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2013 Volume 29 Issue 10
2013, 29(10): 2021-2026
doi: 10.3969/j.issn.1001-4861.2013.00.335
Abstract:
By using hydrothermal method, a cobalt complex, namely, [Co2(L)(Bipy)2]n, (1), was synthesized based on flexible 1,3-bis[3,5-(dicarboxylate)phenoxy]-2-hydroxypropane(H4L) and 4,4'-bipyridine(Bipy). The complex 1 was characterized by infra-red spectrum (IR), UV-Vis spectrum, thermo-gravimetric analysis (TGA), single crystal X-ray diffraction, powder X-ray diffraction and elemental analysis. Complex 1 crystalizes in monoclinic system, space group C2/c. In complex 1, two six-coordinated cobalt atoms were connected by two bidentate carboxylic groups, forming an octahedral dimetallic cluster, which can be considered as a 6-connected node to connect four L ligand molecules and two other dimetallic clusters. The flexible tetracarboxylate ligand L can be considered as a tetrahedral 4-connected node to connect four dimetallic clusters. The two parallel Bipy molecules bridging two dimetallic clusters are transformed into edge during simplification. Thus, the framework of 1 features a sqc422 net. CCDC: 947285.
By using hydrothermal method, a cobalt complex, namely, [Co2(L)(Bipy)2]n, (1), was synthesized based on flexible 1,3-bis[3,5-(dicarboxylate)phenoxy]-2-hydroxypropane(H4L) and 4,4'-bipyridine(Bipy). The complex 1 was characterized by infra-red spectrum (IR), UV-Vis spectrum, thermo-gravimetric analysis (TGA), single crystal X-ray diffraction, powder X-ray diffraction and elemental analysis. Complex 1 crystalizes in monoclinic system, space group C2/c. In complex 1, two six-coordinated cobalt atoms were connected by two bidentate carboxylic groups, forming an octahedral dimetallic cluster, which can be considered as a 6-connected node to connect four L ligand molecules and two other dimetallic clusters. The flexible tetracarboxylate ligand L can be considered as a tetrahedral 4-connected node to connect four dimetallic clusters. The two parallel Bipy molecules bridging two dimetallic clusters are transformed into edge during simplification. Thus, the framework of 1 features a sqc422 net. CCDC: 947285.
2013, 29(10): 2027-2033
doi: 10.3969/j.issn.1001-4861.2013.00.323
Abstract:
GaN micro/nanostructures were synthesized by chemical vapor deposition method (CVD) on Si (100) substrate with catalyst Ni, Ga and NH3 as raw materials. Effect of N2 flow rate on the morphology as well as optical and electrical properties of GaNwere researched. The morphology, structure, composition, optical and electrical properties were characterized by Field emission scanning electron microscopy (SEM), Transmission electron microscopy(TEM), X-ray diffraction (XRD), Energy dispersive X-ray spectroscopy (EDS), Photoluminescence (PL) and Hall effect measurement system (HMS-3000). The results indicate that with the increase of N2 flow rate, the morphology of GaNevolved from microrods to vermicular-like wires and then to smooth nanowires. All samples are hexagonal wurtzite, and show near-band-edge UVemission peaks of 383 nm and blue light emission peaks of about 470 nm. Hall test results show that all samples are p-type. Furthermore, the morphology evolution mechanisms of GaNare analyzed.
GaN micro/nanostructures were synthesized by chemical vapor deposition method (CVD) on Si (100) substrate with catalyst Ni, Ga and NH3 as raw materials. Effect of N2 flow rate on the morphology as well as optical and electrical properties of GaNwere researched. The morphology, structure, composition, optical and electrical properties were characterized by Field emission scanning electron microscopy (SEM), Transmission electron microscopy(TEM), X-ray diffraction (XRD), Energy dispersive X-ray spectroscopy (EDS), Photoluminescence (PL) and Hall effect measurement system (HMS-3000). The results indicate that with the increase of N2 flow rate, the morphology of GaNevolved from microrods to vermicular-like wires and then to smooth nanowires. All samples are hexagonal wurtzite, and show near-band-edge UVemission peaks of 383 nm and blue light emission peaks of about 470 nm. Hall test results show that all samples are p-type. Furthermore, the morphology evolution mechanisms of GaNare analyzed.
2013, 29(10): 2034-2042
doi: 10.3969/j.issn.1001-4861.2013.00.280
Abstract:
The porous carbon nanotubes (CNTs)/activated carbon composite beads were modified by L-tryptophan using epichlorohydrin coupling method. The composite beads were characterized by SEM, N2 adsorption, FTIR, TGAand XPSetc. Then these composite beads were applied to adsorb low density lipoprotein (LDL) by static adsorption experiment in vitro. The results show that the composite beads could be modified by L-tryptophan using epichlorohydrin coupling method. With the increase CNTs mass ratio, the adsorption capacity of LDLincrease. When CNTs ratio is 45wt%, the adsorption amount of LDLreaches 4.623 mg·g-1, is 2.3 times as great as that of beads without CNTs. These should be ascribed to the highly developed 20～100 nm porous structures and the increase of L-tryptophan amount on the composite beads mainly brought about by CNTs, enhancing the LDLadsorption ability onto the composite beads greatly. So the composite beads have good prospects as LDLadsorbent in hemoperfusion.
