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2013 Volume 29 Issue 3
2013, 29(3): 429-436
doi: 10.3969/j.issn.1001-4861.2013.00.051
Abstract:
CdSe/TiO2 nanotube array (TiO2NTA) film was modified by NixCo3-xO4 through the method of ammonia-evaporation induction growth. The films were characterized by X-ray diffraction, field emission scanning electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy and UV-Vis diffuse reflectance spectroscopy. To characterize the photoanodes activity of photoelectrochemical oxidation of water, the chopped linear sweep voltammetry was performed in a three-electrode system under simulated solar irradiation. The results show that CdSe/TiO2NTA is covered by a thin layer of NixCo3-xO4 with the spinel structure in which Ni and Co are both in divalent and trivalent states. The modification of NixCo3-xO4 on the CdSe/TiO2NTA can lower the overpotential of water oxidation by about 430 mV compared with the CdSe/TiO2NTA. The introduction of Ni into the structure of Co3O4 leads to the surface enhancement of trivalent cations (Ni3+ and Co3+) and consequently facilitates the oxidation of water.
CdSe/TiO2 nanotube array (TiO2NTA) film was modified by NixCo3-xO4 through the method of ammonia-evaporation induction growth. The films were characterized by X-ray diffraction, field emission scanning electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy and UV-Vis diffuse reflectance spectroscopy. To characterize the photoanodes activity of photoelectrochemical oxidation of water, the chopped linear sweep voltammetry was performed in a three-electrode system under simulated solar irradiation. The results show that CdSe/TiO2NTA is covered by a thin layer of NixCo3-xO4 with the spinel structure in which Ni and Co are both in divalent and trivalent states. The modification of NixCo3-xO4 on the CdSe/TiO2NTA can lower the overpotential of water oxidation by about 430 mV compared with the CdSe/TiO2NTA. The introduction of Ni into the structure of Co3O4 leads to the surface enhancement of trivalent cations (Ni3+ and Co3+) and consequently facilitates the oxidation of water.
2013, 29(3): 437-443
doi: 10.3969/j.issn.1001-4861.2013.00.063
Abstract:
LiMnPO4 coated LiMn2O4 with different contents were prepared via hydrothermal method, and their structural and electrochemical properties were characterized by XRD, Raman, SEM, TEM and charge-discharge test. Generally, the modification of LiMnPO4 on the surface of the LiMn2O4 could not only increase the reversible capacity, but also upgrade its cyclic performances when cells were operated at 55 ℃. In the case of the 1wt% LiMnPO4 coated LiMn2O4, its reversible capacity is about 109 mAh·g-1 when cell was operated at 55 ℃, which is about 96% of its initial capacity. Moreover, 1wt% LiMnPO4 coated LiMn2O4 exhibits an improved rate capability compared with that of the bare LiMn2O4.
LiMnPO4 coated LiMn2O4 with different contents were prepared via hydrothermal method, and their structural and electrochemical properties were characterized by XRD, Raman, SEM, TEM and charge-discharge test. Generally, the modification of LiMnPO4 on the surface of the LiMn2O4 could not only increase the reversible capacity, but also upgrade its cyclic performances when cells were operated at 55 ℃. In the case of the 1wt% LiMnPO4 coated LiMn2O4, its reversible capacity is about 109 mAh·g-1 when cell was operated at 55 ℃, which is about 96% of its initial capacity. Moreover, 1wt% LiMnPO4 coated LiMn2O4 exhibits an improved rate capability compared with that of the bare LiMn2O4.
2013, 29(3): 444-448
doi: 10.3969/j.issn.1001-4861.2013.00.130
Abstract:
Solvothermal reaction of 1,3-dipyridyl benzene (1,3-dpb) with 4,4'-oxybis(benzoic acid) (H2oba) produced a two dimensional (2D) zinc(Ⅱ) coordination polymer {[Zn(oba)(dpb)]·H2O}n (1). The complex was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c. The neighboring Zn(Ⅱ) ions are linked by oba2- anions and 1,3-dpb to form infinitely 2D sheet, two 2D sheets are interlocked each other to form 2D→2D structure, and these two 2D sheets were linked each other by H-bonding. Two groups of interlocked structures further linked to form bilayer 2D supermolecule network by π-π interaction. In addition, the fluorescence property of 1 was also studied. CCDC: 917714.
Solvothermal reaction of 1,3-dipyridyl benzene (1,3-dpb) with 4,4'-oxybis(benzoic acid) (H2oba) produced a two dimensional (2D) zinc(Ⅱ) coordination polymer {[Zn(oba)(dpb)]·H2O}n (1). The complex was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c. The neighboring Zn(Ⅱ) ions are linked by oba2- anions and 1,3-dpb to form infinitely 2D sheet, two 2D sheets are interlocked each other to form 2D→2D structure, and these two 2D sheets were linked each other by H-bonding. Two groups of interlocked structures further linked to form bilayer 2D supermolecule network by π-π interaction. In addition, the fluorescence property of 1 was also studied. CCDC: 917714.
2013, 29(3): 449-454
doi: 10.3969/j.issn.1001-4861.2013.00.089
Abstract:
In this work, the micro-structure and surface modification of sol-gel silica film were studied, for obtaining hydrophobic coatings with high transparency. Polyethylene glycol (PEG) was added into silica sol to adjust the particle size. Two kinds of surface modification (sol treatment and film treatment respectively) by hexamethyldisilazane (HMDS) were employed and compared. The particle size evolvement was measured by dynamic scattering particle size analyzer. The surface morphology, water contact angle, chemical compositions, and transmittance were characterized by atomic force microscope (AFM), contact angle instrument, transmittance, FTIR and UV-Vis-IR spectrophotometers. Results showed that addition of PEG increased the silica particle size and accordingly the film surface roughness, which gave rise to a significantly improved hydrophobicity. The surface modification was impacted by the particle size. Small particle size is good for sol treatment, while large particle size is good for film treatment. PEG-film after HMDS atmosphere treatment could present superhydrophobicity with water contact angle of 152°, and high transmittance was maintained at the same time.
In this work, the micro-structure and surface modification of sol-gel silica film were studied, for obtaining hydrophobic coatings with high transparency. Polyethylene glycol (PEG) was added into silica sol to adjust the particle size. Two kinds of surface modification (sol treatment and film treatment respectively) by hexamethyldisilazane (HMDS) were employed and compared. The particle size evolvement was measured by dynamic scattering particle size analyzer. The surface morphology, water contact angle, chemical compositions, and transmittance were characterized by atomic force microscope (AFM), contact angle instrument, transmittance, FTIR and UV-Vis-IR spectrophotometers. Results showed that addition of PEG increased the silica particle size and accordingly the film surface roughness, which gave rise to a significantly improved hydrophobicity. The surface modification was impacted by the particle size. Small particle size is good for sol treatment, while large particle size is good for film treatment. PEG-film after HMDS atmosphere treatment could present superhydrophobicity with water contact angle of 152°, and high transmittance was maintained at the same time.
2013, 29(3): 455-464
doi: 10.3969/j.issn.1001-4861.2013.00.108
Abstract:
Four Co(Ⅱ) complexes [Co(btec)0.5(pz)2]n (1), [Co(btec)0.5(pz)3]n (2), [Co(phen)(Hbtc)(H3btc) (H2O)2]·3H2O (3), [Co(Imh)2(anis)2(H2O)] (4), (H4btec=1,2,4,5-benzenetetracarboxylic acid, pz=pyrazole, H3btc=1,3,5-benzene-tricarboxylic acid, phen=1,10-phenanthroline, Imh=imidazole, Hanis=p-anisic acid) were synthesized by hydrothermal method. They were characterized by X-ray single crystal diffraction, IR, elemental analysis, UV-Vis-NIR diffuse reflection spectrum and surface photovoltage spectroscopy (SPS). The structural analyses indicate that 1 is a Co(Ⅱ) polymer with 2D structure. The Co(Ⅱ) ion is four-coordinate in 1; the ones in 2～4 are both six-coordinate. 2 possesses 1D structure, connected by hydrogen bonds into 2D layer. 3 and 4 are molecular complexes, which are networked into 3D and 2D structures by hydrogen bonds, respectively. Four complexes all exhibit obvious surface photovoltage responses within 300～600 nm in SPS, which indicates that they possess certain photo-electric conversion properties. The influences of structure, dimension of complex and coordination micro-environment of center metal ion on the SPS were discussed emphatically. The energy band theory of semiconductor and crystal field theory are combined to analyze and assign SPS response bands. CCDC: 883535, 1; 883536, 2; 883537, 3; 883538, 4.
