) hybrid membranes. While the ratio of St to MMAin the oil phase was 1:3, A∞,b and αs,b/c reached 330 mg·g-1 and 19.21. When excess styrene was added to the oil phase, the stability of W/Omicroemulsion was reduced and large AgCl particles generated in the microemulsion, which significantly decreased A∞,b and αs,b/c of AgCl/poly(MMA-co-St) hybrid membranes. The increase of ω resulted in the formation of more AgCl nanoparticles in the microemulsion, which enhanced A∞,b and αs,b/c of AgCl/poly(MMA-co-St) hybrid membranes. When ω was more than5, A∞,b and αs,b/c of AgCl/poly(MMA-co-St) hybrid membranes decreased because of the aggregation of AgCl particles.
To obtain high performance membranes of polymer-silver salt complexes for the separation of aromatic/aliphatic hydrocarbons, a novel preparation method of AgCl/polymer hybrid membranes has been reported. AgCl nanoparticles were first synthesized in a water-in-oil (W/O) microemulsion, AgCl/polymer hybrid membranes are subsequently prepared via microemulsion in-situ polymerization. In the preparation of AgCl/polymer hybrid membranes, the composition of the microemulsion could not only affect the morphology of AgCl nanoparticles, but also regulate the performance of the hybrid membranes. In this paper, AgCl nanoparticles were synthesized in W/Omicroemulsion using the ionic liquid 1-dodecyl-3-methyl imidazoium chloride (C12mimCl) as the surfactant and methyl methacrylate-styrene (MMA-St) mixture as the oil phase. Aqueous AgNO3 solution was added to the microemulsion as the source of Ag+ ions. Then, AgCl/poly(MMA-co-St) hybrid membranes were prepared by microemulsion in situ polymerization. The influence of the ratio of St to MMAin the oil phase and molar ratio of water to surfactant (ω) on the morphology of AgCl nanoparticles in the microemulsion were characterized by UV-visible spectroscopy (UV-Vis) and transmission electron microscopy (TEM). The scanning electron microscopy (SEM) and the swelling-sorption experiments of the hybrid membranes were employed to explore the relationship between the composition of the microemulsion and the membrane performance. The results showed that the increase in the ratio of St to MMAin the oil phase depressed the polarity of the oil phase, which led to the formation of more AgCl nanoparticles with good dispersion in the hybrid membrane. And these increased significantly the equilibrium swelling-sorption degree in benzene (A∞,b) and the swelling-sorption selectivity of benzene to cyclohexane (αs,b/c) of AgCl/poly(MMA-co-St) hybrid membranes. While the ratio of St to MMAin the oil phase was 1:3, A∞,b and αs,b/c reached 330 mg·g-1 and 19.21. When excess styrene was added to the oil phase, the stability of W/Omicroemulsion was reduced and large AgCl particles generated in the microemulsion, which significantly decreased A∞,b and αs,b/c of AgCl/poly(MMA-co-St) hybrid membranes. The increase of ω resulted in the formation of more AgCl nanoparticles in the microemulsion, which enhanced A∞,b and αs,b/c of AgCl/poly(MMA-co-St) hybrid membranes. When ω was more than5, A∞,b and αs,b/c of AgCl/poly(MMA-co-St) hybrid membranes decreased because of the aggregation of AgCl particles.
2014, (2): 331-336
doi: 10.11862/CJIC.2014.007
Abstract:
TiO2 nanotubes sensitized with trans-dihydroxo[5,10,15,10-tetraphenyl porphyrin] tin(Ⅳ) (abbreviated to SnTPP) were prepared. The photocatalytic activity of SnTPP-sensitized TiO2 nanotubes were evaluated by using p-nitrophenol as a model contaminant under visible light irradiation. Meanwhile, SnTPP-sensitized TiO2 nanoparticles were selected as a reference substance to explore the effect of morphology on the photocatalytic activity of catalysts. The experimental results show that introduction of SnTPP can significantly enhance the visible light photocatalytic activity of TiO2 nanotubes. And TiO2 nanotubes show higher sensitizing effect of SnTPP than TiO2 nanoparticles, indicating that the morphology of a catalyst plays an important role in the photocatalytic process. In addition, the photoelectrochemical behavior of SnTPP-sensitized TiO2 nanotubes was examined and related with the photocatalytic activity. Finally, the sensitizing mechanism of SnTPP was discussed preliminarily.
TiO2 nanotubes sensitized with trans-dihydroxo[5,10,15,10-tetraphenyl porphyrin] tin(Ⅳ) (abbreviated to SnTPP) were prepared. The photocatalytic activity of SnTPP-sensitized TiO2 nanotubes were evaluated by using p-nitrophenol as a model contaminant under visible light irradiation. Meanwhile, SnTPP-sensitized TiO2 nanoparticles were selected as a reference substance to explore the effect of morphology on the photocatalytic activity of catalysts. The experimental results show that introduction of SnTPP can significantly enhance the visible light photocatalytic activity of TiO2 nanotubes. And TiO2 nanotubes show higher sensitizing effect of SnTPP than TiO2 nanoparticles, indicating that the morphology of a catalyst plays an important role in the photocatalytic process. In addition, the photoelectrochemical behavior of SnTPP-sensitized TiO2 nanotubes was examined and related with the photocatalytic activity. Finally, the sensitizing mechanism of SnTPP was discussed preliminarily.