The porous carbon nanotubes (CNTs)/activated carbon composite beads were modified by L-tryptophan using epichlorohydrin coupling method. The composite beads were characterized by SEM, N2 adsorption, FTIR, TGAand XPSetc. Then these composite beads were applied to adsorb low density lipoprotein (LDL) by static adsorption experiment in vitro. The results show that the composite beads could be modified by L-tryptophan using epichlorohydrin coupling method. With the increase CNTs mass ratio, the adsorption capacity of LDLincrease. When CNTs ratio is 45wt%, the adsorption amount of LDLreaches 4.623 mg·g-1, is 2.3 times as great as that of beads without CNTs. These should be ascribed to the highly developed 20～100 nm porous structures and the increase of L-tryptophan amount on the composite beads mainly brought about by CNTs, enhancing the LDLadsorption ability onto the composite beads greatly. So the composite beads have good prospects as LDLadsorbent in hemoperfusion.
2013, 29(10): 2043-2048
doi: 10.3969/j.issn.1001-4861.2013.00.332
Abstract:
Aseparable magnetic photocatalyst (Fe3O4/C/TiO2) was prepared by a hydrothermal reaction with the reaction of FeCl3, glucose and tetrabutyltitanate. The catalyst Fe3O4/C/TiO2 was characterized in terms of particle size, morphology and phase by transmission electron microscopy (TEM), energy dispersive X-ray (EDX) spectrometry, vibration sample magnetometry (VSM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The catalytic activities and mechanism were evaluated by degradation of 2,4,6-trichlorophenol (TCP) aqueous solution. The reaction mechanism was investigated by the fluorescence technique. The results indicate that the catalyst has high degradation abilities and can be easily separated and reused by an external magnetic field. TCPcan be effectively degraded by 97.9% in the use of 1 g·L-1 Fe3O4/C/TiO2 under 18 W UVlight within50 min. Adegradation rate of 95.1% can be maintained after 6 cycles. The hydroxyl radicals (OH) have been detected in the reaction.
Aseparable magnetic photocatalyst (Fe3O4/C/TiO2) was prepared by a hydrothermal reaction with the reaction of FeCl3, glucose and tetrabutyltitanate. The catalyst Fe3O4/C/TiO2 was characterized in terms of particle size, morphology and phase by transmission electron microscopy (TEM), energy dispersive X-ray (EDX) spectrometry, vibration sample magnetometry (VSM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The catalytic activities and mechanism were evaluated by degradation of 2,4,6-trichlorophenol (TCP) aqueous solution. The reaction mechanism was investigated by the fluorescence technique. The results indicate that the catalyst has high degradation abilities and can be easily separated and reused by an external magnetic field. TCPcan be effectively degraded by 97.9% in the use of 1 g·L-1 Fe3O4/C/TiO2 under 18 W UVlight within50 min. Adegradation rate of 95.1% can be maintained after 6 cycles. The hydroxyl radicals (OH) have been detected in the reaction.
2013, 29(10): 2049-2056
doi: 10.3969/j.issn.1001-4861.2013.00.287
Abstract:
Hollow mesoporous aluminosilicate spheres (HMAS) with middle strong acidity have been successfully synthesized by a facile hydrothermal treatment on mesoporous silica spheres (MSS) in zeolite precursor solution. The as-prepared materials were characterized by TEM, SEM, XRD, N2 adsorption-desorption, 27Al NMR and NH3-TPD. The results showed that the hollowing process was associated with a progressive mass redistribution and changes of pores structures. The surfactant cetyltrimethylammonium bromide (CTAB) located in the pores of MSS protected the mesoporous silica spheres from dissolving into strongly basic zeolite precursor solution and acted as the template for mesoporous shell. Under the templating function of CTAB, primary zeolite units were introduced into the mesopore walls of HMAS. The obtained material HMAS had moderate acid strength. Catalytic tests showed that the catalysts exhibited high catalytic activity compared with the MSS and Hβ zeolite for catalytic cracking of 1, 3, 5-triisopropylbenzene.
Hollow mesoporous aluminosilicate spheres (HMAS) with middle strong acidity have been successfully synthesized by a facile hydrothermal treatment on mesoporous silica spheres (MSS) in zeolite precursor solution. The as-prepared materials were characterized by TEM, SEM, XRD, N2 adsorption-desorption, 27Al NMR and NH3-TPD. The results showed that the hollowing process was associated with a progressive mass redistribution and changes of pores structures. The surfactant cetyltrimethylammonium bromide (CTAB) located in the pores of MSS protected the mesoporous silica spheres from dissolving into strongly basic zeolite precursor solution and acted as the template for mesoporous shell. Under the templating function of CTAB, primary zeolite units were introduced into the mesopore walls of HMAS. The obtained material HMAS had moderate acid strength. Catalytic tests showed that the catalysts exhibited high catalytic activity compared with the MSS and Hβ zeolite for catalytic cracking of 1, 3, 5-triisopropylbenzene.
2013, 29(10): 2057-2064
doi: 10.3969/j.issn.1001-4861.2013.00.330
Abstract:
The Bi2WO6/g-C3N4 composite photocatalysts were successfully synthesized by implanting Bi2WO6 nanoparticles into the interlayer and surface of g-C3N4 using a solvothermal method. The prepared samples were characterized by XRD, SEM, TEM, UV-Vis, BET and photogradation of RhBfor comprehensive structural, morphological, specific surface area and visible-light properties. This results show the interlayer structure of g-C3N4 was partially peeled and formed Bi2WO6/g-C3N4 photocatalyst. The 60 wt% Bi2WO6/g-C3N4 photocatalysts possess enhanced photocatalytic activity than the single phase Bi2WO6 and g-C3N4 under visible light, which can be ascribe to its wide visible light reponse, large surface area and high quantum efficiency. In addition, the Bi2WO6/g-C3N4 composite is not only highly stable but also easy to be collected.
