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2015 Volume 31 Issue 11
2015, (11): 2095-2102
doi: 10.11862/CJIC.2015.294
Abstract:
Four mixed-ligand coordination polymers, {[Zn(4-bpdb)(pnba)2]·4H2O}n (1), [Cd(4-bpdb)(pnba)2]n (2), {[Cd2(3-bpdb)2(OAc)4]·5H2O}n (3), and {[Co(3-bpdb)(pnba)2(H2O)2]·2H2O}n (4), (4-bpdb=1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, 3-bpdb=1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene, Hpnba=p-nitrobenzoic acid, HOAc=Acetic acid) were synthesized and characterized. Single crystal X-ray analysis revealed that complex 1 featured a 1D zigzag chain structure and the Zn(Ⅱ) ions adopted slightly distorted tetrahedral coordination geometry. While polymers 2 and 3 possessed 1D ladder-like double chain structures with Cd(Ⅱ) ions in pentagonal bipyramidal coordination geometry. Polymer 3 displayed a 1D linear chain structure where Co(Ⅱ) ions had octahedral geometry. Moreover, the elemental analysis, infrared spectroscopy, thermal analysis, PXRD, and photoluminescence properties of the complexes were also investigated.
Four mixed-ligand coordination polymers, {[Zn(4-bpdb)(pnba)2]·4H2O}n (1), [Cd(4-bpdb)(pnba)2]n (2), {[Cd2(3-bpdb)2(OAc)4]·5H2O}n (3), and {[Co(3-bpdb)(pnba)2(H2O)2]·2H2O}n (4), (4-bpdb=1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, 3-bpdb=1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene, Hpnba=p-nitrobenzoic acid, HOAc=Acetic acid) were synthesized and characterized. Single crystal X-ray analysis revealed that complex 1 featured a 1D zigzag chain structure and the Zn(Ⅱ) ions adopted slightly distorted tetrahedral coordination geometry. While polymers 2 and 3 possessed 1D ladder-like double chain structures with Cd(Ⅱ) ions in pentagonal bipyramidal coordination geometry. Polymer 3 displayed a 1D linear chain structure where Co(Ⅱ) ions had octahedral geometry. Moreover, the elemental analysis, infrared spectroscopy, thermal analysis, PXRD, and photoluminescence properties of the complexes were also investigated.
2015, (11): 2103-2110
doi: 10.11862/CJIC.2015.276
Abstract:
Amicroporous 3D MOF, [Cu5(L)2(H2O)5] (1) (H4L=5,5'-((1H-pyrazole-3,5-dicarbonyl)bis(azanediyl))diisophthalic)) with acylamide-functionalized and π-electron walls in its structure was synthesized and characterized. Topological analysis reveals 1 is of 3,3,4,4,6-c net and its porosity was tested by N2 and CO2 gas adsorption. Meanwhile, 1 can serve as a good host for encapsulating I2 (1.94 mmol·g-1, RT) and exhibits an outstanding performance in reversible adsorption of iodine molecules.
Amicroporous 3D MOF, [Cu5(L)2(H2O)5] (1) (H4L=5,5'-((1H-pyrazole-3,5-dicarbonyl)bis(azanediyl))diisophthalic)) with acylamide-functionalized and π-electron walls in its structure was synthesized and characterized. Topological analysis reveals 1 is of 3,3,4,4,6-c net and its porosity was tested by N2 and CO2 gas adsorption. Meanwhile, 1 can serve as a good host for encapsulating I2 (1.94 mmol·g-1, RT) and exhibits an outstanding performance in reversible adsorption of iodine molecules.
2015, (11): 2111-2118
doi: 10.11862/CJIC.2015.291
Abstract:
Two interpenetrating networks, namely {[Co(bimb)(L)]·H2O}n(1) and {[Co(bbix)(L)]2}n(2) (H2L=4,4'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))dibenzoic acid, bimb=1,1'-(1,4-butanediyl)bis(imidazole), bbix=1,4-bis(benzimidazole-1-ylmethyl)-benzene) have been prepared under hydrothermal condition by varying the bis(imidazole) coligands. Single crystal X-ray diffraction indicates that complex 1 displays 2D→3D 3-fold interpenetrating framework with 4-connected sql topology; 2 shows a 3D 4-connected framework of 66 dia topology with 6-fold interpenetration. The results indicate that the shapes of bis(imidazole) coligands have an important effect on the interpenetrating characters and ultimate frameworks. Moreover, the thermal and magnetic properties of the two complexes have also been studied.
Two interpenetrating networks, namely {[Co(bimb)(L)]·H2O}n(1) and {[Co(bbix)(L)]2}n(2) (H2L=4,4'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))dibenzoic acid, bimb=1,1'-(1,4-butanediyl)bis(imidazole), bbix=1,4-bis(benzimidazole-1-ylmethyl)-benzene) have been prepared under hydrothermal condition by varying the bis(imidazole) coligands. Single crystal X-ray diffraction indicates that complex 1 displays 2D→3D 3-fold interpenetrating framework with 4-connected sql topology; 2 shows a 3D 4-connected framework of 66 dia topology with 6-fold interpenetration. The results indicate that the shapes of bis(imidazole) coligands have an important effect on the interpenetrating characters and ultimate frameworks. Moreover, the thermal and magnetic properties of the two complexes have also been studied.