2014, (2): 337-344
doi: 10.11862/CJIC.2014.065
Abstract:
Nickel ferrite/carbon nanotubes (NF/MWNTs) composites were prepared by impregnation method. The composition, structure, morphology, magnetic property, and adsorption property of the samples were characterized by XRD, SEM, TEM, VSM, UV-Vis, etc. The results indicate that the NF/MWNTs composites not only keep the good adsorption performance of carbon nanotubes, but also have nice loading factor for nickel ferrite and excellent magnetic property. The adsorption behavior of the NF/MWNTs composite with mNF/mMWNTs of 1 on methylene blue solution is in accord with Langmuir model and Freundlich model. The maximum adsorption capacity of the composite can reach 18.87 mg·g-1. Meanwhile, the temperature and pHvalue have positive correlation with the discoloration rate of methylene blue solution. In addition, the NF/MWNTs composites can be recovered easily with magnetism and can be activated simply and conveniently for reuse.
Nickel ferrite/carbon nanotubes (NF/MWNTs) composites were prepared by impregnation method. The composition, structure, morphology, magnetic property, and adsorption property of the samples were characterized by XRD, SEM, TEM, VSM, UV-Vis, etc. The results indicate that the NF/MWNTs composites not only keep the good adsorption performance of carbon nanotubes, but also have nice loading factor for nickel ferrite and excellent magnetic property. The adsorption behavior of the NF/MWNTs composite with mNF/mMWNTs of 1 on methylene blue solution is in accord with Langmuir model and Freundlich model. The maximum adsorption capacity of the composite can reach 18.87 mg·g-1. Meanwhile, the temperature and pHvalue have positive correlation with the discoloration rate of methylene blue solution. In addition, the NF/MWNTs composites can be recovered easily with magnetism and can be activated simply and conveniently for reuse.
2014, (2): 345-352
doi: 10.11862/CJIC.2014.038
Abstract:
Two-phase carbon modified Li2FeSiO4 composites (Li2FeSiO4/(C+G)) were synthesized via solid-state reaction assisted with refluxing. Activated natural graphite was chosen as carbon source. The phase and the microstructure of Li2FeSiO4/(C+G) were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM) and Raman spectrometry (Raman). The effect of activated graphite content on the electrochemical performance of Li2FeSiO4/(C+G) was also investigated. The results show that activated graphite exists in Li2FeSiO4/(C+G) samples in the form of amorphous carbon as well as graphite crystallite. Li2FeSiO4/(C+G) composite prepared with 5wt% activated graphite achieved the excellent electrochemical performance with a higher initial discharge capacity of 170.3 mAh·g-1 and with a capacity retention ratio of 88.7% after 50 cycles.
Two-phase carbon modified Li2FeSiO4 composites (Li2FeSiO4/(C+G)) were synthesized via solid-state reaction assisted with refluxing. Activated natural graphite was chosen as carbon source. The phase and the microstructure of Li2FeSiO4/(C+G) were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM) and Raman spectrometry (Raman). The effect of activated graphite content on the electrochemical performance of Li2FeSiO4/(C+G) was also investigated. The results show that activated graphite exists in Li2FeSiO4/(C+G) samples in the form of amorphous carbon as well as graphite crystallite. Li2FeSiO4/(C+G) composite prepared with 5wt% activated graphite achieved the excellent electrochemical performance with a higher initial discharge capacity of 170.3 mAh·g-1 and with a capacity retention ratio of 88.7% after 50 cycles.
2014, (2): 353-358
doi: 10.11862/CJIC.2014.035
Abstract:
High specific surface area worm-like mesoporous chromium oxides were fabricated using the glucose-assisted thermal decomposition approach with chromium nitrate as the metal source. The physicochemical properties of the materials were characterized by XRD, TEM, TPRand N2 adsorption-desorption techniques, and the catalytic activity was evaluated for the oxidation of the toluene. The m-Cr-5 catalyst via 500 ℃ calcination process exhibits the highest specific surface area of 162 m2·g-1, the average pore size of 6.2 nm, and the excellent low temperature reducibility and multiple oxidation-state chromium species coexistence. Compared to the bulk chromium oxide, the factors such as low temperature reducibility, high-surface area, and multiple oxidation-state chromium species coexistence are responsible for the excellent catalytic performance of m-Cr-5 in toluene combustion.
High specific surface area worm-like mesoporous chromium oxides were fabricated using the glucose-assisted thermal decomposition approach with chromium nitrate as the metal source. The physicochemical properties of the materials were characterized by XRD, TEM, TPRand N2 adsorption-desorption techniques, and the catalytic activity was evaluated for the oxidation of the toluene. The m-Cr-5 catalyst via 500 ℃ calcination process exhibits the highest specific surface area of 162 m2·g-1, the average pore size of 6.2 nm, and the excellent low temperature reducibility and multiple oxidation-state chromium species coexistence. Compared to the bulk chromium oxide, the factors such as low temperature reducibility, high-surface area, and multiple oxidation-state chromium species coexistence are responsible for the excellent catalytic performance of m-Cr-5 in toluene combustion.