The Bi2WO6/g-C3N4 composite photocatalysts were successfully synthesized by implanting Bi2WO6 nanoparticles into the interlayer and surface of g-C3N4 using a solvothermal method. The prepared samples were characterized by XRD, SEM, TEM, UV-Vis, BET and photogradation of RhBfor comprehensive structural, morphological, specific surface area and visible-light properties. This results show the interlayer structure of g-C3N4 was partially peeled and formed Bi2WO6/g-C3N4 photocatalyst. The 60 wt% Bi2WO6/g-C3N4 photocatalysts possess enhanced photocatalytic activity than the single phase Bi2WO6 and g-C3N4 under visible light, which can be ascribe to its wide visible light reponse, large surface area and high quantum efficiency. In addition, the Bi2WO6/g-C3N4 composite is not only highly stable but also easy to be collected.
2013, 29(10): 2065-2070
doi: 10.3969/j.issn.1001-4861.2013.00.324
Abstract:
Alarge-sized SiO2 macroporous material modified by fixing Cu2+ on its surface was employed as the support for the immobilization of laccase. The effects of immobilization time, pHvalue and the amount of enzyme provided on the immobilization were investigated, and the activity and stability of the immobilized enzyme were also studied. The results show that the adsorption equilibrium is reached after about 5 hours. The optimum conditions for immobilization of laccase were at the immobilization pHof 4.5 and the ratio of enzyme to support of 5 mg·g-1, and in this case, the activity recovery of the immobilized laccase is 100.4%. Comparing with the free laccase, both the optimum working pHand temperature of the immobilized laccase are higher and the ranges are wider. The experiments show that the immobilization improves the pHstability and the thermal stability of laccase significantly. The Km of the immobilized laccase is higher than the free laccase's. The immobilized laccase has good operational stability, the remained activity is 72.7% after 10 times of reaction with the substrate.
Alarge-sized SiO2 macroporous material modified by fixing Cu2+ on its surface was employed as the support for the immobilization of laccase. The effects of immobilization time, pHvalue and the amount of enzyme provided on the immobilization were investigated, and the activity and stability of the immobilized enzyme were also studied. The results show that the adsorption equilibrium is reached after about 5 hours. The optimum conditions for immobilization of laccase were at the immobilization pHof 4.5 and the ratio of enzyme to support of 5 mg·g-1, and in this case, the activity recovery of the immobilized laccase is 100.4%. Comparing with the free laccase, both the optimum working pHand temperature of the immobilized laccase are higher and the ranges are wider. The experiments show that the immobilization improves the pHstability and the thermal stability of laccase significantly. The Km of the immobilized laccase is higher than the free laccase's. The immobilized laccase has good operational stability, the remained activity is 72.7% after 10 times of reaction with the substrate.
2013, 29(10): 2071-2078
doi: 10.3969/j.issn.1001-4861.2013.00.325
Abstract:
Aiming at the simplification of synthesis routes and the improvement of photoluminescence quantum yields (PL QYs), a facile and fast method has been developed to synthesize CdTe quantum dots (QDs) precursor in aqueous phase by sonoelectrochemistry without the protection of N2. The high qualities, water-soluble, near-infrared-emitting CdTe QDs were obtained by refluxing of the precursors in oil bath. The morphology, structure and composition of the products were investigated by HRTEMand XRD. The influences of sonoelectrochemical and refluxing parameters on the PLproperties of products were studied. By adjusting the current pulse width, reaction time and reaction temperature, the size- and morphology-controlled CdTe QDs precursors were obtained. CdTe QDs with different emission wavelengths were obtained by followed refluxing. The as-prepared QDs with near-infrared emission of 602 nm were used in the labeling of Hela cell and imaging by confocal laser scanning microscopy (CLSM). Compared with traditional synthesis, sonoelectrochemical route is facile and controllable in the synthesis for water-soluble high-quality QDs, which extends its application in the preparation of nanomaterials.
Aiming at the simplification of synthesis routes and the improvement of photoluminescence quantum yields (PL QYs), a facile and fast method has been developed to synthesize CdTe quantum dots (QDs) precursor in aqueous phase by sonoelectrochemistry without the protection of N2. The high qualities, water-soluble, near-infrared-emitting CdTe QDs were obtained by refluxing of the precursors in oil bath. The morphology, structure and composition of the products were investigated by HRTEMand XRD. The influences of sonoelectrochemical and refluxing parameters on the PLproperties of products were studied. By adjusting the current pulse width, reaction time and reaction temperature, the size- and morphology-controlled CdTe QDs precursors were obtained. CdTe QDs with different emission wavelengths were obtained by followed refluxing. The as-prepared QDs with near-infrared emission of 602 nm were used in the labeling of Hela cell and imaging by confocal laser scanning microscopy (CLSM). Compared with traditional synthesis, sonoelectrochemical route is facile and controllable in the synthesis for water-soluble high-quality QDs, which extends its application in the preparation of nanomaterials.