2015, (11): 2119-2127
doi: 10.11862/CJIC.2015.278
Abstract:
Modifying of ZSM-5 molecular sieve in acid and alkaline solution was studied at 80 ℃. For the post synthesis, dealumination prior to desilication step was critical for the following mesopore formation by desilication and the effect of alkaline concentration on the crystallinity, porosity, morphology and acidity of zeolite was investigated by deep characterization of BET, XRD, FT-IR, NH3-TPD, and TEM. It was found that the microporous structure was well reserved in acid dealumination alone, alkaline desilication could promote smaller mesopore. However, acid dealumination before desilication facilitated the mesopore formation resulting in larger pore volume. When the concentration of alkaline solution was increased to 0.6 mol·L-1, both the pore volume and Sext/Smicro firstly increased and then decreased. The sample via post treatment of 2 mol·L-1 HCl and 0.4 mol·L-1 NaOHsolution was found to have higher proportion of mesopores, less amount of acid sites, especially strong acidity. Methanol conversion to gasoline reaction was carried out in a fixed reactor at 400 ℃, 0.1 MPa and WHSV=2.1 h-1. The sample subjected to 2 mol·L-1 HCl acid solution and 0.4 mol·L-1 NaOH solution exhibited greater improvement: the yield of gasoline range increased to 34wt% from 30wt%, the lifetime was prolonged to 135 h relative to parent ZSM-5 and the content of aromatics was decreased from 73wt% to 20wt%. The results were well rationalized by alterations of acidic properties, mesopore formation and improved diffusivity.
Modifying of ZSM-5 molecular sieve in acid and alkaline solution was studied at 80 ℃. For the post synthesis, dealumination prior to desilication step was critical for the following mesopore formation by desilication and the effect of alkaline concentration on the crystallinity, porosity, morphology and acidity of zeolite was investigated by deep characterization of BET, XRD, FT-IR, NH3-TPD, and TEM. It was found that the microporous structure was well reserved in acid dealumination alone, alkaline desilication could promote smaller mesopore. However, acid dealumination before desilication facilitated the mesopore formation resulting in larger pore volume. When the concentration of alkaline solution was increased to 0.6 mol·L-1, both the pore volume and Sext/Smicro firstly increased and then decreased. The sample via post treatment of 2 mol·L-1 HCl and 0.4 mol·L-1 NaOHsolution was found to have higher proportion of mesopores, less amount of acid sites, especially strong acidity. Methanol conversion to gasoline reaction was carried out in a fixed reactor at 400 ℃, 0.1 MPa and WHSV=2.1 h-1. The sample subjected to 2 mol·L-1 HCl acid solution and 0.4 mol·L-1 NaOH solution exhibited greater improvement: the yield of gasoline range increased to 34wt% from 30wt%, the lifetime was prolonged to 135 h relative to parent ZSM-5 and the content of aromatics was decreased from 73wt% to 20wt%. The results were well rationalized by alterations of acidic properties, mesopore formation and improved diffusivity.
2015, (11): 2128-2134
doi: 10.11862/CJIC.2015.299
Abstract:
Porous carbon materials were prepared from freeze-dried porous carrots as carbon sources through carbonization at 600 ℃ in nitrogen atmosphere, followed by KOH activation. The microstructures and capacitive properties of carbon materials were examined by FTIR, XRD, SEM, TEM, CV, CD and EIS. Electrochemical results indicated that, after being activated, porous carbon showed a significant improvement in specific surface area (from 7 m2·g-1 to 147 m2·g-1). Moreover, activated carbon displayed a maximum specific capacitance of 414 F·g-1. Even when the current increased to 4 A·g-1, its capacitance retention reached 74.5%. While non-activated carbon had only 253 F·g-1 and 45.1% retention. Additionally, activated carbon exhibited high electrochemical stability with 94% retention after 8000 cycles. The remarkable improvement in capacitive performance was strongly related to the significant improvement of specific surface area and the increase of mesopore.
Porous carbon materials were prepared from freeze-dried porous carrots as carbon sources through carbonization at 600 ℃ in nitrogen atmosphere, followed by KOH activation. The microstructures and capacitive properties of carbon materials were examined by FTIR, XRD, SEM, TEM, CV, CD and EIS. Electrochemical results indicated that, after being activated, porous carbon showed a significant improvement in specific surface area (from 7 m2·g-1 to 147 m2·g-1). Moreover, activated carbon displayed a maximum specific capacitance of 414 F·g-1. Even when the current increased to 4 A·g-1, its capacitance retention reached 74.5%. While non-activated carbon had only 253 F·g-1 and 45.1% retention. Additionally, activated carbon exhibited high electrochemical stability with 94% retention after 8000 cycles. The remarkable improvement in capacitive performance was strongly related to the significant improvement of specific surface area and the increase of mesopore.
2015, (11): 2135-2142
doi: 10.11862/CJIC.2015.280
Abstract:
The optical absorption spectra of the nano-composite films dispersed by Ag, Au and Cu nano-particles were simulated by the classical Mie theory. It was found that the optical absorption spectra exhibit surface plasmon resonance (SPR) absorption peaks in visible region. The positions and intensities of the SPR absorption peaks are strongly affected by the real part (εm1) and imaginary part (εm2) of dielectric constant of metal and refractive index (ns) of dielectric. The SPRabsorption position in visible region of the composite film is strongly dependent on ns rather than εm1 and εm2. The simulated optical absorption spectra of the composite films dispersed by Ag, Au and Cu by Mie theory in this study are in good agreement with the reported experiment results, especially showing a close SPR peak positions to each other.
The optical absorption spectra of the nano-composite films dispersed by Ag, Au and Cu nano-particles were simulated by the classical Mie theory. It was found that the optical absorption spectra exhibit surface plasmon resonance (SPR) absorption peaks in visible region. The positions and intensities of the SPR absorption peaks are strongly affected by the real part (εm1) and imaginary part (εm2) of dielectric constant of metal and refractive index (ns) of dielectric. The SPRabsorption position in visible region of the composite film is strongly dependent on ns rather than εm1 and εm2. The simulated optical absorption spectra of the composite films dispersed by Ag, Au and Cu by Mie theory in this study are in good agreement with the reported experiment results, especially showing a close SPR peak positions to each other.