2014, (2): 359-365
doi: 10.11862/CJIC.2014.041
Abstract:
Various morphologies of Cu2O thin films were prepared on indium tin oxide (ITO) conducting glass using electrodeposition approach with diverse addictive agents. The obtained samples were characterized by XPS, XRD, SEMand UV-Vis spectroscopy to study the microstructure, morphology and optical properties of the films, respectively. The degradation of methylene blue over different morphologies of Cu2O thin films was evaluated in H2O2-Cu2O system. The results indicate that the as-prepared Cu2O micrometer crystals are of high-purity. More than 92.1% of methylene blue can be degraded in 3 h by Cu2O. Recycling results reveal that more than 92.4% of methylene blue can be decomposed within 8 cycles. And the degradation rate could still reach 82.4% after 11 cycles.
Various morphologies of Cu2O thin films were prepared on indium tin oxide (ITO) conducting glass using electrodeposition approach with diverse addictive agents. The obtained samples were characterized by XPS, XRD, SEMand UV-Vis spectroscopy to study the microstructure, morphology and optical properties of the films, respectively. The degradation of methylene blue over different morphologies of Cu2O thin films was evaluated in H2O2-Cu2O system. The results indicate that the as-prepared Cu2O micrometer crystals are of high-purity. More than 92.1% of methylene blue can be degraded in 3 h by Cu2O. Recycling results reveal that more than 92.4% of methylene blue can be decomposed within 8 cycles. And the degradation rate could still reach 82.4% after 11 cycles.
2014, (2): 366-370
doi: 10.11862/CJIC.2014.013
Abstract:
Anew dinuclear copper(Ⅱ) complex [Cu2(L)4(2,2'-bipy)2]·H2O (1) has been synthesized with 2-(4-methylbenzoyl)benzoic acid (HL) and 2,2'-bipyridine (2,2'-bipy) as ligands. Its crystal belongs to a triclinic system with space group P1, a=1.01257(15) nm, b=1.3125(2) nm, c=1.3170(2) nm, α=82.985(2)°, β=76.437(2)°, γ=88.290(2)°, V=1.6887(4) nm3, Dc=1.391 g·cm-3, Z=2, F(000)=732, GooF=1.027. Final R1=0.0375, wR2=0.0914. The crystal structure shows that two neighboring copper(Ⅱ) ions are linked together by two bridging2-(4-methylbenzoyl)benzoic acid anions, and their each end position coordinates with one 2-(4-methylbenzoyl)benzoic acid anion and one 2,2'-bipyridine molecule, forming a dinuclear structure. The fluorescent and magnetic properties of the title complex were discussed. The results show that the title complex has two emission bands at 472 and 476 nm, respectively, with the best excitation wavelength at 608 nm, and it is a paramagnetism system in temperatures range of 2~100 K. CCDC: 918797.
Anew dinuclear copper(Ⅱ) complex [Cu2(L)4(2,2'-bipy)2]·H2O (1) has been synthesized with 2-(4-methylbenzoyl)benzoic acid (HL) and 2,2'-bipyridine (2,2'-bipy) as ligands. Its crystal belongs to a triclinic system with space group P1, a=1.01257(15) nm, b=1.3125(2) nm, c=1.3170(2) nm, α=82.985(2)°, β=76.437(2)°, γ=88.290(2)°, V=1.6887(4) nm3, Dc=1.391 g·cm-3, Z=2, F(000)=732, GooF=1.027. Final R1=0.0375, wR2=0.0914. The crystal structure shows that two neighboring copper(Ⅱ) ions are linked together by two bridging2-(4-methylbenzoyl)benzoic acid anions, and their each end position coordinates with one 2-(4-methylbenzoyl)benzoic acid anion and one 2,2'-bipyridine molecule, forming a dinuclear structure. The fluorescent and magnetic properties of the title complex were discussed. The results show that the title complex has two emission bands at 472 and 476 nm, respectively, with the best excitation wavelength at 608 nm, and it is a paramagnetism system in temperatures range of 2~100 K. CCDC: 918797.
2014, (2): 371-378
doi: 10.11862/CJIC.2014.029
Abstract:
Cross-condensation of two different phthalonitriles, namely 4,5-bis[(4-methyloxycarbonyl)phenoxy]phthalonitrile (1) and 4-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}phthalonitrile(2), in the presence of Zn(OAc)2·2H2Oand 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) followed by transesterification in refluxing n-pentanol afforded six phthalocyaninato zinc(Ⅱ) complexes modulated with different numbers of pentyloxycarbonyl and/or triethylene glycol monomethyl ether groups. Simple silica-gel column chromatography leads to the successful separation of all these six compounds, namely Zn[Pc(BP)4](3), Zn[Pc(BP)3(TEG)](4), Zn[Pc(BP)2(TEG)2]-opp(5), Zn[Pc(BP)2(TEG)2]-adj(6), Zn[Pc(BP)(TEG)3](7), and Zn[Pc(TEG)4](8). In addition, the six complexes have been characterized with elemental analysis, MALDI-TOFmass, UV-Vis spectroscopy, 1H NMR, and 2D COSYspectroscopy. The electrochemical properties have also been investigated.
Cross-condensation of two different phthalonitriles, namely 4,5-bis[(4-methyloxycarbonyl)phenoxy]phthalonitrile (1) and 4-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}phthalonitrile(2), in the presence of Zn(OAc)2·2H2Oand 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) followed by transesterification in refluxing n-pentanol afforded six phthalocyaninato zinc(Ⅱ) complexes modulated with different numbers of pentyloxycarbonyl and/or triethylene glycol monomethyl ether groups. Simple silica-gel column chromatography leads to the successful separation of all these six compounds, namely Zn[Pc(BP)4](3), Zn[Pc(BP)3(TEG)](4), Zn[Pc(BP)2(TEG)2]-opp(5), Zn[Pc(BP)2(TEG)2]-adj(6), Zn[Pc(BP)(TEG)3](7), and Zn[Pc(TEG)4](8). In addition, the six complexes have been characterized with elemental analysis, MALDI-TOFmass, UV-Vis spectroscopy, 1H NMR, and 2D COSYspectroscopy. The electrochemical properties have also been investigated.