Four Co(Ⅱ) complexes [Co(btec)0.5(pz)2]n (1), [Co(btec)0.5(pz)3]n (2), [Co(phen)(Hbtc)(H3btc) (H2O)2]·3H2O (3), [Co(Imh)2(anis)2(H2O)] (4), (H4btec=1,2,4,5-benzenetetracarboxylic acid, pz=pyrazole, H3btc=1,3,5-benzene-tricarboxylic acid, phen=1,10-phenanthroline, Imh=imidazole, Hanis=p-anisic acid) were synthesized by hydrothermal method. They were characterized by X-ray single crystal diffraction, IR, elemental analysis, UV-Vis-NIR diffuse reflection spectrum and surface photovoltage spectroscopy (SPS). The structural analyses indicate that 1 is a Co(Ⅱ) polymer with 2D structure. The Co(Ⅱ) ion is four-coordinate in 1; the ones in 2～4 are both six-coordinate. 2 possesses 1D structure, connected by hydrogen bonds into 2D layer. 3 and 4 are molecular complexes, which are networked into 3D and 2D structures by hydrogen bonds, respectively. Four complexes all exhibit obvious surface photovoltage responses within 300～600 nm in SPS, which indicates that they possess certain photo-electric conversion properties. The influences of structure, dimension of complex and coordination micro-environment of center metal ion on the SPS were discussed emphatically. The energy band theory of semiconductor and crystal field theory are combined to analyze and assign SPS response bands. CCDC: 883535, 1; 883536, 2; 883537, 3; 883538, 4.
2013, 29(3): 465-473
doi: 10.3969/j.issn.1001-4861.2013.00.078
Abstract:
A new mesoporous zirconium phosphonate(NTAZP) was synthesized by using nitrilotris(methylene)-triphosphonic acid (ATMP) and zirconium dichloride oxide octahydrate. The as-prepared mesoporous materials were characterized by XRD, FTIR, TG-DTA and SEM techniques. Fe3+-based aminotrialkylene zirconium phosphonate catalyst was obtained by using NTAZP as the support and by treating the support with an aqueous solution of Fe(NO3)3. The results indicate that the structure and morphology of NTAZP are not changed after loading, and ferric species are mainly anchored on NTAZP via the coordinative interactions between Fe3+ and N atoms inside the mesoporous channel. The supported ferric species NTAZP (NTAZP-Fe3+) with a good thermal stability are highly catalytic active for formaldehyde oxidation in relatively mild reaction conditions. The Fe-based catalyst can prevent Fe3+ from dissolving into the water, and can be recycled to avoid secondary pollution. NTAZP-Fe3+ is a high-efficient and green catalyst in small-molecule aldehydes oxidation.
A new mesoporous zirconium phosphonate(NTAZP) was synthesized by using nitrilotris(methylene)-triphosphonic acid (ATMP) and zirconium dichloride oxide octahydrate. The as-prepared mesoporous materials were characterized by XRD, FTIR, TG-DTA and SEM techniques. Fe3+-based aminotrialkylene zirconium phosphonate catalyst was obtained by using NTAZP as the support and by treating the support with an aqueous solution of Fe(NO3)3. The results indicate that the structure and morphology of NTAZP are not changed after loading, and ferric species are mainly anchored on NTAZP via the coordinative interactions between Fe3+ and N atoms inside the mesoporous channel. The supported ferric species NTAZP (NTAZP-Fe3+) with a good thermal stability are highly catalytic active for formaldehyde oxidation in relatively mild reaction conditions. The Fe-based catalyst can prevent Fe3+ from dissolving into the water, and can be recycled to avoid secondary pollution. NTAZP-Fe3+ is a high-efficient and green catalyst in small-molecule aldehydes oxidation.
2013, 29(3): 474-478
doi: 10.3969/j.issn.1001-4861.2013.00.085
Abstract:
Ag nanoparticles were successfully synthesized with a high yield by a polyol process, and the uniform spherical Ag@YF3:Eu3+ core-shell structural nanomaterials were fabricated via a facile direct precipitation method, then the structure and properties were characterized. XRD patterns show that the orthogonal phase YF3:Eu3+ nanocrystals are coated on the surface of Ag cores. TEM images indicate that the obtained composites have obvious core-shell structure and uniform spherical morphology, the diameter of the Ag core is of 80～100 nm, the size of the Ag@YF3:Eu3+ composite is about 150～180 nm, the surface is rough and the coating is complete. Electron diffraction pattern indicates that the samples are polycrystalline. The photoluminescence spectra indicate that the core-shell structural composites have good luminescence, the strong emission peak is near 593 nm corresponding to 5D0→7F1 magnetic dipole transition of Eu3+, the fluorescent intensity is weaker but the lifetime is stronger than that of the pure YF3:Eu3+, which indicates that the fluorescent of YF3:Eu3+ is quenched by Ag cores.
Ag nanoparticles were successfully synthesized with a high yield by a polyol process, and the uniform spherical Ag@YF3:Eu3+ core-shell structural nanomaterials were fabricated via a facile direct precipitation method, then the structure and properties were characterized. XRD patterns show that the orthogonal phase YF3:Eu3+ nanocrystals are coated on the surface of Ag cores. TEM images indicate that the obtained composites have obvious core-shell structure and uniform spherical morphology, the diameter of the Ag core is of 80～100 nm, the size of the Ag@YF3:Eu3+ composite is about 150～180 nm, the surface is rough and the coating is complete. Electron diffraction pattern indicates that the samples are polycrystalline. The photoluminescence spectra indicate that the core-shell structural composites have good luminescence, the strong emission peak is near 593 nm corresponding to 5D0→7F1 magnetic dipole transition of Eu3+, the fluorescent intensity is weaker but the lifetime is stronger than that of the pure YF3:Eu3+, which indicates that the fluorescent of YF3:Eu3+ is quenched by Ag cores.
2013, 29(3): 479-485
doi: 10.3969/j.issn.1001-4861.2013.00.057
Abstract:
Cobalt ferrite/expanded graphite complex particles (CF/EG) and cobalt ferrite/expanded graphite/polypyrrole composites (CF/EG/PPy) were prepared by chemical co-precipitation method and in-situ emulsion polymerization, respectively. The composition, structures, morphology, electrical and magnetic properties, and oil/water separation property of samples were characterized by means of modern analytical techniques. The results indicated that CF particles embedded in layers of EG, and there was some interaction between the core (CF/EG) and shell (PPy) in the CF/EG/PPy composites. The oil/water separation effect of samples was proportional to the spacing of layers in EG, their sequence was EG>CF/EG>CF/EG/PPy. The CF/EG complex particles with magnetism could be easily recovered and had good performance for repeated use. And its efficiency by cycling of five times was not less than 90%.
Cobalt ferrite/expanded graphite complex particles (CF/EG) and cobalt ferrite/expanded graphite/polypyrrole composites (CF/EG/PPy) were prepared by chemical co-precipitation method and in-situ emulsion polymerization, respectively. The composition, structures, morphology, electrical and magnetic properties, and oil/water separation property of samples were characterized by means of modern analytical techniques. The results indicated that CF particles embedded in layers of EG, and there was some interaction between the core (CF/EG) and shell (PPy) in the CF/EG/PPy composites. The oil/water separation effect of samples was proportional to the spacing of layers in EG, their sequence was EG>CF/EG>CF/EG/PPy. The CF/EG complex particles with magnetism could be easily recovered and had good performance for repeated use. And its efficiency by cycling of five times was not less than 90%.