2015, (11): 2143-2151
doi: 10.11862/CJIC.2015.290
Abstract:
MgZn2 phase is the main reinforcement in the high strength-toughness aluminum alloy, such as Al-Zn-Mg-Cu (7××× series). These alloys can be strengthened by solution and aging heat treatment. The precipitation sequence is recognized as: supersaturated solute→GP area→metastable η' phase→stable η(MgZn2) phase. Therefore, it is important to know the quantum behavior and phase formation mechanism of MgZn2. But till to now, the concerned research has been rarely reported. Besides, the magnetic property of MgZn2 is also important when the aluminum alloy is processed in the presence of magnetic field. By using the first principles method, the electronic and magnetic properties of MgZn2 were calculated and analyzd in detail. The computing results on the band structure and density of state demonstrates that Zn-Mg bond is generated through the interaction of two sp hybrid state, which are from Zn4s-4p hybridized orbit and Mg3s-3p hybridized orbit separately. Especially nearby the Fermi level an intense interaction takes place between the Zn4p and Mg3p orbits. The Mulliken population distribution computation illustrates that the overlapped population distribution of Zn1-Mg or Zn2-Mg almost equals to zero. Here, it is noted that the Zn1 and Zn2 just means the Zn atoms located individually at the edge and the interior of lattice. The calculation outcome of electron density shows that the electron density distribution of Mg-Zn has an obvious locality. Combining these results with the electronegativity difference of Mg and Zn, it is regarded that the Zn-Mg is polar covalent bond. The difference of Zn1-Mg bond and Zn2-Mg bond is that the contribution of Zn24s orbit to the bond formation is higher than that of Zn14s orbit in -10~-6 eV, the contribution of Zn14s orbit to the bond formation is higher than that of Zn24s orbit in 2~5 eV. The population distribution also demonstrates that the overlapped population of Zn1-Zn1 is -1.15, which proves that the electrons are in the antibonding orbit; nevertheless, the population distribution of Zn2-Zn2 is 1.08 and the corresponding electrons are in the bonding orbital. The population distribution and electron density calculating results reveal that the Mg-Mg bond is covalent bond while the Zn1-Zn2 bond is metallic bond. Furthermore, the studies on the integrated spin density of state demonstrate that the MgZn2 phase shows paramagnetism, which stems mainly from the two unpaired electrons in the Zn1-Mg bond, and the paramagnetism of MgZn2 will make a magnetoplastic effect in Al-Zn-Mg-Cu (7××× series) high strength-toughness aluminum alloy in the presence of magnetic field.
MgZn2 phase is the main reinforcement in the high strength-toughness aluminum alloy, such as Al-Zn-Mg-Cu (7××× series). These alloys can be strengthened by solution and aging heat treatment. The precipitation sequence is recognized as: supersaturated solute→GP area→metastable η' phase→stable η(MgZn2) phase. Therefore, it is important to know the quantum behavior and phase formation mechanism of MgZn2. But till to now, the concerned research has been rarely reported. Besides, the magnetic property of MgZn2 is also important when the aluminum alloy is processed in the presence of magnetic field. By using the first principles method, the electronic and magnetic properties of MgZn2 were calculated and analyzd in detail. The computing results on the band structure and density of state demonstrates that Zn-Mg bond is generated through the interaction of two sp hybrid state, which are from Zn4s-4p hybridized orbit and Mg3s-3p hybridized orbit separately. Especially nearby the Fermi level an intense interaction takes place between the Zn4p and Mg3p orbits. The Mulliken population distribution computation illustrates that the overlapped population distribution of Zn1-Mg or Zn2-Mg almost equals to zero. Here, it is noted that the Zn1 and Zn2 just means the Zn atoms located individually at the edge and the interior of lattice. The calculation outcome of electron density shows that the electron density distribution of Mg-Zn has an obvious locality. Combining these results with the electronegativity difference of Mg and Zn, it is regarded that the Zn-Mg is polar covalent bond. The difference of Zn1-Mg bond and Zn2-Mg bond is that the contribution of Zn24s orbit to the bond formation is higher than that of Zn14s orbit in -10~-6 eV, the contribution of Zn14s orbit to the bond formation is higher than that of Zn24s orbit in 2~5 eV. The population distribution also demonstrates that the overlapped population of Zn1-Zn1 is -1.15, which proves that the electrons are in the antibonding orbit; nevertheless, the population distribution of Zn2-Zn2 is 1.08 and the corresponding electrons are in the bonding orbital. The population distribution and electron density calculating results reveal that the Mg-Mg bond is covalent bond while the Zn1-Zn2 bond is metallic bond. Furthermore, the studies on the integrated spin density of state demonstrate that the MgZn2 phase shows paramagnetism, which stems mainly from the two unpaired electrons in the Zn1-Mg bond, and the paramagnetism of MgZn2 will make a magnetoplastic effect in Al-Zn-Mg-Cu (7××× series) high strength-toughness aluminum alloy in the presence of magnetic field.
2015, (11): 2152-2158
doi: 10.11862/CJIC.2015.285
Abstract:
Based on the similarity of crystal structure between Bi2MoO6 and BiOI, Bi2MoO6 photocatalyst with hollow structure was prepared by in-situ transformation method using BiOIas self-sacrificing template. The phase and morphology of the intermediates obtained at different reaction temperatures and times during BiOI microspheres transforming to hollow Bi2MoO6 were analyzed. The results showed that the best conditions for preparing Bi2MoO6 hollow microspheres were 8 h and 120 ℃. Besides, the structure, morphology, specific surface area and optical property of the as-prepared Bi2MoO6 hollow microspheres were studied. The results indicated that the surface of the obtained Bi2MoO6 hollow microspheres were relatively loose, and the specific surface area was 61 m2·g-1. Methyl orange (MO) was selected as a pollutant model to evaluate the visible-light photocatalytic activity of the prepared materials. As a result, MOwas completely degraded by Bi2MoO6 hollow microspheres in80 minutes. The photocatalytic activity of Bi2MoO6 hollow microspheres was obviously superior to Bi2MoO6 sheets and the intermediates obtained at different reaction times.