2013, 29(10): 2079-2084
doi: 10.3969/j.issn.1001-4861.2013.00.336
Abstract:
The mononuclear containing N-donor ligand Ni(Ⅱ) complex [Ni(py)3(H2O)3](1,5-nds) (py=pyridine, 1,5-nds=1,5-naphthalene-disulfonate anion) was synthesized by slow evaporation method in water. It was characterized by X-ray crystal diffraction, IR, thermal analysis, UV-Vis spectroscopy, etc. The characterization results of X-ray single crystal diffraction show that the crystal of the complex crystallized in monoclinic system with space group C2/c. The unit cell parameters include a=1.56946(17) nm, b=1.21995(12) nm, c=1.45471(16) nm, β=14.5471(16)°, V=2.7651(5) nm3, Z=4. The magnetic and fluorescent properties of the complex were studied. CCDC: 947286.
The mononuclear containing N-donor ligand Ni(Ⅱ) complex [Ni(py)3(H2O)3](1,5-nds) (py=pyridine, 1,5-nds=1,5-naphthalene-disulfonate anion) was synthesized by slow evaporation method in water. It was characterized by X-ray crystal diffraction, IR, thermal analysis, UV-Vis spectroscopy, etc. The characterization results of X-ray single crystal diffraction show that the crystal of the complex crystallized in monoclinic system with space group C2/c. The unit cell parameters include a=1.56946(17) nm, b=1.21995(12) nm, c=1.45471(16) nm, β=14.5471(16)°, V=2.7651(5) nm3, Z=4. The magnetic and fluorescent properties of the complex were studied. CCDC: 947286.
2013, 29(10): 2085-2090
doi: 10.3969/j.issn.1001-4861.2013.00.298
Abstract:
Reaction of L-O-Phosphoserine (H2OPSer) and 1,10-phenanthroline (phen) and Cu(CH3COO)2·H2Oin water-ethanol at ambient temperature afforded the remarkably copper complex [Cu(OPSer)(phen)(H2O)]·3H2O(1). The structure has been determined by single-crystal X-ray diffraction analysis and further characterized by infrared spectra (IR), elemental analysis, thermal analysis and magnetic measurements. The chiral copper(Ⅱ) mononuclear complex self-assembled via intermolecular hydrogen bonding interactions into 3Dsupramolecular network and was further consolidated by the π-π stacking interactions. The magnetic susceptibilities (1.8～300 K) indicated that the monnuclear(Ⅱ) cores were ferromanetic coupling (g=2.07,zJ'=0.044). CCDC: 760116.
Reaction of L-O-Phosphoserine (H2OPSer) and 1,10-phenanthroline (phen) and Cu(CH3COO)2·H2Oin water-ethanol at ambient temperature afforded the remarkably copper complex [Cu(OPSer)(phen)(H2O)]·3H2O(1). The structure has been determined by single-crystal X-ray diffraction analysis and further characterized by infrared spectra (IR), elemental analysis, thermal analysis and magnetic measurements. The chiral copper(Ⅱ) mononuclear complex self-assembled via intermolecular hydrogen bonding interactions into 3Dsupramolecular network and was further consolidated by the π-π stacking interactions. The magnetic susceptibilities (1.8～300 K) indicated that the monnuclear(Ⅱ) cores were ferromanetic coupling (g=2.07,zJ'=0.044). CCDC: 760116.
2013, 29(10): 2091-2098
doi: 10.3969/j.issn.1001-4861.2013.00.245
Abstract:
The particle, rod, and spherical flower-like nano-ZnO with the uniform morphology and size were prepared through a simple direct precipitation method and hydrothermal method. Then nano-ZnO was modified by the silane coupling agent anilino-methyl-triethoxysilane (KH-42) (m-ZnO), and the nanocomposites consisted of m-ZnOand polyaniline (m-ZnO@PANI) were synthesized by Pickering emulsion polymerization method. XRD, SEM, HRTEM, FTIR, UV-Vis, TGwere used to characterize the shape, composition and structure of the nano-ZnO and m-ZnO@PANI nanocomposite. The photocatalytic activity of m-ZnO@PANI nanocomposites under UV-vis and visible light irradiation was evaluated by using nanocomposites as photocatalysts to degrade methylene blue (MB) dye molecules in aqueous solution. The results indicate that the nanocomposites have strong absorption of UVand visible light and good photocatalytic efficiency under UV-Vis and visible light irradiation. The photocatalytic efficiency of the rod nanocomposite is the best among them. The photodegradation rates under UV-Vis irradiation and visible light irradiation are 98.2% and 97.1% respectively. Furthermore, the recycled photodegradation efficiency of nanocomposite is stable and the second cycle photodegradation rate under UV-Vis irradiation was 96.0%.
The particle, rod, and spherical flower-like nano-ZnO with the uniform morphology and size were prepared through a simple direct precipitation method and hydrothermal method. Then nano-ZnO was modified by the silane coupling agent anilino-methyl-triethoxysilane (KH-42) (m-ZnO), and the nanocomposites consisted of m-ZnOand polyaniline (m-ZnO@PANI) were synthesized by Pickering emulsion polymerization method. XRD, SEM, HRTEM, FTIR, UV-Vis, TGwere used to characterize the shape, composition and structure of the nano-ZnO and m-ZnO@PANI nanocomposite. The photocatalytic activity of m-ZnO@PANI nanocomposites under UV-vis and visible light irradiation was evaluated by using nanocomposites as photocatalysts to degrade methylene blue (MB) dye molecules in aqueous solution. The results indicate that the nanocomposites have strong absorption of UVand visible light and good photocatalytic efficiency under UV-Vis and visible light irradiation. The photocatalytic efficiency of the rod nanocomposite is the best among them. The photodegradation rates under UV-Vis irradiation and visible light irradiation are 98.2% and 97.1% respectively. Furthermore, the recycled photodegradation efficiency of nanocomposite is stable and the second cycle photodegradation rate under UV-Vis irradiation was 96.0%.