2013, 29(3): 486-492
doi: 10.3969/j.issn.1001-4861.2013.00.062
Abstract:
Four new substituted phthalonitriles such as 3-(5-aminonaphthoxy) phthalonitrile(C18H11N3O), 4-(5-aminonaphthoxy) phthalonitrile(C18H11N3O), 3-biphenyloxy-phthalonitrile(C20H12N2O) and 4-biphenyloxy-phthalonitrile(C20H12N2O) have been synthesized, which are converted into the corresponding phthalocyanine-zinc(Ⅱ) complexes with aryloxy substitunents:tetra-alpha-(5-aminonaphthoxy) phthalocyanines zinc(Ⅱ) (C72H44N12O4Zn), tetra-β-(5-aminonaphthoxy) phthalocyanines zinc(Ⅱ)(C72H44N12O4Zn), tetra-alpha-biphenyloxy-phthalocyanines zinc(Ⅱ)(C80H48N8O4Zn) and tetra-β-biphenyloxy-phthalocyanines zinc(Ⅱ)(C80H48N8O4Zn). Their maximum absorption wavelength, molar extinction coefficient, emission wavelength, fluorescence quantum yields (ФF), the singlet oxygen quantum yields(ΦΔ), and photodegradation constant(k) have been measured by the UV-Vis absorption and fluorescence spectra. The structure-activity relationship have been discussed in comparision with their analogues. The results show that tetra-alpha-biphenyloxy-phthalocyanines zinc(Ⅱ) has large extinction coefficient in the red visible region of the light with relatively higher singlet oxygen quantum yield, it is a promising photosensitizer for use in photodynamic therapy.
Four new substituted phthalonitriles such as 3-(5-aminonaphthoxy) phthalonitrile(C18H11N3O), 4-(5-aminonaphthoxy) phthalonitrile(C18H11N3O), 3-biphenyloxy-phthalonitrile(C20H12N2O) and 4-biphenyloxy-phthalonitrile(C20H12N2O) have been synthesized, which are converted into the corresponding phthalocyanine-zinc(Ⅱ) complexes with aryloxy substitunents:tetra-alpha-(5-aminonaphthoxy) phthalocyanines zinc(Ⅱ) (C72H44N12O4Zn), tetra-β-(5-aminonaphthoxy) phthalocyanines zinc(Ⅱ)(C72H44N12O4Zn), tetra-alpha-biphenyloxy-phthalocyanines zinc(Ⅱ)(C80H48N8O4Zn) and tetra-β-biphenyloxy-phthalocyanines zinc(Ⅱ)(C80H48N8O4Zn). Their maximum absorption wavelength, molar extinction coefficient, emission wavelength, fluorescence quantum yields (ФF), the singlet oxygen quantum yields(ΦΔ), and photodegradation constant(k) have been measured by the UV-Vis absorption and fluorescence spectra. The structure-activity relationship have been discussed in comparision with their analogues. The results show that tetra-alpha-biphenyloxy-phthalocyanines zinc(Ⅱ) has large extinction coefficient in the red visible region of the light with relatively higher singlet oxygen quantum yield, it is a promising photosensitizer for use in photodynamic therapy.
2013, 29(3): 493-499
doi: 10.3969/j.issn.1001-4861.2013.00.018
Abstract:
The BaZrO3 material was synthesized by the citric acid method. A series of Ru/BaZrO3 catalyst samples were prepared using the above BaZrO3 calcined at different temperatures as the support. The support materials and catalyst samples were characterized by X-ray diffraction (XRD), H2 temperature programmed reduction (H2-TPR), CO2 temperature programmed desorption (CO2-TPD), N2 adsorption-desorption isotherms and scanning electron microscopy (SEM). The results show that the catalytic performance is greatly influenced by the calcination temperature of the BaZrO3 support. The highest catalytic activity for ammonia synthesis is obtained on the Ru-based catalyst with the support calcined at 750 ℃. The ammonia concentration of RBZ-750 can achieve to 9.12% under the condition of 425 ℃, 5 MPa and 10 000 h-1. The strong mental-support interaction and electron conductivity of the support may be the key factors for the high activity at low reaction temperature.
The BaZrO3 material was synthesized by the citric acid method. A series of Ru/BaZrO3 catalyst samples were prepared using the above BaZrO3 calcined at different temperatures as the support. The support materials and catalyst samples were characterized by X-ray diffraction (XRD), H2 temperature programmed reduction (H2-TPR), CO2 temperature programmed desorption (CO2-TPD), N2 adsorption-desorption isotherms and scanning electron microscopy (SEM). The results show that the catalytic performance is greatly influenced by the calcination temperature of the BaZrO3 support. The highest catalytic activity for ammonia synthesis is obtained on the Ru-based catalyst with the support calcined at 750 ℃. The ammonia concentration of RBZ-750 can achieve to 9.12% under the condition of 425 ℃, 5 MPa and 10 000 h-1. The strong mental-support interaction and electron conductivity of the support may be the key factors for the high activity at low reaction temperature.
2013, 29(3): 500-506
doi: 10.3969/j.issn.1001-4861.2013.00.104
Abstract:
V2O5 micro-nanorods were fabricated via calcining the as-synthesized precursors prepared by electrospinning technique route using NH4VO3 and PVP as regent. The physicochemical properties of the catalysts were characterized by Thermogravimetric and Differential thermal analysis (TG-DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and UV-Vis diffuse reflectance spectra(UV-Vis). The photocatalytic activity of V2O5 micro-nanorod toward the decomposition of Methylene Blue (MB) was investigated. The results indicated that calcination temperature had a great influence on the morphologies and crystalline phases of the micro-nanorod. 550 ℃ micro-nanorod exhibited the highest activity for degrading MB under Visible light, and the photocatalytic mechanism of V2O5 micro-nanorod was also presented.
V2O5 micro-nanorods were fabricated via calcining the as-synthesized precursors prepared by electrospinning technique route using NH4VO3 and PVP as regent. The physicochemical properties of the catalysts were characterized by Thermogravimetric and Differential thermal analysis (TG-DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and UV-Vis diffuse reflectance spectra(UV-Vis). The photocatalytic activity of V2O5 micro-nanorod toward the decomposition of Methylene Blue (MB) was investigated. The results indicated that calcination temperature had a great influence on the morphologies and crystalline phases of the micro-nanorod. 550 ℃ micro-nanorod exhibited the highest activity for degrading MB under Visible light, and the photocatalytic mechanism of V2O5 micro-nanorod was also presented.
2013, 29(3): 507-515
doi: 10.3969/j.issn.1001-4861.2013.00.088
Abstract:
The aim of this study is to investigate effects of dopamine (DA) on physiochemical properties of calcium phosphate cement (CPC) and in vitro degradation of DA from CPC. DA was dissolved in Tris (Hydroxymethyl) aminomethane-hydrochloric acid buffer solution and mixed the solution with CPC powders after oxidized for 2 d in air. Orthogonal test was used to optimize the preparation of CPC with respect to the DA concentration, ratio of liquid to solid and pH values. Compressive tests, Gilmore needle tests, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) were used to characterize the physiochemical properties of CPC. Scanning electron microscope (SEM) and UV-Vis spectrophotometry were used to observe the micro-morphology of CPC and in vitro degradation of DA from CPC, respectively. Compressive test and orthogonal analysis indicated that the optimal combination CPC was DA concentration 40 mg·mL-1, ratio of liquid to solid 0.3 mL·g-1 and pH value 8.5, which had the highest compressive strength with significant difference (p<0.01) compared with that of CPC-Blank. Setting time of the optimal combination CPC decreased slight but no significant difference compared to that of CPC-Blank, which could satisfied with the clinical demands. XRD and FTIR demonstrated that the addition of DA promoted the conversion of dicalcium phosphate dehydrate (DCPD). SEM found that there were more platy structure, lots of nubbly crystals and less porosity in optimal combination CPC compared with CPC-Blank. Cumulative release of DA from CPC was 29.7% and the pH values of immersion solution were safe for human body during in vitro degradation.