Based on the similarity of crystal structure between Bi2MoO6 and BiOI, Bi2MoO6 photocatalyst with hollow structure was prepared by in-situ transformation method using BiOIas self-sacrificing template. The phase and morphology of the intermediates obtained at different reaction temperatures and times during BiOI microspheres transforming to hollow Bi2MoO6 were analyzed. The results showed that the best conditions for preparing Bi2MoO6 hollow microspheres were 8 h and 120 ℃. Besides, the structure, morphology, specific surface area and optical property of the as-prepared Bi2MoO6 hollow microspheres were studied. The results indicated that the surface of the obtained Bi2MoO6 hollow microspheres were relatively loose, and the specific surface area was 61 m2·g-1. Methyl orange (MO) was selected as a pollutant model to evaluate the visible-light photocatalytic activity of the prepared materials. As a result, MOwas completely degraded by Bi2MoO6 hollow microspheres in80 minutes. The photocatalytic activity of Bi2MoO6 hollow microspheres was obviously superior to Bi2MoO6 sheets and the intermediates obtained at different reaction times.
2015, (11): 2159-2166
doi: 10.11862/CJIC.2015.285
Abstract:
An acylhydrazone-type Schiff base containing sulfur, 2-thiophenecarboxylic acid (2-hydroxly- 4-diethylamino-benzylidene)-hydrazide monohydrate (H2L·H2O, 1), was synthesized in the ethanol, and a complex [Cu(phen)L] (2) constructed from the H2L and phenanthroline was prepared by using diffusion method. The compounds 1 and 2 were characterized by elemental analyses, IR, UV spectra and X-ray diffraction analysis. The results reveal that the ligand 1 belongs to orthorhombic P21212 space group, while the complex 2 belongs to monoclinic P21/c space group. The Cu(Ⅱ) atom locate in a distorted square-pyramidal coordination, in which ligand H2L is deprotonated and coordinates to the Cu(Ⅱ) ion via carbonyl oxygen, phenolate oxygen and imine nitrogen atoms. The quantum chemical calculation for 1 and 2 was performed by means of Gaussian09 program at B3LYP/6-31G(d) and UB3LYP/6-31G(d) basis set, respectively. After optimization of molecular geometry of 1 and 2, molecular stability, energy and composition of frontier molecular orbitals and electronic spectra have been analyzed and discussed． The antioxidative activity of the compounds has been studied.
An acylhydrazone-type Schiff base containing sulfur, 2-thiophenecarboxylic acid (2-hydroxly- 4-diethylamino-benzylidene)-hydrazide monohydrate (H2L·H2O, 1), was synthesized in the ethanol, and a complex [Cu(phen)L] (2) constructed from the H2L and phenanthroline was prepared by using diffusion method. The compounds 1 and 2 were characterized by elemental analyses, IR, UV spectra and X-ray diffraction analysis. The results reveal that the ligand 1 belongs to orthorhombic P21212 space group, while the complex 2 belongs to monoclinic P21/c space group. The Cu(Ⅱ) atom locate in a distorted square-pyramidal coordination, in which ligand H2L is deprotonated and coordinates to the Cu(Ⅱ) ion via carbonyl oxygen, phenolate oxygen and imine nitrogen atoms. The quantum chemical calculation for 1 and 2 was performed by means of Gaussian09 program at B3LYP/6-31G(d) and UB3LYP/6-31G(d) basis set, respectively. After optimization of molecular geometry of 1 and 2, molecular stability, energy and composition of frontier molecular orbitals and electronic spectra have been analyzed and discussed． The antioxidative activity of the compounds has been studied.
2015, (11): 2167-2173
doi: 10.11862/CJIC.2015.234
Abstract:
Nanosized TiO2 with deposited CuO(CuO/TiO2) photocatalysts were synthesized by impregnation and thermal decomposition method. The photocatalytic water splitting for hydrogen evolution was investigated over CuO/TiO2 with ethylene glycol as an electron donor. The effect of CuO loading, irradiation time, photocatalyst amount, initial concentration of the ethylene glycol solution on the reaction rate of photocatalytic hydrogen evolution was studied. The possible reaction mechanism was also discussed. The results show that the optimal hydrogen evolution rate reachs 604.5 μmol·h-1·g-1 under irradiation of 300 W Xe lamp. The CuO/TiO2 photocatalyst possesses enhanced optical absorption property, which can help to reduce the electron-hole recombination because the photo-generated electrons in TiO2 can be readily transferred to CuO. We suggest that ethylene glycol as electron donor may be further oxidized via glycolic acid.
Nanosized TiO2 with deposited CuO(CuO/TiO2) photocatalysts were synthesized by impregnation and thermal decomposition method. The photocatalytic water splitting for hydrogen evolution was investigated over CuO/TiO2 with ethylene glycol as an electron donor. The effect of CuO loading, irradiation time, photocatalyst amount, initial concentration of the ethylene glycol solution on the reaction rate of photocatalytic hydrogen evolution was studied. The possible reaction mechanism was also discussed. The results show that the optimal hydrogen evolution rate reachs 604.5 μmol·h-1·g-1 under irradiation of 300 W Xe lamp. The CuO/TiO2 photocatalyst possesses enhanced optical absorption property, which can help to reduce the electron-hole recombination because the photo-generated electrons in TiO2 can be readily transferred to CuO. We suggest that ethylene glycol as electron donor may be further oxidized via glycolic acid.
2015, (11): 2174-2180
doi: 10.11862/CJIC.2015.298
Abstract:
The porous TiO2 film photoanodes were prepared based on TiO2 hollow spheres as the main substrate and TiO2 nanosheets as the scaffold in dye sensitized solar cell by doctor blade method. The results indicated that the highest photoelectric conversion efficiency reached 4.53% when the amount of TiO2 nanosheets as scaffold was 20wt% in film, which was higher than that of nonporous TiO2 film (4.06%) and that of no scaffold TiO2 film (4.17%). Furthermore, the photoelectric conversion efficiency improved to 7.06% when the thickness of the porous TiO2 film with 20wt% nanosheets was controlled 33 μm. The enhanced photoelectric conversion efficiency can be attributed the cooperation effect of the effective electron transmission and the large adsorption amount of dye molecules in scaffold structure. This research designed scaffold structure provides a new idea for the preparation of porous TiO2 film to enhance performance of dye sensitized solar cell.