2013, 29(10): 2099-2104
doi: 10.3969/j.issn.1001-4861.2013.00.263
Abstract:
The tricyclohexyltin R-mandeliate was synthesized by the reaction of the tricyclohexyltin hydroxide with the R-mandelic acid. Its structure has been determined by X-ray single crystal diffraction. The crystal belongs to orthorhombic with space group P21212 a=0.80641(4) nm, b=1.76868(9) nm, c=1.83479(8) nm, V=2.6169(2) nm3, Z=4, Dc=1.318 g·cm-3, μ(Mo Kα)=9.98 cm-1, F(000)=1080, R1=0.0390, wR2=0.1039. The tin atom has a distorted tetrahedral geometry.The study on title complex has been performed,with quantum chemistry calculation by means of G03Wpackage and taking Lanl2dz basis set. The stabilities of the complex,the orbital energies and composition characteristics of some frontier molecular orbitals have been investigated. The properties of thermogravimetric analysis and photoluminescent behavior and electrochemical of the complex have also been discussed.
The tricyclohexyltin R-mandeliate was synthesized by the reaction of the tricyclohexyltin hydroxide with the R-mandelic acid. Its structure has been determined by X-ray single crystal diffraction. The crystal belongs to orthorhombic with space group P21212 a=0.80641(4) nm, b=1.76868(9) nm, c=1.83479(8) nm, V=2.6169(2) nm3, Z=4, Dc=1.318 g·cm-3, μ(Mo Kα)=9.98 cm-1, F(000)=1080, R1=0.0390, wR2=0.1039. The tin atom has a distorted tetrahedral geometry.The study on title complex has been performed,with quantum chemistry calculation by means of G03Wpackage and taking Lanl2dz basis set. The stabilities of the complex,the orbital energies and composition characteristics of some frontier molecular orbitals have been investigated. The properties of thermogravimetric analysis and photoluminescent behavior and electrochemical of the complex have also been discussed.
2013, 29(10): 2105-2109
doi: 10.3969/j.issn.1001-4861.2013.00.328
Abstract:
Graphite oxide was synthesized via Hummers method with flake graphite as raw material. After centrifugation and washing to clean out the remnant slat, ethylenediamine (EDA) was added into the dispersion to react with graphene oxides giving rise to functional graphene sheets (FGS). The dried FGScan interact with microwaves strongly, producing superheating which results in decomposing the grafted EDAmolecules and in-situ doping graphene sheets. The morphology, structure, and components of the as-produced graphene were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), energy dispersion spectrum (EDS). The results showed that nitrogen-doped graphene sheets (NGS) can be successfully synthesized via this strategy. The synthesized nitrogen-doped graphene was transparent.
Graphite oxide was synthesized via Hummers method with flake graphite as raw material. After centrifugation and washing to clean out the remnant slat, ethylenediamine (EDA) was added into the dispersion to react with graphene oxides giving rise to functional graphene sheets (FGS). The dried FGScan interact with microwaves strongly, producing superheating which results in decomposing the grafted EDAmolecules and in-situ doping graphene sheets. The morphology, structure, and components of the as-produced graphene were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), energy dispersion spectrum (EDS). The results showed that nitrogen-doped graphene sheets (NGS) can be successfully synthesized via this strategy. The synthesized nitrogen-doped graphene was transparent.
Solvothermal Synthesis of Fe3O4 Nanospheres and Study on the Catalytic Degradation of Xylenol Orange
2013, 29(10): 2110-2118
doi: 10.3969/j.issn.1001-4861.2013.00.267
Abstract:
This paper reports a facile one-pot solvothermal approach for the preparation of 200nm-size Fe3O4 nanospheres with uniform morphology and monodispersity at 160 ℃. During this preparation process, FeCl3·6H2O was used as a single iron source, 1, 2-propylene glycol as solvent and reducing agent, urea as a homogeneous precipitant and maleic acid as an additive. The as-prepared Fe3O4 nanospheres not only had high magnetization saturation value and but also displayed high catalytic activity during the process of xylenol orange (XO) being oxidized degradation by hydrogen peroxide (H2O2). The measurement of UV-Vis spectra indicated that the decolorization rate of xylenol orange was only 6.2% with the oxidation of hydrogen peroxide without Fe3O4 catalyst. However, when Fe3O4 nanospheres were added to the solution, they showed excellent catalytic activity and the decolorization rate of XOcould be increased to 100% within 1h. The experiment also revealed that Fe3O4 nanospheres remained high catalytic activity and stability of material structure after recycling catalyzing of 10 times.
This paper reports a facile one-pot solvothermal approach for the preparation of 200nm-size Fe3O4 nanospheres with uniform morphology and monodispersity at 160 ℃. During this preparation process, FeCl3·6H2O was used as a single iron source, 1, 2-propylene glycol as solvent and reducing agent, urea as a homogeneous precipitant and maleic acid as an additive. The as-prepared Fe3O4 nanospheres not only had high magnetization saturation value and but also displayed high catalytic activity during the process of xylenol orange (XO) being oxidized degradation by hydrogen peroxide (H2O2). The measurement of UV-Vis spectra indicated that the decolorization rate of xylenol orange was only 6.2% with the oxidation of hydrogen peroxide without Fe3O4 catalyst. However, when Fe3O4 nanospheres were added to the solution, they showed excellent catalytic activity and the decolorization rate of XOcould be increased to 100% within 1h. The experiment also revealed that Fe3O4 nanospheres remained high catalytic activity and stability of material structure after recycling catalyzing of 10 times.