2014, (2): 379-383
doi: 10.11862/CJIC.2014.018
Abstract:
Acomplex based on Zn (Ⅱ) and terphenyl-2,2',4,4'-tetracarboxylic acid, namely, [Zn2(tpta)0.5(H2tpta)(dpe)(H2O)2]n (H4tpta=terphenyl-2,2',4,4'-tetracarboxylic acid, dpe=1,2-di(4-pyridyl)ethylene) has been hydrother-mally synthesized and characterized by elemental analysis, IRspectroscopy, single-crystal X-ray diffraction analysis, thermal stability analysis and fluorescent analysis. The complex crystallizes in triclinic system, space group P1 with a=1.0174(2) nm, b=1.0341(2) nm, c=1.8831(4) nm, α=96.147(4)°, β=96.866(4)°, γ=98.023(4)°, V=1.9322(7) nm3, Z=2, Dc=1.640 g·cm-3, μ=1.320 mm-1, F(000)=974, and the final R1=0.0669, wR2=0.1332 for I>2σ(I). Complex 1 features an unusual 2Dbilayer motif with ring dinuclear Zn2 units, which is further linked to each other by O-H…Ohydrogen bonds to complete the final 3Dsupramolecular architecture. In additional, complex 1 shows good thermal stability and luminescent property. CCDC: 913522.
Acomplex based on Zn (Ⅱ) and terphenyl-2,2',4,4'-tetracarboxylic acid, namely, [Zn2(tpta)0.5(H2tpta)(dpe)(H2O)2]n (H4tpta=terphenyl-2,2',4,4'-tetracarboxylic acid, dpe=1,2-di(4-pyridyl)ethylene) has been hydrother-mally synthesized and characterized by elemental analysis, IRspectroscopy, single-crystal X-ray diffraction analysis, thermal stability analysis and fluorescent analysis. The complex crystallizes in triclinic system, space group P1 with a=1.0174(2) nm, b=1.0341(2) nm, c=1.8831(4) nm, α=96.147(4)°, β=96.866(4)°, γ=98.023(4)°, V=1.9322(7) nm3, Z=2, Dc=1.640 g·cm-3, μ=1.320 mm-1, F(000)=974, and the final R1=0.0669, wR2=0.1332 for I>2σ(I). Complex 1 features an unusual 2Dbilayer motif with ring dinuclear Zn2 units, which is further linked to each other by O-H…Ohydrogen bonds to complete the final 3Dsupramolecular architecture. In additional, complex 1 shows good thermal stability and luminescent property. CCDC: 913522.
2014, (2): 384-390
doi: 10.11862/CJIC.2014.015
Abstract:
One coordination complex constructed from dicarboxylate acid and N-heterocyclic ligand as mixed ligands, namely, [Mn(mip)(NDC)]n (1) (mip=2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, NDC= naphthalene-1,4-dicarboxylic acid) has been synthesized by hydrothermal reaction. Complex 1 was characterized by elemental analysis, infrared spectrum (IR), single crystal X-ray diffraction, UV-Vis spectrum, and thermogravimetric analysis (TGA). Complex 1 crystallizes in monoclinic, space group P21/n with a=1.24580(7) nm, b=1.47450(9) nm, c=1.36544(8) nm, β=97.6440(1)°. In1, the metal ions Mn(Ⅱ) act as distorted octahedral geometry, being surrounded by four carboxylate oxygen atoms from three NDC ligands and two donor nitrogen atoms from one mip molecule. Complex 1 shows 2D (4,4) sheet topology. TGanalysis shows two clear courses of weight loss, which corresponds to the decomposition of different ligands. The structure-related solid-state uorescence spectra of free ligands and complex 1 have been determined, and the result displays that complex 1 should be acted as potential luminescent material. CCDC: 919758.
One coordination complex constructed from dicarboxylate acid and N-heterocyclic ligand as mixed ligands, namely, [Mn(mip)(NDC)]n (1) (mip=2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, NDC= naphthalene-1,4-dicarboxylic acid) has been synthesized by hydrothermal reaction. Complex 1 was characterized by elemental analysis, infrared spectrum (IR), single crystal X-ray diffraction, UV-Vis spectrum, and thermogravimetric analysis (TGA). Complex 1 crystallizes in monoclinic, space group P21/n with a=1.24580(7) nm, b=1.47450(9) nm, c=1.36544(8) nm, β=97.6440(1)°. In1, the metal ions Mn(Ⅱ) act as distorted octahedral geometry, being surrounded by four carboxylate oxygen atoms from three NDC ligands and two donor nitrogen atoms from one mip molecule. Complex 1 shows 2D (4,4) sheet topology. TGanalysis shows two clear courses of weight loss, which corresponds to the decomposition of different ligands. The structure-related solid-state uorescence spectra of free ligands and complex 1 have been determined, and the result displays that complex 1 should be acted as potential luminescent material. CCDC: 919758.