The porous TiO2 film photoanodes were prepared based on TiO2 hollow spheres as the main substrate and TiO2 nanosheets as the scaffold in dye sensitized solar cell by doctor blade method. The results indicated that the highest photoelectric conversion efficiency reached 4.53% when the amount of TiO2 nanosheets as scaffold was 20wt% in film, which was higher than that of nonporous TiO2 film (4.06%) and that of no scaffold TiO2 film (4.17%). Furthermore, the photoelectric conversion efficiency improved to 7.06% when the thickness of the porous TiO2 film with 20wt% nanosheets was controlled 33 μm. The enhanced photoelectric conversion efficiency can be attributed the cooperation effect of the effective electron transmission and the large adsorption amount of dye molecules in scaffold structure. This research designed scaffold structure provides a new idea for the preparation of porous TiO2 film to enhance performance of dye sensitized solar cell.
2015, (11): 2181-2187
doi: 10.11862/CJIC.2015.296
Abstract:
Nano-structure NixCo1-xFe2O4 (x=0, 0.3, 0.5, 0.7, 1) microspheres were synthesized in ethylene glycol (EG) solution, using FeCl3·6H2O, CoCl2·6H2O, NiCl2·H2O and NH4Ac as the starting materials through solvothermal method. The influence of the amount of Ni2+ on the magnetic and absorbing properties was studied. The structure, morphology, magnetic properties and wave absorbing properties of the products were characterized by XRD, SEM, TEM, Vibration sample magnetometer (VSM) and network vector analyzer. Results show that monodispersed NixCo1-xFe2O4 hollow microsphere ferrites are single-crystal cubic spinel structure with the average diameter of 200 nm． When x=0, the value of maximum saturation magnetization is 81.7 emu·g-1 and the reflection loss in 1 658.8 MHz has a minimum value of -16.9 dB.
Nano-structure NixCo1-xFe2O4 (x=0, 0.3, 0.5, 0.7, 1) microspheres were synthesized in ethylene glycol (EG) solution, using FeCl3·6H2O, CoCl2·6H2O, NiCl2·H2O and NH4Ac as the starting materials through solvothermal method. The influence of the amount of Ni2+ on the magnetic and absorbing properties was studied. The structure, morphology, magnetic properties and wave absorbing properties of the products were characterized by XRD, SEM, TEM, Vibration sample magnetometer (VSM) and network vector analyzer. Results show that monodispersed NixCo1-xFe2O4 hollow microsphere ferrites are single-crystal cubic spinel structure with the average diameter of 200 nm． When x=0, the value of maximum saturation magnetization is 81.7 emu·g-1 and the reflection loss in 1 658.8 MHz has a minimum value of -16.9 dB.
2015, (11): 2188-2196
doi: 10.11862/CJIC.2015.277
Abstract:
Seven diculear platinum complexes with the new chiral ligand, (1iR,1iiR,2iR,2iiR)-Ni, Nii-(1,3-phenylenebis(methylene))dicyclohexane-1,2-diamine (HL), were designed, synthesized and spectrally characterized by IR, 1H NMR, 13C NMR, ESI-MS and microanalyses. The cytotoxicities of targeted dinuclear platinum compounds against human HepG-2, A549, HCT-116 and MCF-7 cell lines were evaluated by MTT assay. Results indicated that all compounds exhibited positive activity to HepG-2, A549 and HCT-116 cell lines, but none of them showed activity to MCF-7 cell line. Among them, compound P7, owing to 3-hydroxycyclobutane-1,1-dicarboxylate as the leaving group, gave better antitumor activity than carboplatin against HepG-2 and A549 cell lines, and close cytotoxicity to oxaliplatin against HCT-116 cell line.
Seven diculear platinum complexes with the new chiral ligand, (1iR,1iiR,2iR,2iiR)-Ni, Nii-(1,3-phenylenebis(methylene))dicyclohexane-1,2-diamine (HL), were designed, synthesized and spectrally characterized by IR, 1H NMR, 13C NMR, ESI-MS and microanalyses. The cytotoxicities of targeted dinuclear platinum compounds against human HepG-2, A549, HCT-116 and MCF-7 cell lines were evaluated by MTT assay. Results indicated that all compounds exhibited positive activity to HepG-2, A549 and HCT-116 cell lines, but none of them showed activity to MCF-7 cell line. Among them, compound P7, owing to 3-hydroxycyclobutane-1,1-dicarboxylate as the leaving group, gave better antitumor activity than carboplatin against HepG-2 and A549 cell lines, and close cytotoxicity to oxaliplatin against HCT-116 cell line.
2015, (11): 2197-2204
doi: 10.11862/CJIC.2015.279
Abstract:
Ti1-xVxO2 films with dominant {211} facets were deposited by direct current reactive magnetron sputtering with Ti and Vtargets (99.99% purity) at room temperature. We study the composition, crystal structure and visible-light photocatalytic properties of the films as a function of power of Vtarget. The results showed that crystal phase of Ti1-xVxO2 films was anatase with (211) preferred orientation, but the films deposited at different power of Vtarget had different crystallinities. With the increase of power of Vtarget, the relative contents of Velement increased gradually, meanwhile, crystal grain and deposition rate also increased. In addition, the surface roughness of the film had a maximum value when the power of Vtarget was 150 W. The addition of Velement gives rise to the band gap of TiO2 films narrowing down. As a result, the optical absorption edge of the Ti1-xVxO2 films shifts towards visible-light zone, improving the visible-light photocatalytic activity of the films. When the power of Vtarget came to 150 W, the value of band gap of the Ti1-xVxO2 film was about 2.82 eV, and the film degraded ~80% RhBdyes after 2 h visible-light irradiation. This can be attributed to the synergistic effect of narrow band gap, high energy facet {211}, and high crystallinity.