2013, 29(10): 2119-2125
doi: 10.3969/j.issn.1001-4861.2013.00.279
Abstract:
The results show that all alloys are composed of V-based solid solution with body-centered-cube (BCC) structure and C14 Laves phase with hexagonal structure. The addition of Bincreases the discharge capacity of Ti0.26Zr0.07V0.24Mn0.1Ni0.33 alloy electrode and Ti0.26Zr0.07V0.24Mn0.1Ni0.33B0.1 alloy delivers the discharge capacity of 476.7 mAh·g-1at discharge current of 60 mA·g-1. The addition of Bdecreases the high-rate discharge ability of the alloy electrode in some extent. EISindicates that addition of Bdecreases the dynamic performance, which makes the charge transfer resistance (Rct) increases and the exchange current density (I0) decreases markedly. Considerable improvement in the high-temperature dischargeability is observed by addition of B, and the discharge capacity is up to 525.6 mAh·g-1 at 343 Kfor Ti0.26Zr0.07V0.24Mn0.1Ni0.33B0.025 alloy electrode.
The results show that all alloys are composed of V-based solid solution with body-centered-cube (BCC) structure and C14 Laves phase with hexagonal structure. The addition of Bincreases the discharge capacity of Ti0.26Zr0.07V0.24Mn0.1Ni0.33 alloy electrode and Ti0.26Zr0.07V0.24Mn0.1Ni0.33B0.1 alloy delivers the discharge capacity of 476.7 mAh·g-1at discharge current of 60 mA·g-1. The addition of Bdecreases the high-rate discharge ability of the alloy electrode in some extent. EISindicates that addition of Bdecreases the dynamic performance, which makes the charge transfer resistance (Rct) increases and the exchange current density (I0) decreases markedly. Considerable improvement in the high-temperature dischargeability is observed by addition of B, and the discharge capacity is up to 525.6 mAh·g-1 at 343 Kfor Ti0.26Zr0.07V0.24Mn0.1Ni0.33B0.025 alloy electrode.
2013, 29(10): 2126-2132
doi: 10.3969/j.issn.1001-4861.2013.00.251
Abstract:
TiO2 nanorod arrays were synthesized through the one-step hydrothermal process. The influence of deionized water to the morphology of nanorod arrays instead of absolute ethyl alcohol as precursor was also investigated. The results showed that a layer of TiO2 microsphere can be synthesized on the top of the nanorod arrays, which serve as the basic unit for the growth of microsphere and finally result in complex TiO2 nanorod arrays film. The XRDand TEMresults suggeste that the nanorod arrays film is consisted of single-crystalline TiO2with tetragonal rutile phase structures. After the assembling of dye sensitized solar cells with the as-synthesized samples, the open-circuit voltage and short-circuit current density and fill factor were measured out as Voc=0.63 V, Jsc=10.9 mA·cm-2 and FF=56.3%, respectively. The energy conversion efficiency (η) is approximately 4.1%.
TiO2 nanorod arrays were synthesized through the one-step hydrothermal process. The influence of deionized water to the morphology of nanorod arrays instead of absolute ethyl alcohol as precursor was also investigated. The results showed that a layer of TiO2 microsphere can be synthesized on the top of the nanorod arrays, which serve as the basic unit for the growth of microsphere and finally result in complex TiO2 nanorod arrays film. The XRDand TEMresults suggeste that the nanorod arrays film is consisted of single-crystalline TiO2with tetragonal rutile phase structures. After the assembling of dye sensitized solar cells with the as-synthesized samples, the open-circuit voltage and short-circuit current density and fill factor were measured out as Voc=0.63 V, Jsc=10.9 mA·cm-2 and FF=56.3%, respectively. The energy conversion efficiency (η) is approximately 4.1%.
2013, 29(10): 2133-2139
doi: 10.3969/j.issn.1001-4861.2013.00.238
Abstract:
Using tetrabutyl orthotitanate as Ti source, hydrofluoric acid as Fsource and ethanol as solvent, well crystallized anatase-phase F-modified TiO2 hollow microspheres have been synthesized via a solvothermal process. The structure and properties of the resulting samples were characterized by XRD, SEM, FTIR, XPS. The results indicated that the fluorizated TiO2 hollow microspheres had an anatase phase, the fluorine atoms were mainly distributed on the surface of TiO2, and existed in forms of chemical-adsorption. Hollow anatase TiO2 microspheres were achieved by Ostwald ripening under solvothermal conditions. Compared to pure titania, the fluorizated TiO2 hollow microspheres showed a much higher degradation efficiency, and degradation rate of which can be up to 98% during the photodegradation of methyl orange with the initial concentration of 20 mg·L-1 for 30 minutes. The mechanism for the great improvement for photocatalytic activity can be attributed to the unique structure of hollow microsphere and the fluorine modification, because the strong electron withdrawing ability of the surface ≡Ti-Fgroups reduces the recombination of photogenerated electrons and holes, and enhances the formation of free OHradicals.