The aim of this study is to investigate effects of dopamine (DA) on physiochemical properties of calcium phosphate cement (CPC) and in vitro degradation of DA from CPC. DA was dissolved in Tris (Hydroxymethyl) aminomethane-hydrochloric acid buffer solution and mixed the solution with CPC powders after oxidized for 2 d in air. Orthogonal test was used to optimize the preparation of CPC with respect to the DA concentration, ratio of liquid to solid and pH values. Compressive tests, Gilmore needle tests, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) were used to characterize the physiochemical properties of CPC. Scanning electron microscope (SEM) and UV-Vis spectrophotometry were used to observe the micro-morphology of CPC and in vitro degradation of DA from CPC, respectively. Compressive test and orthogonal analysis indicated that the optimal combination CPC was DA concentration 40 mg·mL-1, ratio of liquid to solid 0.3 mL·g-1 and pH value 8.5, which had the highest compressive strength with significant difference (p<0.01) compared with that of CPC-Blank. Setting time of the optimal combination CPC decreased slight but no significant difference compared to that of CPC-Blank, which could satisfied with the clinical demands. XRD and FTIR demonstrated that the addition of DA promoted the conversion of dicalcium phosphate dehydrate (DCPD). SEM found that there were more platy structure, lots of nubbly crystals and less porosity in optimal combination CPC compared with CPC-Blank. Cumulative release of DA from CPC was 29.7% and the pH values of immersion solution were safe for human body during in vitro degradation.
2013, 29(3): 516-522
doi: 10.3969/j.issn.1001-4861.2013.00.029
Abstract:
The complexes {[Ln(Hbidc)(bidc)(H2O)3]·3H2O}n (Ln=Eu 1, Dy 2; H2bidc=benzimidazole-5,6-dicarboxylic acid)have been obtained by hydrothermal method and characterized by X-ray single-crystal diffraction. The two complexes belong to monoclinic system, P21/c space group. Complexes 1 and 2 have similar 1D chain structures. Ln3+ ion is nine-coordinated by six oxygen atoms of carboxylate groups and three oxygen atom of water molecules. Ln3+ ions are linked by bmdc ligands to form a 1D helical chain. The right- and left-handed chains are further connected to form 3D network via interchain hydrogen bonds and π-π stacking interactions. The two complexes behave characteristic fluorescence of Eu3+ and Dy3+ ions, respectively. CCDC: 883519, 1; 883518, 2.
The complexes {[Ln(Hbidc)(bidc)(H2O)3]·3H2O}n (Ln=Eu 1, Dy 2; H2bidc=benzimidazole-5,6-dicarboxylic acid)have been obtained by hydrothermal method and characterized by X-ray single-crystal diffraction. The two complexes belong to monoclinic system, P21/c space group. Complexes 1 and 2 have similar 1D chain structures. Ln3+ ion is nine-coordinated by six oxygen atoms of carboxylate groups and three oxygen atom of water molecules. Ln3+ ions are linked by bmdc ligands to form a 1D helical chain. The right- and left-handed chains are further connected to form 3D network via interchain hydrogen bonds and π-π stacking interactions. The two complexes behave characteristic fluorescence of Eu3+ and Dy3+ ions, respectively. CCDC: 883519, 1; 883518, 2.
2013, 29(3): 523-527
doi: 10.3969/j.issn.1001-4861.2013.00.119
Abstract:
The electronic structure of LiMnPO4 positive electrode material for lithium ion battery was calculated by the first principles method based on the density functional theory (DFT). The calculated results demonstrate that the change for the atomic populations of O and P is slight, and the transfer of electrons to the metal atoms is obviously strengthened after the intercalation of Li+ ions. There is a weak interaction between Li+ ions and O2- ions, and the obtained electric charge of oxygen atom reduces, and then the atomic population decreases after deintercalation of Li+ ions. As a result, lithium element exists in the LiMnPO4 positive electrode material mainly in form of ions. In the LiMnPO4 and MnPO4, Mn atoms have magnetic properties, and the magnetic moment values are 4.78μB and 3.84μB, respectively. However, the magnetic properties of the rest atoms approximate to zero. For oxygen anion, with negative charge, and P and Mn is positive ion. There is an effective overlap between O2p, P3s, P3p orbits and Mn3d, O2p orbits, and then forms the covalent bonds. During the discharge, the electrons enter the positive electrode from external circuit, and most of the electrons mainly fill in the Mn atoms.
The electronic structure of LiMnPO4 positive electrode material for lithium ion battery was calculated by the first principles method based on the density functional theory (DFT). The calculated results demonstrate that the change for the atomic populations of O and P is slight, and the transfer of electrons to the metal atoms is obviously strengthened after the intercalation of Li+ ions. There is a weak interaction between Li+ ions and O2- ions, and the obtained electric charge of oxygen atom reduces, and then the atomic population decreases after deintercalation of Li+ ions. As a result, lithium element exists in the LiMnPO4 positive electrode material mainly in form of ions. In the LiMnPO4 and MnPO4, Mn atoms have magnetic properties, and the magnetic moment values are 4.78μB and 3.84μB, respectively. However, the magnetic properties of the rest atoms approximate to zero. For oxygen anion, with negative charge, and P and Mn is positive ion. There is an effective overlap between O2p, P3s, P3p orbits and Mn3d, O2p orbits, and then forms the covalent bonds. During the discharge, the electrons enter the positive electrode from external circuit, and most of the electrons mainly fill in the Mn atoms.
2013, 29(3): 528-536
doi: 10.3969/j.issn.1001-4861.2013.00.055
Abstract:
Mesoporous TiO2 was synthesized by a hydrolysis-precipitation method using a renewable biological resource of nano-cellulose as the template and TiCl4 as the precursor. The photocatalytic activity of TiO2 was evaluated using the degradation of methyl orange under ultraviolet light irradiation as a model reaction. N2 adsorption- desorption, transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetry-differential Scanning Calorimetry (TG/DSC), fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used for catalyst characterization. The results show that TiO2 synthesized with acid nano-cellulose template exhibits high activity under UV irradiation. The material exhibits mesoporous structure with specific area of 192 m2·g-1, average pore size of 5.03 nm, and pore volume of 0.35 cm3·g-1. The addition of acid nano-cellulose template can reduce the amount of surface OH- of TiO2, hydroxyl groups of long-chain cellulose and surface hydroxyl groups of TiO2 bonding can inhibit the TiO2 precursor growth and aggregation, and inhibit the phase transformation from anatase to rutile.
Mesoporous TiO2 was synthesized by a hydrolysis-precipitation method using a renewable biological resource of nano-cellulose as the template and TiCl4 as the precursor. The photocatalytic activity of TiO2 was evaluated using the degradation of methyl orange under ultraviolet light irradiation as a model reaction. N2 adsorption- desorption, transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetry-differential Scanning Calorimetry (TG/DSC), fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used for catalyst characterization. The results show that TiO2 synthesized with acid nano-cellulose template exhibits high activity under UV irradiation. The material exhibits mesoporous structure with specific area of 192 m2·g-1, average pore size of 5.03 nm, and pore volume of 0.35 cm3·g-1. The addition of acid nano-cellulose template can reduce the amount of surface OH- of TiO2, hydroxyl groups of long-chain cellulose and surface hydroxyl groups of TiO2 bonding can inhibit the TiO2 precursor growth and aggregation, and inhibit the phase transformation from anatase to rutile.