Ti1-xVxO2 films with dominant {211} facets were deposited by direct current reactive magnetron sputtering with Ti and Vtargets (99.99% purity) at room temperature. We study the composition, crystal structure and visible-light photocatalytic properties of the films as a function of power of Vtarget. The results showed that crystal phase of Ti1-xVxO2 films was anatase with (211) preferred orientation, but the films deposited at different power of Vtarget had different crystallinities. With the increase of power of Vtarget, the relative contents of Velement increased gradually, meanwhile, crystal grain and deposition rate also increased. In addition, the surface roughness of the film had a maximum value when the power of Vtarget was 150 W. The addition of Velement gives rise to the band gap of TiO2 films narrowing down. As a result, the optical absorption edge of the Ti1-xVxO2 films shifts towards visible-light zone, improving the visible-light photocatalytic activity of the films. When the power of Vtarget came to 150 W, the value of band gap of the Ti1-xVxO2 film was about 2.82 eV, and the film degraded ~80% RhBdyes after 2 h visible-light irradiation. This can be attributed to the synergistic effect of narrow band gap, high energy facet {211}, and high crystallinity.
2015, (11): 2205-2212
doi: 10.11862/CJIC.2015.297
Abstract:
Four new cobalt and nickel complexes containing a polypyridine-amine ligand were designed and prepared, namely, [M(L1)](BF4)2 (L1=N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine; C1, M=Co; C2, M=Ni) and [M(L2)](BF4)n (L2=N,N,N',N'-tetrakis(2-pyridylmethyl)propane-1,3-diamine; C3 M=Co, n=3; C4, M=Ni, n=2). These complexes were characterized by infrared spectroscopy (IR) and element analysis (EA). The structures of the complexes were determined by X-ray single crystal diffraction. The four complexes all belong to the monoclinic crystal system but with different space groups (C1, Cc; C2, P21/n; C3, C2/c; C4, P21/c). Different three-dimensional packing structures were found for these complexes.
Four new cobalt and nickel complexes containing a polypyridine-amine ligand were designed and prepared, namely, [M(L1)](BF4)2 (L1=N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine; C1, M=Co; C2, M=Ni) and [M(L2)](BF4)n (L2=N,N,N',N'-tetrakis(2-pyridylmethyl)propane-1,3-diamine; C3 M=Co, n=3; C4, M=Ni, n=2). These complexes were characterized by infrared spectroscopy (IR) and element analysis (EA). The structures of the complexes were determined by X-ray single crystal diffraction. The four complexes all belong to the monoclinic crystal system but with different space groups (C1, Cc; C2, P21/n; C3, C2/c; C4, P21/c). Different three-dimensional packing structures were found for these complexes.
2015, (11): 2213-2220
doi: 10.11862/CJIC.2015.295
Abstract:
Four complexes, {[Ag(L)]NO3}n (1), {[Ag(L)(H2O)]BF4}n (2), {[Ag2(L)3](SbF6)2}n (3), {[Ag(L)]ClO4}n (4), were synthesized by treating chelating ligand trans-bis(benzoylacetone)-1,4-diaminocyclohexane (L) with AgX (X=NO3-, BF4-, SbF6-, ClO4-). The structures of these complexes were characterized by elemental analysis, infrared spectroscopy, and X-ray single-crystal diffraction. In the solid state, the ligands in the 2D networks of 1 and 2 exhibited two types of coordination modes: in 1, the CN bonds of the bridging ligand, 1,4-diaminocyclohexane, were axial, while in 2, the CNbonds were equatorial. On the other hand, the ligands in 3 exhibited two types of coordination modes, which formed only 1Dcomplexes. Moreover, the ligands in 4 exhibited only one type of coordination mode, which formed a 2D network. Anions in 2,3 were not coordinated to Ag(Ⅰ); However, 1 and 4 were coordinated to Ag(Ⅰ). Meanwhile, the solid-state fluorescence of ligands and complexes was studied at room temperature.
Four complexes, {[Ag(L)]NO3}n (1), {[Ag(L)(H2O)]BF4}n (2), {[Ag2(L)3](SbF6)2}n (3), {[Ag(L)]ClO4}n (4), were synthesized by treating chelating ligand trans-bis(benzoylacetone)-1,4-diaminocyclohexane (L) with AgX (X=NO3-, BF4-, SbF6-, ClO4-). The structures of these complexes were characterized by elemental analysis, infrared spectroscopy, and X-ray single-crystal diffraction. In the solid state, the ligands in the 2D networks of 1 and 2 exhibited two types of coordination modes: in 1, the CN bonds of the bridging ligand, 1,4-diaminocyclohexane, were axial, while in 2, the CNbonds were equatorial. On the other hand, the ligands in 3 exhibited two types of coordination modes, which formed only 1Dcomplexes. Moreover, the ligands in 4 exhibited only one type of coordination mode, which formed a 2D network. Anions in 2,3 were not coordinated to Ag(Ⅰ); However, 1 and 4 were coordinated to Ag(Ⅰ). Meanwhile, the solid-state fluorescence of ligands and complexes was studied at room temperature.
2015, (11): 2221-2228
doi: 10.11862/CJIC.2015.267
Abstract:
Under same conditions, ligand derived from Pyrazine was selected and reacted with different Cadmium(Ⅱ) salts, producing two novel coordination compounds [Cd(L)2]n (1) and [Cd2(L)2(CH3COO)2(H2O)2] (2) (HL=4-((3-(pyrazin-2-yl)-1H-pyrazol-1-yl)methyl) benzoic acid), which were characterized by element analysis, TGA, fluorescence spectrum and single X-ray crystal diffraction. Compound 1 crystallizes in the triclinic system with P1 space group, and each Cd(Ⅱ) trigonal bipyramidal are connected to each other to form an infinite 2D sandwich structure. Compound 2 adopts binuclear structure with space group triclinic. Two carboxylate groups coordinated to Cd(Ⅱ) adopt a bidentate chelating mode fashion, which are different from coordination mode of 1. Structural discrepancy in compounds 1 and 2 can be assigned to different chelating modes of carboxylate groups of ligand, as well as ions effect. Superoxide dismutase (SOD) mimetic activity of compound 1 and 2 has been investigated by the modified Marklund method.