2014, (2): 391-397
doi: 10.11862/CJIC.2014.039
Abstract:
Three compounds based on Keggin-type polyoxometalate (POMs) using1,10-phen-5,6-dione (Do) as neutral organic ligand, namely, (HDo)6(PW12O40)2·H2O (1), [Cu(Do)2(H2O)]2[Cu(Do)2(PW12O40)(H2O)](PW12O40)(2) and [Pb(Do)2(PW12O40)](HDo)(3), have been synthesized under hydrothermal conditions and characterized by elemental analyses, infrared spectra, inductively coupled plasma analyses, X-ray photoelectron spectroscopy and single-crystal X-ray diffraction. Compounds 1 and 2 are zero-dimensional structures, and compound 3 exhibits one-dimensional chain. The thermal stabilities and photoluminescent properties of three compounds have also been investigated. CCDC: 767622, 1; 767623, 2; 767619, 2.
Three compounds based on Keggin-type polyoxometalate (POMs) using1,10-phen-5,6-dione (Do) as neutral organic ligand, namely, (HDo)6(PW12O40)2·H2O (1), [Cu(Do)2(H2O)]2[Cu(Do)2(PW12O40)(H2O)](PW12O40)(2) and [Pb(Do)2(PW12O40)](HDo)(3), have been synthesized under hydrothermal conditions and characterized by elemental analyses, infrared spectra, inductively coupled plasma analyses, X-ray photoelectron spectroscopy and single-crystal X-ray diffraction. Compounds 1 and 2 are zero-dimensional structures, and compound 3 exhibits one-dimensional chain. The thermal stabilities and photoluminescent properties of three compounds have also been investigated. CCDC: 767622, 1; 767623, 2; 767619, 2.
2014, (2): 398-404
doi: 10.11862/CJIC.2014.060
Abstract:
Monodispersed and uniform hierarchical MoO2 microspheres were synthesized through a one-pot hydrothermal reduction route. The crystal structure and morphology of the as-prepared products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and UV-Visible absorption spectroscopy. The results indicate that the MoO2 microspheres with the size of 1.5 to 3.5 μm are assembled by tiny nanoflakes or nanoparticles. Comparative experimental results reveal that the parameters of synthetic conditions, such as the amount of reducing agent citric acid (C6H8O7, CA) and mineralizer Na2CO3, greatly affect the growth of monodisperse MoO2 microspheres. The orientated aggregation combining with Ostwald ripening growth mechanism of the MoO2 microspheres was proposed, based on the evolution of the structure and the morphology with the extension of reaction time. Photocatalytic results indicate that the prepared MoO2 microspheres exhibit higher photocatalytic activity for the degradation of Rhodamine B (RhB) in the presence of H2O2 under tungsten lamp irradiation.
Monodispersed and uniform hierarchical MoO2 microspheres were synthesized through a one-pot hydrothermal reduction route. The crystal structure and morphology of the as-prepared products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and UV-Visible absorption spectroscopy. The results indicate that the MoO2 microspheres with the size of 1.5 to 3.5 μm are assembled by tiny nanoflakes or nanoparticles. Comparative experimental results reveal that the parameters of synthetic conditions, such as the amount of reducing agent citric acid (C6H8O7, CA) and mineralizer Na2CO3, greatly affect the growth of monodisperse MoO2 microspheres. The orientated aggregation combining with Ostwald ripening growth mechanism of the MoO2 microspheres was proposed, based on the evolution of the structure and the morphology with the extension of reaction time. Photocatalytic results indicate that the prepared MoO2 microspheres exhibit higher photocatalytic activity for the degradation of Rhodamine B (RhB) in the presence of H2O2 under tungsten lamp irradiation.
2014, (2): 405-410
doi: 10.11862/CJIC.2014.012
Abstract:
Layered K2CdSnS4 (1) was synthesized solvothermally and characterized by X-ray single crystal diffraction. The crystals belong to the space group C2/c, with a=1.1021(5) nm, b=1.1030(5) nm, c=1.5151(10) nm, α=90°, β=100.416(12)°, γ=90°, V=1.8114(17) nm3, Z=8, Dc=3.209 g·cm-3, Mr=437.60, μ=6.853 mm-1, F(000)= 1600, λ=0.071073 nm, and the final R=0.1042 and wR=0.2008 for all observed reflections. The compound is comprised of sheets with adamantane-like [Cd2Sn2S10]8- units. UV-Vis reflectance spectrum of compound 1 reveals that 1 is a semiconductor with a band gap of 2.2 eV. CCDC: 424763.
Layered K2CdSnS4 (1) was synthesized solvothermally and characterized by X-ray single crystal diffraction. The crystals belong to the space group C2/c, with a=1.1021(5) nm, b=1.1030(5) nm, c=1.5151(10) nm, α=90°, β=100.416(12)°, γ=90°, V=1.8114(17) nm3, Z=8, Dc=3.209 g·cm-3, Mr=437.60, μ=6.853 mm-1, F(000)= 1600, λ=0.071073 nm, and the final R=0.1042 and wR=0.2008 for all observed reflections. The compound is comprised of sheets with adamantane-like [Cd2Sn2S10]8- units. UV-Vis reflectance spectrum of compound 1 reveals that 1 is a semiconductor with a band gap of 2.2 eV. CCDC: 424763.