2013, 29(3): 537-543
doi: 10.3969/j.issn.1001-4861.2013.00.100
Abstract:
Dicyclohexyltin quinoline-2-carboxylate [Cy4Sn2(μ-OH)2(C9NH6CO2)2]·2[Cy2Sn(C9NH6CO2)2]·2H2O was synthesised by the reaction of tricyclohexyltin hydroxide with quinolinecarboxylic acid. The crystal structures have been determined by X-ray diffraction. It belongs to triclinic system, space group P1. In the unit cell, there are two different kinds of composition and structure of the dicyclohexyltin quinoline-2-carboxylate complex molecules. some of the tin atoms are five-coordination distorted tigonal bipyramidal structure, others are six coordinated distorted octahedron. The study on the title complex has been performed with quantum chemistry calculation. The stabilities, the orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated.The thermal stability,electrochemical properties and, photoluminescent property of complexes have been investigated. CCDC: 865659.
Dicyclohexyltin quinoline-2-carboxylate [Cy4Sn2(μ-OH)2(C9NH6CO2)2]·2[Cy2Sn(C9NH6CO2)2]·2H2O was synthesised by the reaction of tricyclohexyltin hydroxide with quinolinecarboxylic acid. The crystal structures have been determined by X-ray diffraction. It belongs to triclinic system, space group P1. In the unit cell, there are two different kinds of composition and structure of the dicyclohexyltin quinoline-2-carboxylate complex molecules. some of the tin atoms are five-coordination distorted tigonal bipyramidal structure, others are six coordinated distorted octahedron. The study on the title complex has been performed with quantum chemistry calculation. The stabilities, the orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated.The thermal stability,electrochemical properties and, photoluminescent property of complexes have been investigated. CCDC: 865659.
2013, 29(3): 544-550
doi: 10.3969/j.issn.1001-4861.2013.00.004
Abstract:
High-order TiO2 nanotube arrays on titanium foils were prepared in glycerol-based electrolyte containing fluorine and water by electrochemical anodic oxidation in this work. The influence of different dianion additives, different oxidation duration and concentration of electrolyte additives on the effect of the morphology of TiO2 nanotube arrays were investigated. Results showed that the length of TiO2 nanotube arrays in the modified electrolyte were longer than the samples in the unmodified electrolyte. And with the growth of oxidation duration, the diameter of the nanotubes increased, the wall were thinner; moreover better and longer TiO2 nanotube arrays can be prepared in the glycerol-based electrolyte with the range of the concentration of (NH4)2TiF6.
High-order TiO2 nanotube arrays on titanium foils were prepared in glycerol-based electrolyte containing fluorine and water by electrochemical anodic oxidation in this work. The influence of different dianion additives, different oxidation duration and concentration of electrolyte additives on the effect of the morphology of TiO2 nanotube arrays were investigated. Results showed that the length of TiO2 nanotube arrays in the modified electrolyte were longer than the samples in the unmodified electrolyte. And with the growth of oxidation duration, the diameter of the nanotubes increased, the wall were thinner; moreover better and longer TiO2 nanotube arrays can be prepared in the glycerol-based electrolyte with the range of the concentration of (NH4)2TiF6.
Influence of ZnCl2 Activation on Structure and Electrochemical Performance of Carbon Aerogel Spheres
2013, 29(3): 551-556
doi: 10.3969/j.issn.1001-4861.2013.00.123
Abstract:
Carbon aerogel spheres were activated by zinc chloride (ZnCl2), and the activated products were made into the electrodes of supercapacitor. The pore structure of carbon aerogel spheres was investigated by SEM and N2 adsorption. The electrochemical properties were tested by cyclic voltammetry (CV), AC impedance and constant current charge/discharge methods. The experimental results showed that the pore structure of carbon aerogel spheres was improved after ZnCl2 activation, then the surface area and porosity were increased through the increasing of micropore surface area and volume. Consequently the capacitance properties of the prepared electrodes were enhanced, the resistance decreased and the capacitance were increased twice.
Carbon aerogel spheres were activated by zinc chloride (ZnCl2), and the activated products were made into the electrodes of supercapacitor. The pore structure of carbon aerogel spheres was investigated by SEM and N2 adsorption. The electrochemical properties were tested by cyclic voltammetry (CV), AC impedance and constant current charge/discharge methods. The experimental results showed that the pore structure of carbon aerogel spheres was improved after ZnCl2 activation, then the surface area and porosity were increased through the increasing of micropore surface area and volume. Consequently the capacitance properties of the prepared electrodes were enhanced, the resistance decreased and the capacitance were increased twice.
2013, 29(3): 557-564
doi: 10.3969/j.issn.1001-4861.2013.00.120
Abstract:
We report an architecturally controlled synthesis of porous SiO2/TiO2-xCx/C composites with high adsorption capability and efficient visible-light photocatalytic activity. The porous composites are composed of silica particles as the cores and tetrabutyl titanate as the precursor for the TiO2 shell. Ethylene glycol, glycerol, glucose and polyvinyl alcohol were used as the binding agent between the core and the precursory shell, the carbon source and the porosity promoter, respectively. The structure, crystallinity, morphology, and other physical-chemical properties of the samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microcopy (HRTEM), X-ray photoelectron spectroscopy (XPS), fourier transform-infrared spectroscopy (FTIR), N2 adsorption-desorption isotherms measurements and UVVis diffuse reflectance spectroscopy (DRS). The formation mechanism of the porous composites was discussed. Methylene blue solution(MB) was used as model wastewater to evaluate the adsorption and photocatalytic activity of the samples under visible light. The as-synthesized porous composites exhibit both much higher adsorption capability and better photocatalytic activity for the photooxidation of MB than that of the pure silica-titania composite. The adsorption rate reaches 70% within 30 min when polyvinyl alcohol is used as the carbon source, and the sample using glycerol as the carbon source has the best visible- light photocatalytic activity and the degradation rate of MB can be 95% within 40 min.
We report an architecturally controlled synthesis of porous SiO2/TiO2-xCx/C composites with high adsorption capability and efficient visible-light photocatalytic activity. The porous composites are composed of silica particles as the cores and tetrabutyl titanate as the precursor for the TiO2 shell. Ethylene glycol, glycerol, glucose and polyvinyl alcohol were used as the binding agent between the core and the precursory shell, the carbon source and the porosity promoter, respectively. The structure, crystallinity, morphology, and other physical-chemical properties of the samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microcopy (HRTEM), X-ray photoelectron spectroscopy (XPS), fourier transform-infrared spectroscopy (FTIR), N2 adsorption-desorption isotherms measurements and UVVis diffuse reflectance spectroscopy (DRS). The formation mechanism of the porous composites was discussed. Methylene blue solution(MB) was used as model wastewater to evaluate the adsorption and photocatalytic activity of the samples under visible light. The as-synthesized porous composites exhibit both much higher adsorption capability and better photocatalytic activity for the photooxidation of MB than that of the pure silica-titania composite. The adsorption rate reaches 70% within 30 min when polyvinyl alcohol is used as the carbon source, and the sample using glycerol as the carbon source has the best visible- light photocatalytic activity and the degradation rate of MB can be 95% within 40 min.
2013, 29(3): 565-570
doi: 10.3969/j.issn.1001-4861.2013.00.103
Abstract:
In the presence of hexadecyl trimethyl ammonium bromide (CTAB) or fluoride ions (HF), superfine SAPO-11 was obtained via steam-assisted conversion method. The samples were characterized by SEM, XRD, IR, MAS NMR, TPD, TEM, TG-DSC and Nitrogen adsorption-desorption. The introduction of CTAB or HF can not only decrease the particle size, but also control the framework, morphology, pore structure and acid properties of SAPO-11 zeolites. The surfactant (CTAB) promotes the incorporation of Si atoms into the framework and leads to the increase of acid sites. The rod-like SAPO-11 monocrystal with 500 nm can be obtained in the presence of HF. F- ions could contribute to the higher thermal stability of the sample, while they inhibit Si atoms to incorporate into the framework of the zeolite, which causes a significant decrease of acid sites.