Under same conditions, ligand derived from Pyrazine was selected and reacted with different Cadmium(Ⅱ) salts, producing two novel coordination compounds [Cd(L)2]n (1) and [Cd2(L)2(CH3COO)2(H2O)2] (2) (HL=4-((3-(pyrazin-2-yl)-1H-pyrazol-1-yl)methyl) benzoic acid), which were characterized by element analysis, TGA, fluorescence spectrum and single X-ray crystal diffraction. Compound 1 crystallizes in the triclinic system with P1 space group, and each Cd(Ⅱ) trigonal bipyramidal are connected to each other to form an infinite 2D sandwich structure. Compound 2 adopts binuclear structure with space group triclinic. Two carboxylate groups coordinated to Cd(Ⅱ) adopt a bidentate chelating mode fashion, which are different from coordination mode of 1. Structural discrepancy in compounds 1 and 2 can be assigned to different chelating modes of carboxylate groups of ligand, as well as ions effect. Superoxide dismutase (SOD) mimetic activity of compound 1 and 2 has been investigated by the modified Marklund method.
2015, (11): 2229-2235
doi: 10.11862/CJIC.2015.275
Abstract:
Density functional theory(DFT) calculations have been performed to explore the molecular structure and O-H bond dissociation enthalpy(BDE) of luteolin and luteolin-Cr(Ⅲ) complex. Possible antioxidation mechanism between hydrogen peroxide radical·O2H and luteolin has been discussed, and the hydrogen atom transferring mechanism has been analyzed using the natural bond orbital (NBO) theory. Besides the theoretical studies, the experiment was performed to revise the theoretical peroration. According to the experiment, the complex has a higher ·O2H radical scavenging activity than that of luteolin which agrees with that by theoretical studies.
Density functional theory(DFT) calculations have been performed to explore the molecular structure and O-H bond dissociation enthalpy(BDE) of luteolin and luteolin-Cr(Ⅲ) complex. Possible antioxidation mechanism between hydrogen peroxide radical·O2H and luteolin has been discussed, and the hydrogen atom transferring mechanism has been analyzed using the natural bond orbital (NBO) theory. Besides the theoretical studies, the experiment was performed to revise the theoretical peroration. According to the experiment, the complex has a higher ·O2H radical scavenging activity than that of luteolin which agrees with that by theoretical studies.
2015, (11): 2236-2242
doi: 10.11862/CJIC.2015.287
Abstract:
Five transition metal complexes based on the 5-hydroxy-pyridine-2-carboxylic acid (H2L) were synthesized under hydrothermal conditions, namely, [M(HL)2(H2O)2] (M=Zn, 1; Mn, 2; Co, 3; Ni, 4), [Cu(HL)2] (5). Compounds 1~5 were structurally characterized by the elemental analyses, infrared spectra, and single crystal X-ray diffractions. The structural analyses show that 1~5 are discrete mononuclear complexes, which are extended to form the 3D supramolecular frameworks by hydrogen bonds interactions. The solid-state photoluminescence of 1 and thermal properties of 1~5 were further explored, respectively.
Five transition metal complexes based on the 5-hydroxy-pyridine-2-carboxylic acid (H2L) were synthesized under hydrothermal conditions, namely, [M(HL)2(H2O)2] (M=Zn, 1; Mn, 2; Co, 3; Ni, 4), [Cu(HL)2] (5). Compounds 1~5 were structurally characterized by the elemental analyses, infrared spectra, and single crystal X-ray diffractions. The structural analyses show that 1~5 are discrete mononuclear complexes, which are extended to form the 3D supramolecular frameworks by hydrogen bonds interactions. The solid-state photoluminescence of 1 and thermal properties of 1~5 were further explored, respectively.
2015, (11): 2243-2248
doi: 10.11862/CJIC.2015.283
Abstract:
Thioether-containing pyridylalkylamide ligands 2-(methylsulfanyl)-N-[2-(pyridine-2-yl)methyl]acetamide (HL1) and 2-(methylsulfanyl)-N-[2-(pyridine-2-yl)ethyl]acetamide (HL2) were synthesized and fully characterized. Three copper complexes {[Cu(L1)(CH3OH)](OTf)}n (1), (OTf=triflate), {[Cu(L2)(OTf)]·CH3OH}n (2) and [Cu(HL2)(CH3OH)Cl] (3) were synthesized and characterized with X-ray diffraction methods. The single-crystal X-ray analyses indicate that complex 1 and 2 form 1Dcoordination polymers, while complex 3 is a mononuclear copper complex. The coordination modes of the copper ion are analyzed and the reasons are interpreted.
Thioether-containing pyridylalkylamide ligands 2-(methylsulfanyl)-N-[2-(pyridine-2-yl)methyl]acetamide (HL1) and 2-(methylsulfanyl)-N-[2-(pyridine-2-yl)ethyl]acetamide (HL2) were synthesized and fully characterized. Three copper complexes {[Cu(L1)(CH3OH)](OTf)}n (1), (OTf=triflate), {[Cu(L2)(OTf)]·CH3OH}n (2) and [Cu(HL2)(CH3OH)Cl] (3) were synthesized and characterized with X-ray diffraction methods. The single-crystal X-ray analyses indicate that complex 1 and 2 form 1Dcoordination polymers, while complex 3 is a mononuclear copper complex. The coordination modes of the copper ion are analyzed and the reasons are interpreted.
2015, (11): 2249-2256
doi: 10.11862/CJIC.2015.281
Abstract:
Three lathanide(Ⅲ) complexes, namely [Ln(HL)(NO3)3(CH3OH)2] (Ln=La, 1; Ce, 2) and [Nd(HL)(NO3)3(H2O)]CH3OH(3) (HL=2-acetylpyridine picolinohydrazone), have been isolated and characterized by elemental analyses, infrared spectra and single-crystal X-ray diffraction analyses. The results reveal that in the isostructure complexes 1 and 2, the eleven coordinated Ln(Ⅲ) ion with mono-capped pentagonal antiprism coordination geometry is surrounded by one HL ligand with N2O donor sets, three bidentate nitrate anion and two methanol molecules. In the complex 3, the Nd(Ⅲ) ion is coordinated by one HL ligand with N2O donor sets, three bidentate nitrate anions and one water molecule, thus exhibiting bicapped square antiprism coordination geometry. Furthermore, all the complexes have excellent antitumor activity towards Lovo human colorectal cancer, BGC823 and SGC7901 human gastric cancer cell lines.