2014, (2): 411-418
doi: 10.11862/CJIC.2014.030
Abstract:
An intriguing supramolecular complex NiL2 (HL: (E)-4-methyl-N'-(pyridin-2-ylmethylene) benzenesul-fonohydrazide) with novel Ni-O (sulfonyl) coordination bond has been synthesized and characterized. The structural studies indicate that two types of dimers are assembled via intermolecular offset face-to-face π…π stacking (OFF) and edge-to-face C-H…π (EF) interactions between two pyridyl rings in the crystal structure of NiL2. Each dimer exists in two enantiomeric forms. The DFTcalculation indicates that the parallel fourfold aryl embrace (P4AE) interactions, with one OFFinteraction and two EFinteractions, are stronger than that of only OFF, which can be called synergistic effects. The spectral studies show that the ratio of Ni(Ⅱ) to HLis 1:2 in this compound. CCDC: 773667.
An intriguing supramolecular complex NiL2 (HL: (E)-4-methyl-N'-(pyridin-2-ylmethylene) benzenesul-fonohydrazide) with novel Ni-O (sulfonyl) coordination bond has been synthesized and characterized. The structural studies indicate that two types of dimers are assembled via intermolecular offset face-to-face π…π stacking (OFF) and edge-to-face C-H…π (EF) interactions between two pyridyl rings in the crystal structure of NiL2. Each dimer exists in two enantiomeric forms. The DFTcalculation indicates that the parallel fourfold aryl embrace (P4AE) interactions, with one OFFinteraction and two EFinteractions, are stronger than that of only OFF, which can be called synergistic effects. The spectral studies show that the ratio of Ni(Ⅱ) to HLis 1:2 in this compound. CCDC: 773667.
2014, (2): 419-424
doi: 10.11862/CJIC.2014.043
Abstract:
Athree-dimensional transition metal copper macrocyclic complex {[CuL][VO3]2·0.67H2O}n (L=5,12-dimethyl-1,8-dihydroxyethyl-1,3,6,8,10,13-hexaazacyclotetradecane) has been isolated from the reactions of [CuL](ClO4)2 with NH4VO3, and structurally characterized by elemental analysis, IR, TG, UVspectrum and X-ray diffraction. The title compound crystallizes in the trigonal system, space group R3 with a=1.6877(12) nm, b=1.6877(12) nm, c=2.1630(3) nm, Mr=591.90, V=5.3354(10) nm3, Z=9, Dc=1.654 g·cm-3, F(000)=2739, μ=1.714 mm-1, the final R=0.0470 and wR=0.1347. The Cu(Ⅱ) atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic Lligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedrons in axial positions. The title compound shows a three-dimensional structure, which is constructed by the links of hexanuclear [V6O18]6- rings with [CuL]2+, forming one-dimensional channels occupied by guest water molecules. CCDC: 902742.
Athree-dimensional transition metal copper macrocyclic complex {[CuL][VO3]2·0.67H2O}n (L=5,12-dimethyl-1,8-dihydroxyethyl-1,3,6,8,10,13-hexaazacyclotetradecane) has been isolated from the reactions of [CuL](ClO4)2 with NH4VO3, and structurally characterized by elemental analysis, IR, TG, UVspectrum and X-ray diffraction. The title compound crystallizes in the trigonal system, space group R3 with a=1.6877(12) nm, b=1.6877(12) nm, c=2.1630(3) nm, Mr=591.90, V=5.3354(10) nm3, Z=9, Dc=1.654 g·cm-3, F(000)=2739, μ=1.714 mm-1, the final R=0.0470 and wR=0.1347. The Cu(Ⅱ) atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic Lligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedrons in axial positions. The title compound shows a three-dimensional structure, which is constructed by the links of hexanuclear [V6O18]6- rings with [CuL]2+, forming one-dimensional channels occupied by guest water molecules. CCDC: 902742.
2014, (2): 425-430
doi: 10.11862/CJIC.2014.004
Abstract:
Two new Schiff bases, N,N'-bis(5-chlorosalicylidene)-1,3-diaminopentane (H2CAP) and N,N'-bis(5-bromosalicylidene)-1,3-diaminopentane (H2BAP), and their copper(Ⅱ) complexes, [Cu(CAP)] (1), [Cu(BAP)] (2) and [Cu(CAP)0.5(BAP)0.5] (3), have been prepared and structurally characterized by elemental analysis, IRand electronic spectroscopy. The complexes have also been characterized by single-crystal X-ray diffraction studies. The Cu atom in each of the complexes is in a tetrahedrally distorted square planar coordination. By combination of complex 1 and 2, a new aggregation 3 was formed. There are interesting alternate arrangement of Cl and Br substituent groups in the crystal packing of the aggregation. CCDC: 889058, 1; 889059, 2; 889057, 3.
Two new Schiff bases, N,N'-bis(5-chlorosalicylidene)-1,3-diaminopentane (H2CAP) and N,N'-bis(5-bromosalicylidene)-1,3-diaminopentane (H2BAP), and their copper(Ⅱ) complexes, [Cu(CAP)] (1), [Cu(BAP)] (2) and [Cu(CAP)0.5(BAP)0.5] (3), have been prepared and structurally characterized by elemental analysis, IRand electronic spectroscopy. The complexes have also been characterized by single-crystal X-ray diffraction studies. The Cu atom in each of the complexes is in a tetrahedrally distorted square planar coordination. By combination of complex 1 and 2, a new aggregation 3 was formed. There are interesting alternate arrangement of Cl and Br substituent groups in the crystal packing of the aggregation. CCDC: 889058, 1; 889059, 2; 889057, 3.