In the presence of hexadecyl trimethyl ammonium bromide (CTAB) or fluoride ions (HF), superfine SAPO-11 was obtained via steam-assisted conversion method. The samples were characterized by SEM, XRD, IR, MAS NMR, TPD, TEM, TG-DSC and Nitrogen adsorption-desorption. The introduction of CTAB or HF can not only decrease the particle size, but also control the framework, morphology, pore structure and acid properties of SAPO-11 zeolites. The surfactant (CTAB) promotes the incorporation of Si atoms into the framework and leads to the increase of acid sites. The rod-like SAPO-11 monocrystal with 500 nm can be obtained in the presence of HF. F- ions could contribute to the higher thermal stability of the sample, while they inhibit Si atoms to incorporate into the framework of the zeolite, which causes a significant decrease of acid sites.
2013, 29(3): 571-576
doi: 10.3969/j.issn.1001-4861.2013.00.082
Abstract:
Submicrometer rod-like ZnO was prepared by wet-chemical technique at 70 ℃. The material was characterized by UV-vis spectroscopy (UV-Vis), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. The optimized geometry of crystal violet (CV) was calculated at DFT/B3LYP level with 6-311G* basis set. Meanwhile, the surface-enhanced Raman scattering (SERS) activity of submicrometer rod-like ZnO was investigated using CV as a probe molecular. Results show that the rod-like submicrometer ZnO has high purity and crystallinity, which belongs to the Wurtzite-type structure. The enhancement factor of CV adsorbed on rod-like ZnO is up to 1.2×102, which is attributed to chemical enhancement.
Submicrometer rod-like ZnO was prepared by wet-chemical technique at 70 ℃. The material was characterized by UV-vis spectroscopy (UV-Vis), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. The optimized geometry of crystal violet (CV) was calculated at DFT/B3LYP level with 6-311G* basis set. Meanwhile, the surface-enhanced Raman scattering (SERS) activity of submicrometer rod-like ZnO was investigated using CV as a probe molecular. Results show that the rod-like submicrometer ZnO has high purity and crystallinity, which belongs to the Wurtzite-type structure. The enhancement factor of CV adsorbed on rod-like ZnO is up to 1.2×102, which is attributed to chemical enhancement.
2013, 29(3): 577-582
doi: 10.3969/j.issn.1001-4861.2013.00.046
Abstract:
The Polyethylene Glycol(PEG)stabilized RuB nanoparticles showed an excellent catalytic performance for selective hydrogenation of benzene to cyclohexene. Without ZnSO4, a maximum cyclohexene yield of 29% was obtained. The good performance of this catalyst system is attributed to the great hydrophilic property of RuB nanoparticles caused by PEG.
The Polyethylene Glycol(PEG)stabilized RuB nanoparticles showed an excellent catalytic performance for selective hydrogenation of benzene to cyclohexene. Without ZnSO4, a maximum cyclohexene yield of 29% was obtained. The good performance of this catalyst system is attributed to the great hydrophilic property of RuB nanoparticles caused by PEG.
2013, 29(3): 583-588
doi: 10.3969/j.issn.1001-4861.2013.00.097
Abstract:
By using a Gemini quaternary ammonium as surfactant synthesized in laboratory and adjusting the different pH values, in this study, using the hydrothermal method, the different sheet-like cluster microspheres was self-assembled by Bi2WO6 nano-sheets. This study analyzed and characterized the effect of pH value on synthesis of Bi2WO6 sheet-like cluster microspheres, phase structure, composition, crystal morphology and photoluminescence properties, and explore its possible growth mechanism. The results show that different pH values caused a significant impact in Bi2WO6 sheet-like cluster microspheres phase structure, morphology and photoluminescence properties, when A multi-quaternary ammonium cationic dispersant as structure directing agents in the growth stage of Bi2WO6 Microspheres. With the increasing of pH value, sheet- like clusters Bi2WO6 microspheres showed obvious trend growth in the (131) direction, when pH=5, Bi2WO6 microspheres can reach a maximum luminous intensity.
By using a Gemini quaternary ammonium as surfactant synthesized in laboratory and adjusting the different pH values, in this study, using the hydrothermal method, the different sheet-like cluster microspheres was self-assembled by Bi2WO6 nano-sheets. This study analyzed and characterized the effect of pH value on synthesis of Bi2WO6 sheet-like cluster microspheres, phase structure, composition, crystal morphology and photoluminescence properties, and explore its possible growth mechanism. The results show that different pH values caused a significant impact in Bi2WO6 sheet-like cluster microspheres phase structure, morphology and photoluminescence properties, when A multi-quaternary ammonium cationic dispersant as structure directing agents in the growth stage of Bi2WO6 Microspheres. With the increasing of pH value, sheet- like clusters Bi2WO6 microspheres showed obvious trend growth in the (131) direction, when pH=5, Bi2WO6 microspheres can reach a maximum luminous intensity.
2013, 29(3): 589-594
doi: 10.3969/j.issn.1001-4861.2013.00.081
Abstract:
The two-dimensional coordination polymer, [Mn(NAA)2(H2O)2]n (1) (HNAA=α-naphthylacetic acid) has been synthesized and characterized by single-crystal X- ray diffraction studies, elemental analysis and FTIR spectrum. Structural determination reveals that it crystallizes in monoclinic space group C2/c. Crystal data: a=3.713 3 (5) nm, b=0.625 4(5) nm, c=0.889 7(5) nm; β=99.706 (5)°, Z=4. Each Mn(Ⅱ) atom is six-coordinated with a distorted octahedral geometry. The NAA- anion acts as a μ2- bridge linking Mn(Ⅱ) atoms generating a two-dimensional network with (4, 4) topology, which are further bridged to form three-dimensional supramolecular structure by C-H…O hydrogen bonding and C-H…π interactions. The thermal stability,luminescence property and antibacterial activity of 1 were investigated. CCDC: 847386.
The two-dimensional coordination polymer, [Mn(NAA)2(H2O)2]n (1) (HNAA=α-naphthylacetic acid) has been synthesized and characterized by single-crystal X- ray diffraction studies, elemental analysis and FTIR spectrum. Structural determination reveals that it crystallizes in monoclinic space group C2/c. Crystal data: a=3.713 3 (5) nm, b=0.625 4(5) nm, c=0.889 7(5) nm; β=99.706 (5)°, Z=4. Each Mn(Ⅱ) atom is six-coordinated with a distorted octahedral geometry. The NAA- anion acts as a μ2- bridge linking Mn(Ⅱ) atoms generating a two-dimensional network with (4, 4) topology, which are further bridged to form three-dimensional supramolecular structure by C-H…O hydrogen bonding and C-H…π interactions. The thermal stability,luminescence property and antibacterial activity of 1 were investigated. CCDC: 847386.
2013, 29(3): 595-604
doi: 10.3969/j.issn.1001-4861.2013.00.033
Abstract:
4-(5'-aminonaphtalene-3'-sulfonic acid)azo-(2″-N-(4''', 6'''-dichloro-S-triazine) benzene-5″-(β-sulfatoethyl sulfonyl)-2-methyl anthraquinone (2a), 4-(2'-aminobenzenesulfonic acid)azo-(2″-N-(4''', 6'''-dichloro-S-triazine)-3″-benzensulfonic acid)-2-methyl anthraquinone, 4-(5'-aminonaphtalene-3'-sulfonic acid)azo-(2″-N-(4''', 6'''-dichloro-S-triazine)benzen-5″-(β-sulfatoethyl sulfonyl)-2-methyl anthraquinone and 4-(p-(β-sulfatoethyl sulfonyl) azo-(2″-N-(4''', 6'''-dichloro-S-triazine) naphtalene-5″sulfonic acid)-2-methyl anthraquinone with FeⅢ,CoⅡ metal complexes were prepared and used for determination of mutagenic and teratogenic effects in Ames/Salmonella/Microsome Test and in embryos of rats. 2a-Fe and 2a-Co were not mutagenic for both TA98 and TA100 strains with and without metabolic activator S9mix.