Using tetrabutyl orthotitanate as Ti source, hydrofluoric acid as Fsource and ethanol as solvent, well crystallized anatase-phase F-modified TiO2 hollow microspheres have been synthesized via a solvothermal process. The structure and properties of the resulting samples were characterized by XRD, SEM, FTIR, XPS. The results indicated that the fluorizated TiO2 hollow microspheres had an anatase phase, the fluorine atoms were mainly distributed on the surface of TiO2, and existed in forms of chemical-adsorption. Hollow anatase TiO2 microspheres were achieved by Ostwald ripening under solvothermal conditions. Compared to pure titania, the fluorizated TiO2 hollow microspheres showed a much higher degradation efficiency, and degradation rate of which can be up to 98% during the photodegradation of methyl orange with the initial concentration of 20 mg·L-1 for 30 minutes. The mechanism for the great improvement for photocatalytic activity can be attributed to the unique structure of hollow microsphere and the fluorine modification, because the strong electron withdrawing ability of the surface ≡Ti-Fgroups reduces the recombination of photogenerated electrons and holes, and enhances the formation of free OHradicals.
2013, 29(10): 2140-2144
doi: 10.3969/j.issn.1001-4861.2013.00.318
Abstract:
Two microporous lanthanide supramolecular complexes [Ln(CCA)(OH)(phen)(H2O)]n·n(phen)·nH2O(Ln=Yb, 1; Er, 2; H2CCA=2-carboxycinnamic acid; phen=1,10-phenanthraline) were obtained through hydrothermal reaction and characterized by elemental analysis, IRand single-crystal X-ray diffraction. The results show that the two complexes are isostructural and in the two complexes, dinuclear Ln2(OH)2 units are linked by CCA2-ligands to form 1Dinfinite double-stranded chains. There are two kinds of phen ligands. One adopts a chelating-bidentate coordination mode, the other is not involved in the coordination and acts as templating ligands, which leads to the formation of supramolecular networks with microporous structures. CCDC: 917027, 1; 917028, 2.
Two microporous lanthanide supramolecular complexes [Ln(CCA)(OH)(phen)(H2O)]n·n(phen)·nH2O(Ln=Yb, 1; Er, 2; H2CCA=2-carboxycinnamic acid; phen=1,10-phenanthraline) were obtained through hydrothermal reaction and characterized by elemental analysis, IRand single-crystal X-ray diffraction. The results show that the two complexes are isostructural and in the two complexes, dinuclear Ln2(OH)2 units are linked by CCA2-ligands to form 1Dinfinite double-stranded chains. There are two kinds of phen ligands. One adopts a chelating-bidentate coordination mode, the other is not involved in the coordination and acts as templating ligands, which leads to the formation of supramolecular networks with microporous structures. CCDC: 917027, 1; 917028, 2.
2013, 29(10): 2145-2149
doi: 10.3969/j.issn.1001-4861.2013.00.334
Abstract:
The effect of CuOdoping on B-site order of 0.94Pb(Mg1/3Nb2/3)O3-0.06PbTiO3 (abbreviated as PMN-6PT) ceramics with different sintering temperatures was studied. The Raman and XRDresults revealed that under different sintering temperature, ion substitution was different, which had different influence to B-site order. Sintering temperature at 950 ℃, Cu2+ ions entered the crystal lattice and made no difference in the B-site order. However, Sintering temperature at 1080 ℃, Cu1+ ions entered the crystal lattice and had an effect in the B-site order. The dependence of dielectric constant on temperature illustrated an obvious relaxor characteristic for CuOdoped PMN-based ceramics, which was in accord with Raman spectra analysis.
The effect of CuOdoping on B-site order of 0.94Pb(Mg1/3Nb2/3)O3-0.06PbTiO3 (abbreviated as PMN-6PT) ceramics with different sintering temperatures was studied. The Raman and XRDresults revealed that under different sintering temperature, ion substitution was different, which had different influence to B-site order. Sintering temperature at 950 ℃, Cu2+ ions entered the crystal lattice and made no difference in the B-site order. However, Sintering temperature at 1080 ℃, Cu1+ ions entered the crystal lattice and had an effect in the B-site order. The dependence of dielectric constant on temperature illustrated an obvious relaxor characteristic for CuOdoped PMN-based ceramics, which was in accord with Raman spectra analysis.
2013, 29(10): 2150-2156
doi: 10.3969/j.issn.1001-4861.2013.00.302
Abstract:
Two novel structural copper complexes: [Cu3(Ipz)3] (1) and [Cu(SO4)(Ipz)4]·2H2O·CH3OH (2) were synthesized by the hydrothermal reaction and the solution method, respectively. The complexes were characterized by elemental analysis, IRspectroscopy, UVspectrum and single crystal X-ray diffraction. Structural analyses have revealed that the complex 1 is crystallized in the orthorhombic system with Pnma space group. The complex 2 is crystallized in the Triclinic system with P1 space group. In the structure of the two complexes, the oxidation state of Cu atoms are +1 and +2, respectively, the coordinate environment of the metal and the coordinate model of the ligand are absolutely different. In the complex 1, copper is a two coordination atom, connected with ligand forming a nine-membered ring. However, the complex 2 is a six coordination atom, using coordinate sulfate group to form an infinite chain. Additionally, by using the quantum chemistry method electronic characteristic of the two complexes were performed, in the mean time, the luminescent spectrum of complex 1 was analyzed. CCDC: 900585, 1; 900586, 2.