2014, (2): 431-441
doi: 10.11862/CJIC.2014.001
Abstract:
BiOI/Bi2WO6 photocatalysts with various BiOIamounts were prepared by a simple deposition method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) and low temperature nitrogen adsorption. The photocatalytic performance of BiOI/Bi2WO6 catalysts was evaluated using the photodegradation of methyl orange (MO) and phenol in an aqueous solution under UVand visible light irradiation. The results indicate that compared with commercial Degussa P25 and pure Bi2WO6, the 13.2% BiOI/Bi2WO6 photocatalyst shows much higher UVand visible light photocatalytic performance. The obviously increased photocatalytic activity could be mainly attributed to the effective transfer of the photogenerated electrons and holes at the interface of Bi2WO6 and BiOI, which reduces the recombination of electron-hole pairs. Atransfer process of photogenerated carriers is proposed based on the band structures of BiOIand Bi2WO6. Radical scavengers experiments demonstrate that ·OH, h+, ·O2-and H2O2, especially h+, together dominate the photodegradation process of MOand phenol.
BiOI/Bi2WO6 photocatalysts with various BiOIamounts were prepared by a simple deposition method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) and low temperature nitrogen adsorption. The photocatalytic performance of BiOI/Bi2WO6 catalysts was evaluated using the photodegradation of methyl orange (MO) and phenol in an aqueous solution under UVand visible light irradiation. The results indicate that compared with commercial Degussa P25 and pure Bi2WO6, the 13.2% BiOI/Bi2WO6 photocatalyst shows much higher UVand visible light photocatalytic performance. The obviously increased photocatalytic activity could be mainly attributed to the effective transfer of the photogenerated electrons and holes at the interface of Bi2WO6 and BiOI, which reduces the recombination of electron-hole pairs. Atransfer process of photogenerated carriers is proposed based on the band structures of BiOIand Bi2WO6. Radical scavengers experiments demonstrate that ·OH, h+, ·O2-and H2O2, especially h+, together dominate the photodegradation process of MOand phenol.
2014, (2): 442-450
doi: 10.11862/CJIC.2014.019
Abstract:
Three-dimensional (3D) hierarchical silver nanomaterials (HSNs) were prepared by a simple surfactant-free wet-chemical method at room temperature. The as-prepared HSNs exhibit spherical morphologies and are constructed with many 2Dnanoflakes as building blocks. Field emission scanning electron microscopy (FESEM) studies show that diammonium 2-(carboxymethyl)-2-hydroxysuccinate (diammonium hydrogen citrate) (C6H14N2O7) plays a key role in the formation of such HSNs. X-ray diffraction (XRD) and transmission electron microscopy (TEM) results confirm the formation of HSNs. The optical properties and surface-enhanced Raman scattering (SERS) effect were also investigated by UV-Vis and Raman spectra. The HSNs could be served as highly sensitive surface-enhanced Raman scattering (SERS) substrates for chemical detection.
Three-dimensional (3D) hierarchical silver nanomaterials (HSNs) were prepared by a simple surfactant-free wet-chemical method at room temperature. The as-prepared HSNs exhibit spherical morphologies and are constructed with many 2Dnanoflakes as building blocks. Field emission scanning electron microscopy (FESEM) studies show that diammonium 2-(carboxymethyl)-2-hydroxysuccinate (diammonium hydrogen citrate) (C6H14N2O7) plays a key role in the formation of such HSNs. X-ray diffraction (XRD) and transmission electron microscopy (TEM) results confirm the formation of HSNs. The optical properties and surface-enhanced Raman scattering (SERS) effect were also investigated by UV-Vis and Raman spectra. The HSNs could be served as highly sensitive surface-enhanced Raman scattering (SERS) substrates for chemical detection.
2014, (2): 451-458
doi: 10.11862/CJIC.2014.046
Abstract:
Dense tin oxide films were solvothermally grown from the tin oxide seed films fabricated on glass substrates by sol-gel technique. The morphology and crystal structure of the tin oxide films were characterized by using scanning electron microscopy and X-ray diffraction techniques. The results reveal that the films are composed of cassiterite-type tin oxide crystals with size of 7~10 nm. The film quality can be improved significantly when the sodium dodecylbenzenesulfonate is used as the surfactant during the solvothermal reaction. The gas sensor, which is directly connected tin oxide films to the test circuits by using tweezers with special gripping surfaces, exhibits good sensing performance to nitrogen dioxide gas under mild testing conditions, i.e. room temperature, ambient pressure, and dry air background. The sensor can achieve a detection limit of 0.5 μL·L-1.
Dense tin oxide films were solvothermally grown from the tin oxide seed films fabricated on glass substrates by sol-gel technique. The morphology and crystal structure of the tin oxide films were characterized by using scanning electron microscopy and X-ray diffraction techniques. The results reveal that the films are composed of cassiterite-type tin oxide crystals with size of 7~10 nm. The film quality can be improved significantly when the sodium dodecylbenzenesulfonate is used as the surfactant during the solvothermal reaction. The gas sensor, which is directly connected tin oxide films to the test circuits by using tweezers with special gripping surfaces, exhibits good sensing performance to nitrogen dioxide gas under mild testing conditions, i.e. room temperature, ambient pressure, and dry air background. The sensor can achieve a detection limit of 0.5 μL·L-1.