4-(5'-aminonaphtalene-3'-sulfonic acid)azo-(2″-N-(4''', 6'''-dichloro-S-triazine) benzene-5″-(β-sulfatoethyl sulfonyl)-2-methyl anthraquinone (2a), 4-(2'-aminobenzenesulfonic acid)azo-(2″-N-(4''', 6'''-dichloro-S-triazine)-3″-benzensulfonic acid)-2-methyl anthraquinone, 4-(5'-aminonaphtalene-3'-sulfonic acid)azo-(2″-N-(4''', 6'''-dichloro-S-triazine)benzen-5″-(β-sulfatoethyl sulfonyl)-2-methyl anthraquinone and 4-(p-(β-sulfatoethyl sulfonyl) azo-(2″-N-(4''', 6'''-dichloro-S-triazine) naphtalene-5″sulfonic acid)-2-methyl anthraquinone with FeⅢ,CoⅡ metal complexes were prepared and used for determination of mutagenic and teratogenic effects in Ames/Salmonella/Microsome Test and in embryos of rats. 2a-Fe and 2a-Co were not mutagenic for both TA98 and TA100 strains with and without metabolic activator S9mix.
2013, 29(3): 605-612
doi: 10.3969/j.issn.1001-4861.2013.00.102
Abstract:
Bi3.25Sm0.75Ti3O12 (BSmT) nanowires of 40 nm in diameter were synthesized through a one-step hydrothermal process. The BSmT nanowires are of layered perovskites. The results of UV-Visible diffuse reflectance spectra (DRS) demonstrate that the band gap of BSmT nanowires is about 2.67 eV. The BSmT nanowires exhibit higher photocatalytic activity than that of the traditional N doped TiO2 (N-TiO2) and pure bismuth titanate (Bi4Ti3O12, BIT). 92.0% methyl orange (MO) (0.01 mmol·L-1) is decolorized after visible light irradiation for 360 min. The high photocatalytic performance of BSmT photocatalyst could be attributed to the strong visible light absorption and the recombination restraint of the e-/h+ pairs resulting from doping of Sm3+ ions. In addition, after 4 recycles, there is no significant decrease in the photocatalytic activity, indicating that BSmT is a stable photocatalyst for degradation of MO under visible light irradiation.
Bi3.25Sm0.75Ti3O12 (BSmT) nanowires of 40 nm in diameter were synthesized through a one-step hydrothermal process. The BSmT nanowires are of layered perovskites. The results of UV-Visible diffuse reflectance spectra (DRS) demonstrate that the band gap of BSmT nanowires is about 2.67 eV. The BSmT nanowires exhibit higher photocatalytic activity than that of the traditional N doped TiO2 (N-TiO2) and pure bismuth titanate (Bi4Ti3O12, BIT). 92.0% methyl orange (MO) (0.01 mmol·L-1) is decolorized after visible light irradiation for 360 min. The high photocatalytic performance of BSmT photocatalyst could be attributed to the strong visible light absorption and the recombination restraint of the e-/h+ pairs resulting from doping of Sm3+ ions. In addition, after 4 recycles, there is no significant decrease in the photocatalytic activity, indicating that BSmT is a stable photocatalyst for degradation of MO under visible light irradiation.
2013, 29(3): 613-620
doi: 10.3969/j.issn.1001-4861.2013.00.107
Abstract:
The interactions of the Ru(Ⅱ) complex, [Ru(phen)2(Hecip)]2+ (phen=1,10-phenanthroline, Hecip=N-ethyl-4-([1,10]-phenanthroline[5,6-f]imidazol-2-yl)carbazole), with calf thymus DNA (CT DNA) were studied by using absorption spectroscopy, binding stoichiometry, viscosity measurement and photoactivated cleavage. A tight 2:1 complex is formed by the Ru(Ⅱ) polypyridyl complex and CT DNA with a binding constant exceeding 105 mol-1·L and with a binding mode of intercalation. Furthermore, the complex exhibits efficient DNA cleavage activity on UV (365 nm) irradiation via a mechanistic pathway involving formation of singlet oxygen as the reactive species. On the other hand, the cytotoxic activity of the complex was tested by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) method. The complex shows prominent anticancer activity against selected tumor cell lines with IC50 values lower than those of cisplatin. Further flow cytometry experiments show that the cytotoxic Ru(Ⅱ) complex can cause cell cycle arrest in the S phase.
The interactions of the Ru(Ⅱ) complex, [Ru(phen)2(Hecip)]2+ (phen=1,10-phenanthroline, Hecip=N-ethyl-4-([1,10]-phenanthroline[5,6-f]imidazol-2-yl)carbazole), with calf thymus DNA (CT DNA) were studied by using absorption spectroscopy, binding stoichiometry, viscosity measurement and photoactivated cleavage. A tight 2:1 complex is formed by the Ru(Ⅱ) polypyridyl complex and CT DNA with a binding constant exceeding 105 mol-1·L and with a binding mode of intercalation. Furthermore, the complex exhibits efficient DNA cleavage activity on UV (365 nm) irradiation via a mechanistic pathway involving formation of singlet oxygen as the reactive species. On the other hand, the cytotoxic activity of the complex was tested by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) method. The complex shows prominent anticancer activity against selected tumor cell lines with IC50 values lower than those of cisplatin. Further flow cytometry experiments show that the cytotoxic Ru(Ⅱ) complex can cause cell cycle arrest in the S phase.
2013, 29(3): 621-627
doi: 10.3969/j.issn.1001-4861.2013.00.037
Abstract:
This paper reports two metal phosphonates [Mn(2-bppH2)2(H2O)]n (1) and [Cu(2-bppH2)2]·xCH3OH (2) based on 2-(benzoimidazol-2-yl)phenylphosphonic acid (2-bppH3). Compound 1 has a one-dimensional chain structure in which Mn atoms are bridged by O-P-O units to form infinite chains. While compound 2 shows discrete mononuclear structure. Antiferromagnetic interactions are mediated between the MnⅡ ions through the O-P-O bridge in compound 1. CCDC: 913645, 1; 913643, 2.
This paper reports two metal phosphonates [Mn(2-bppH2)2(H2O)]n (1) and [Cu(2-bppH2)2]·xCH3OH (2) based on 2-(benzoimidazol-2-yl)phenylphosphonic acid (2-bppH3). Compound 1 has a one-dimensional chain structure in which Mn atoms are bridged by O-P-O units to form infinite chains. While compound 2 shows discrete mononuclear structure. Antiferromagnetic interactions are mediated between the MnⅡ ions through the O-P-O bridge in compound 1. CCDC: 913645, 1; 913643, 2.
2013, 29(3): 628-634
doi: 10.3969/j.issn.1001-4861.2013.00.069
Abstract:
In order to take advantage of large specific surface area, the nanosheets obtained by delaminating ZnAl layered double hydroxides (ZnAl-LDHs) in formamide were stabilized by cellulose in aqueous solution. The structure, composition and morphology of the resulting nanocomposites of ZnAl-LDHs nanosheets and carboxymethyl cellulose were characterized by XRD, FTIR, SEM, TEM, C, H, and N elemental analysis, ICP and ion chromatograph techniques. In addition, the performance of ZnAl-LDHs nanosheets on phosphorus removal was investigated. The results show that the nanocomposites have high selectivity and adsorption capacity toward phosphate. The selectivity sequences are as follows: H2PO4->SO42->Cl->NO3-. The maximum adsorption capacity could reach 40 mg of P per gram of LDHs approximately.