Three lathanide(Ⅲ) complexes, namely [Ln(HL)(NO3)3(CH3OH)2] (Ln=La, 1; Ce, 2) and [Nd(HL)(NO3)3(H2O)]CH3OH(3) (HL=2-acetylpyridine picolinohydrazone), have been isolated and characterized by elemental analyses, infrared spectra and single-crystal X-ray diffraction analyses. The results reveal that in the isostructure complexes 1 and 2, the eleven coordinated Ln(Ⅲ) ion with mono-capped pentagonal antiprism coordination geometry is surrounded by one HL ligand with N2O donor sets, three bidentate nitrate anion and two methanol molecules. In the complex 3, the Nd(Ⅲ) ion is coordinated by one HL ligand with N2O donor sets, three bidentate nitrate anions and one water molecule, thus exhibiting bicapped square antiprism coordination geometry. Furthermore, all the complexes have excellent antitumor activity towards Lovo human colorectal cancer, BGC823 and SGC7901 human gastric cancer cell lines.
2015, (11): 2257-2264
doi: 10.11862/CJIC.2015.282
Abstract:
The self-assembled monolayers (SAMs) of aniline and alkyl substituted anilines grafted on n-Si(111) crystalline surface were prepared in the presence of lauroyl peroxide, and the photoelectrodes of polyanilines/n-Si(111) crystalline were prepared based on polymerizations between the SAMs and anilines. Additionally, the polyanilines with sulfonic acid group (SPANI) substituted n-Si(111) crystalline photoelectrodes were prepared via the above samples to fabricate SPANI/n-Si(111) electrodes (Si-SPANIs). Electrochemical studies indicate that the electrode based on 4-bromoaniline (Si-PANI) is better than that of 4-ethynylaniline (Si-C=C-PANI), and the electrode from 4-vinylaniline (Si-C-C-PANI) is the poorest. In addition, anion ring substitution is important in promoting photoelectric conversion of the electrodes. An electrode with high photocurrent density of 15.4 mA·cm-2 and photoelectric transformation efficiency of 13% was obtained.
The self-assembled monolayers (SAMs) of aniline and alkyl substituted anilines grafted on n-Si(111) crystalline surface were prepared in the presence of lauroyl peroxide, and the photoelectrodes of polyanilines/n-Si(111) crystalline were prepared based on polymerizations between the SAMs and anilines. Additionally, the polyanilines with sulfonic acid group (SPANI) substituted n-Si(111) crystalline photoelectrodes were prepared via the above samples to fabricate SPANI/n-Si(111) electrodes (Si-SPANIs). Electrochemical studies indicate that the electrode based on 4-bromoaniline (Si-PANI) is better than that of 4-ethynylaniline (Si-C=C-PANI), and the electrode from 4-vinylaniline (Si-C-C-PANI) is the poorest. In addition, anion ring substitution is important in promoting photoelectric conversion of the electrodes. An electrode with high photocurrent density of 15.4 mA·cm-2 and photoelectric transformation efficiency of 13% was obtained.
2015, (11): 2265-2271
doi: 10.11862/CJIC.2015.303
Abstract:
Two complexes [Cd(L)(H2O)(NO3)2] (1) and [Cd(L)I2]·CH3OH (2) (L=4-hydroxy-N-((quinolin-8-yl)methylene)benzohydrazide) have been synthesized and structurally determined by single-crystal X-ray diffraction. The results show that the Cd(Ⅱ) ion in 1 with a mono-capped trigonal prismatic geometry is surrounded by one acylhydrazone ligand with N2O donor set, one water molecule, one mono-dendate and one bidendate nitrate anions. However, the coordination geometry of the Cd(Ⅱ) ion in 1 is a distorted tetragonal pyramid with oxygen and two nitrogen atoms provided by the ligand L and two iodide anions. The thermal stabilities and luminescent properties of both complexes are also investigated in detail.
Two complexes [Cd(L)(H2O)(NO3)2] (1) and [Cd(L)I2]·CH3OH (2) (L=4-hydroxy-N-((quinolin-8-yl)methylene)benzohydrazide) have been synthesized and structurally determined by single-crystal X-ray diffraction. The results show that the Cd(Ⅱ) ion in 1 with a mono-capped trigonal prismatic geometry is surrounded by one acylhydrazone ligand with N2O donor set, one water molecule, one mono-dendate and one bidendate nitrate anions. However, the coordination geometry of the Cd(Ⅱ) ion in 1 is a distorted tetragonal pyramid with oxygen and two nitrogen atoms provided by the ligand L and two iodide anions. The thermal stabilities and luminescent properties of both complexes are also investigated in detail.
2015, (11): 2272-2278
doi: 10.11862/CJIC.2015.284
Abstract:
Two coordination polymers {[Zn(BIDPT)(pht)]2·2H2O·CH3OH}n (1) and {[Cd5(BIDPT)4(pht)5]·H2O}n (2) based on mixed-ligands, BIDPT (4,4'-bis(imidazol-l-yl)diphenyl thioether) and H2pht (phthalic acid), have been synthesized by mild hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, IRspectra. The results show that 1 and 2 feature 2D networks. Compound 1 crystallizes in the orthorhombic system, space group Pbcn. Compound 2 crystallizes in the monoclinic system of the P21/c space group. The thermal stability and luminescent properties of compounds 1 and 2 are also investigated.
Two coordination polymers {[Zn(BIDPT)(pht)]2·2H2O·CH3OH}n (1) and {[Cd5(BIDPT)4(pht)5]·H2O}n (2) based on mixed-ligands, BIDPT (4,4'-bis(imidazol-l-yl)diphenyl thioether) and H2pht (phthalic acid), have been synthesized by mild hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, IRspectra. The results show that 1 and 2 feature 2D networks. Compound 1 crystallizes in the orthorhombic system, space group Pbcn. Compound 2 crystallizes in the monoclinic system of the P21/c space group. The thermal stability and luminescent properties of compounds 1 and 2 are also investigated.