2014, (2): 459-465
doi: 10.11862/CJIC.2014.010
Abstract:
Treatment of 2-substituted benzoic acids (2-isopropylbenzoic acid and salicylic acid) with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) mediated by PPh3 at room temperature produced two 1,4-disubstituted 2,3-dicyano-5,6-dichlorobenzenes (2 and 3) in good yields. Heating a chloroform solution of 2 and 3 to the reflux temperature in the presence of phenylamine generated amide derivatives 4 and 5, respectively. All the target compounds were fully characterized by elemental analysis, MSand 1H NMRspectrometry, and the structures of compounds 2 and 3 were further confirmed by single-crystal determination. 1,4-Bis(2-isopropylbenzoate)-2,3-dicyano-5,6-dichlorobenzene (2) crystallizes in monoclinic space group P21/c with cell parameters: a=1.2875(3) nm, b=1.5186(2) nm, c=1.5726(3) nm, β=122.23(3)°, V=2.6010(1) nm3, Dc=1.331 g·cm-3, Z=4, F(000)=1080, R1=0.0572, wR2=0.1260. 1,4-Bis(2-hydroxybenzoate)-2,3-dicyano-5,6-dichlorobenzene (3) crystallizes in triclinic space group P1 with cell parameters: a=0.87776(16) nm, b=1.13111(15) nm, c=1.18639(17) nm, α=69.290 (2)°, β=89.409 (3)°, γ=67.878 (2)°, V=1.0104(3) nm3, Dc=1.542 g·cm-3, Z=2, F(000)=476, R1=0.0383, wR2=0.0931. Strong π-π stacking interactions and intermolecular hydrogen bonds of the structures (2 and 3) stabilized the two intermediates. CCDC: 921957, 2; 935976, 3.
Treatment of 2-substituted benzoic acids (2-isopropylbenzoic acid and salicylic acid) with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) mediated by PPh3 at room temperature produced two 1,4-disubstituted 2,3-dicyano-5,6-dichlorobenzenes (2 and 3) in good yields. Heating a chloroform solution of 2 and 3 to the reflux temperature in the presence of phenylamine generated amide derivatives 4 and 5, respectively. All the target compounds were fully characterized by elemental analysis, MSand 1H NMRspectrometry, and the structures of compounds 2 and 3 were further confirmed by single-crystal determination. 1,4-Bis(2-isopropylbenzoate)-2,3-dicyano-5,6-dichlorobenzene (2) crystallizes in monoclinic space group P21/c with cell parameters: a=1.2875(3) nm, b=1.5186(2) nm, c=1.5726(3) nm, β=122.23(3)°, V=2.6010(1) nm3, Dc=1.331 g·cm-3, Z=4, F(000)=1080, R1=0.0572, wR2=0.1260. 1,4-Bis(2-hydroxybenzoate)-2,3-dicyano-5,6-dichlorobenzene (3) crystallizes in triclinic space group P1 with cell parameters: a=0.87776(16) nm, b=1.13111(15) nm, c=1.18639(17) nm, α=69.290 (2)°, β=89.409 (3)°, γ=67.878 (2)°, V=1.0104(3) nm3, Dc=1.542 g·cm-3, Z=2, F(000)=476, R1=0.0383, wR2=0.0931. Strong π-π stacking interactions and intermolecular hydrogen bonds of the structures (2 and 3) stabilized the two intermediates. CCDC: 921957, 2; 935976, 3.
2014, (2): 466-472
doi: 10.11862/CJIC.2014.036
Abstract:
The electrochemical behavior of CuInxGa1-xSe2 (CIGS) was investigated by cyclic voltammetry (CV) in ionic liquid Reline. The insertion of indium (In) into the CISthin films involved two routes: co-deposition with Cu2+ and Se or trivalent indium ion (In3+). The insertion of gallium (Ga) into the quaternary solid phase (Cu-In-Ga-Se) utilized two routes: co-deposition (with Cu2+, In3+, Se4+) and Ga3+ directly added to Ga. The effects of electrodeposition potential, bath temperature and main salt concentration on CIGSthin films were researched. Cu1.00In0.78Ga0.27Se2.13 thin films were obtained and satisfactory control of film composition and Ga/(Ga+In) was achieved by the choice of process parameters. The standard CIGSsample was calibrated by an inductively coupled plasma optical emission. The morphological properties were detected by scanning electron microscopy. The XRDresult shows that the incorporation of Ga into CISphase and forms CIGSphase.
The electrochemical behavior of CuInxGa1-xSe2 (CIGS) was investigated by cyclic voltammetry (CV) in ionic liquid Reline. The insertion of indium (In) into the CISthin films involved two routes: co-deposition with Cu2+ and Se or trivalent indium ion (In3+). The insertion of gallium (Ga) into the quaternary solid phase (Cu-In-Ga-Se) utilized two routes: co-deposition (with Cu2+, In3+, Se4+) and Ga3+ directly added to Ga. The effects of electrodeposition potential, bath temperature and main salt concentration on CIGSthin films were researched. Cu1.00In0.78Ga0.27Se2.13 thin films were obtained and satisfactory control of film composition and Ga/(Ga+In) was achieved by the choice of process parameters. The standard CIGSsample was calibrated by an inductively coupled plasma optical emission. The morphological properties were detected by scanning electron microscopy. The XRDresult shows that the incorporation of Ga into CISphase and forms CIGSphase.