In order to take advantage of large specific surface area, the nanosheets obtained by delaminating ZnAl layered double hydroxides (ZnAl-LDHs) in formamide were stabilized by cellulose in aqueous solution. The structure, composition and morphology of the resulting nanocomposites of ZnAl-LDHs nanosheets and carboxymethyl cellulose were characterized by XRD, FTIR, SEM, TEM, C, H, and N elemental analysis, ICP and ion chromatograph techniques. In addition, the performance of ZnAl-LDHs nanosheets on phosphorus removal was investigated. The results show that the nanocomposites have high selectivity and adsorption capacity toward phosphate. The selectivity sequences are as follows: H2PO4->SO42->Cl->NO3-. The maximum adsorption capacity could reach 40 mg of P per gram of LDHs approximately.
2013, 29(3): 635-641
doi: 10.3969/j.issn.1001-4861.2013.00.094
Abstract:
Cadmium Sulfide (CdS) nanowires (NWs) were synthesized by templating bionanotubes self-assembled from bis(N-amido-glycylglycine)-1,7-heptane dicarboxylate using cadmium chloride (CdCl2) and sodium sulfide (Na2S) as Cd and S precursors. The-COOH groups from the bionanotube surface act as chelating agents to coordinate Cd2+ ions and facilitate further growth of CdS nanocrystals on the bionanotube. The morphology, structure and composition of CdS embedded bionanowires were characterized by Transmission Electron Microscopy (TEM), High Resolution Transmission Electron Microscopy (HRTEM), Selected Area Electron Diffraction (SAED), UV, steady state Photoluminescence (PL) and Energy-dispersive X-ray spectroscopy (EDS) techniques. The results show that the resulting CdS embedded bionanowires, (4±0.6) μm in length and (400±55) nm in diameter, are coated by CdS nanoparticles with diameter of (5.5±0.3) nm. This work presents an effective direct-growth strategy on biomolecular templates to synthesize monodispersed QD-coated nanowires at room temperature by using coordination between -COOH and Cd2+, which has not accomplished previously by any other non-biotemplating synthetic methods.
Cadmium Sulfide (CdS) nanowires (NWs) were synthesized by templating bionanotubes self-assembled from bis(N-amido-glycylglycine)-1,7-heptane dicarboxylate using cadmium chloride (CdCl2) and sodium sulfide (Na2S) as Cd and S precursors. The-COOH groups from the bionanotube surface act as chelating agents to coordinate Cd2+ ions and facilitate further growth of CdS nanocrystals on the bionanotube. The morphology, structure and composition of CdS embedded bionanowires were characterized by Transmission Electron Microscopy (TEM), High Resolution Transmission Electron Microscopy (HRTEM), Selected Area Electron Diffraction (SAED), UV, steady state Photoluminescence (PL) and Energy-dispersive X-ray spectroscopy (EDS) techniques. The results show that the resulting CdS embedded bionanowires, (4±0.6) μm in length and (400±55) nm in diameter, are coated by CdS nanoparticles with diameter of (5.5±0.3) nm. This work presents an effective direct-growth strategy on biomolecular templates to synthesize monodispersed QD-coated nanowires at room temperature by using coordination between -COOH and Cd2+, which has not accomplished previously by any other non-biotemplating synthetic methods.
2013, 29(3): 642-648
doi: 10.3969/j.issn.1001-4861.2013.00.115
Abstract:
A coordination polymer [Ni(Pht)(bbim-4)]n (Pht=o-phthalate acid anion,bbim-4=1, 1'-(1, 4-butanediyl)bis(imidazole) was synthesized by hydrothermal reaction and characterized by elemental analysis, powder X-ray diffraction, TGA and X-ray single crystal diffraction. The crystal belongs to monoclinic system, space group C2/c. Coordination polymer [Ni(Pht)(bbim-4)]n is a three-dimensional porous coordination polymer with triangular channels. The coordination polymer shows an overall ferromagnetic behavior. Gas sorption studies suggest that the coordination polymer has selectivity in adsorption of N2 and CO2 gas. CCDC: 818068.
A coordination polymer [Ni(Pht)(bbim-4)]n (Pht=o-phthalate acid anion,bbim-4=1, 1'-(1, 4-butanediyl)bis(imidazole) was synthesized by hydrothermal reaction and characterized by elemental analysis, powder X-ray diffraction, TGA and X-ray single crystal diffraction. The crystal belongs to monoclinic system, space group C2/c. Coordination polymer [Ni(Pht)(bbim-4)]n is a three-dimensional porous coordination polymer with triangular channels. The coordination polymer shows an overall ferromagnetic behavior. Gas sorption studies suggest that the coordination polymer has selectivity in adsorption of N2 and CO2 gas. CCDC: 818068.
2013, 29(3): 649-653
doi: 10.3969/j.issn.1001-4861.2013.00.080
Abstract:
A new centrosymmetric hexanuclear iron(Ⅲ) complex [NaFe6L6(MeO)6]Cl has been synthesized from the tridentate Schiff base ligand 2-[1-(2-hydroxyethylimino)ethyl]phenol (H2L) and sodium dicyanamide with iron(Ⅲ) chloride in methanol. The complex was characterized by elemental analyses, infrared spectroscopy, and X-ray single crystal determination. The crystal of the complex crystallizes as triclinic space group P1, with a=1.162 5(2) nm, b=1.396 4(2) nm, c=1.504 2(2) nm, α=66.154(7)°, β=68.809(7)°, γ=73.296(7)°, V=2.053 6(5) nm3, Z=1, R1=0.059 3, wR2=0.156 4. Thermal stability and antimicrobial activity of the complex were studied. CCDC: 889111.
A new centrosymmetric hexanuclear iron(Ⅲ) complex [NaFe6L6(MeO)6]Cl has been synthesized from the tridentate Schiff base ligand 2-[1-(2-hydroxyethylimino)ethyl]phenol (H2L) and sodium dicyanamide with iron(Ⅲ) chloride in methanol. The complex was characterized by elemental analyses, infrared spectroscopy, and X-ray single crystal determination. The crystal of the complex crystallizes as triclinic space group P1, with a=1.162 5(2) nm, b=1.396 4(2) nm, c=1.504 2(2) nm, α=66.154(7)°, β=68.809(7)°, γ=73.296(7)°, V=2.053 6(5) nm3, Z=1, R1=0.059 3, wR2=0.156 4. Thermal stability and antimicrobial activity of the complex were studied. CCDC: 889111.
2013, 29(3): 654-658
doi: 10.3969/j.issn.1001-4861.2013.00.099
Abstract:
The title complex has been synthesized with 4'-(p-methoxylphenyl)-2,2':6',2″-terpyridine (meophtpy) and zinc sulfate heptahydrate (NiSO4·7H2O), sodium perchlorate (NaClO4) with solvothermal method and characterized by IR, UV and X-ray diffraction. It crystallizes in monoclinic space group P21/c. The crystal structure shows that the nickel atom is coordinated with six nitrogen atoms from two terpyridine molecules, forming six-coordinated octahedral coordination geometry. There are three abosrpsion peaks 235.5, 278.5 and 342 nm which are the typical absorption spectrum of terpyridine complexes. The fluerescence are peaked at 396 nm. Following a cyclic voltammetry measurement a typical reduction peak of Ni2+ at -0.82 V was found. CCDC: 899537.
The title complex has been synthesized with 4'-(p-methoxylphenyl)-2,2':6',2″-terpyridine (meophtpy) and zinc sulfate heptahydrate (NiSO4·7H2O), sodium perchlorate (NaClO4) with solvothermal method and characterized by IR, UV and X-ray diffraction. It crystallizes in monoclinic space group P21/c. The crystal structure shows that the nickel atom is coordinated with six nitrogen atoms from two terpyridine molecules, forming six-coordinated octahedral coordination geometry. There are three abosrpsion peaks 235.5, 278.5 and 342 nm which are the typical absorption spectrum of terpyridine complexes. The fluerescence are peaked at 396 nm. Following a cyclic voltammetry measurement a typical reduction peak of Ni2+ at -0.82 V was found. CCDC: 899537.