Two novel structural copper complexes: [Cu3(Ipz)3] (1) and [Cu(SO4)(Ipz)4]·2H2O·CH3OH (2) were synthesized by the hydrothermal reaction and the solution method, respectively. The complexes were characterized by elemental analysis, IRspectroscopy, UVspectrum and single crystal X-ray diffraction. Structural analyses have revealed that the complex 1 is crystallized in the orthorhombic system with Pnma space group. The complex 2 is crystallized in the Triclinic system with P1 space group. In the structure of the two complexes, the oxidation state of Cu atoms are +1 and +2, respectively, the coordinate environment of the metal and the coordinate model of the ligand are absolutely different. In the complex 1, copper is a two coordination atom, connected with ligand forming a nine-membered ring. However, the complex 2 is a six coordination atom, using coordinate sulfate group to form an infinite chain. Additionally, by using the quantum chemistry method electronic characteristic of the two complexes were performed, in the mean time, the luminescent spectrum of complex 1 was analyzed. CCDC: 900585, 1; 900586, 2.
2013, 29(10): 2157-2161
doi: 10.3969/j.issn.1001-4861.2013.00.321
Abstract:
A 2D complex {[Mn(4,4'-bibp)(MPA)]·4H2O}n (1), based on mixed-ligands bibp (bibp=4,4'-bisimidazol-ylbiphenyl) and H2MPA (H2MPA=m-phthalic acid), has been synthesized by hydrothermal method and charac-terized by elemental analysis, IRspectra, XRD, TGA, and the crystal structure was determined by single-crystal X-ray diffraction. The complex crystallizes in the triclinic system, space group Pl, and features 2Dbilayer structure. Magnetic susceptibility measurement of complex 1 indicates the presence of weak antiferromagnetic interactions between the neighboring Mn(Ⅱ) ions. CCDC: 928642.
A 2D complex {[Mn(4,4'-bibp)(MPA)]·4H2O}n (1), based on mixed-ligands bibp (bibp=4,4'-bisimidazol-ylbiphenyl) and H2MPA (H2MPA=m-phthalic acid), has been synthesized by hydrothermal method and charac-terized by elemental analysis, IRspectra, XRD, TGA, and the crystal structure was determined by single-crystal X-ray diffraction. The complex crystallizes in the triclinic system, space group Pl, and features 2Dbilayer structure. Magnetic susceptibility measurement of complex 1 indicates the presence of weak antiferromagnetic interactions between the neighboring Mn(Ⅱ) ions. CCDC: 928642.
2013, 29(10): 2162-2168
doi: 10.3969/j.issn.1001-4861.2013.00.320
Abstract:
The new complex [Zn(gly)(phen)(H2O)2]2·2OH·SO4·4H2O(gly=Glycine acid cation, phen=1, 10-phenanthroline) has been synthesized and structurally characterized by X-ray single crystal diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis and fluorescence spectrum. The complex crystal data: triclinic, space group Pl, a=1.17163(9) nm, b=1.28022(10) nm, c=1.34849(10) nm, α=74.4800°, β=85.4240(10) °, γ=69.8070°, V=1.8289(2) nm3, Z=2. The TG-DTGof the complex was analyzed, and the E and lnA were figured out by Coasts-Redfem method and Achar method. Fluorescence spectrum showed that the complex has very strong luminescence at 370 nm. CCDC: 876328.
The new complex [Zn(gly)(phen)(H2O)2]2·2OH·SO4·4H2O(gly=Glycine acid cation, phen=1, 10-phenanthroline) has been synthesized and structurally characterized by X-ray single crystal diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis and fluorescence spectrum. The complex crystal data: triclinic, space group Pl, a=1.17163(9) nm, b=1.28022(10) nm, c=1.34849(10) nm, α=74.4800°, β=85.4240(10) °, γ=69.8070°, V=1.8289(2) nm3, Z=2. The TG-DTGof the complex was analyzed, and the E and lnA were figured out by Coasts-Redfem method and Achar method. Fluorescence spectrum showed that the complex has very strong luminescence at 370 nm. CCDC: 876328.
2013, 29(10): 2169-2175
doi: 10.3969/j.issn.1001-4861.2013.00.326
Abstract:
Anatase nanoporous TiO2 spheres were synthesized via a modified sol-gel method. By controlling the concentration of the precursor, size-controlled nanoporous TiO2 spheres with high dye-loading were achieved. The synthesized spheres with different sizes (100 nm, 175 nm, 225 nm, 475 nm) were used as scattering layers on a TiO2 nanoparticle film by electrophoresis deposition method to form bi-layered dye-sensitized solar cells (DSSCs). Scattering effect of the layers with different sized spheres was studied. It was proved that the 475nm-sized spheres showed optium light scattering effect. Due to the scattering effect, an overall photoelectric conversion efficiency of 6.3% has been achieved, a 30% increase compared with the nanoparticle-based photoanode.
Anatase nanoporous TiO2 spheres were synthesized via a modified sol-gel method. By controlling the concentration of the precursor, size-controlled nanoporous TiO2 spheres with high dye-loading were achieved. The synthesized spheres with different sizes (100 nm, 175 nm, 225 nm, 475 nm) were used as scattering layers on a TiO2 nanoparticle film by electrophoresis deposition method to form bi-layered dye-sensitized solar cells (DSSCs). Scattering effect of the layers with different sized spheres was studied. It was proved that the 475nm-sized spheres showed optium light scattering effect. Due to the scattering effect, an overall photoelectric conversion efficiency of 6.3% has been achieved, a 30% increase compared with the nanoparticle-based photoanode.
2013, 29(10): 2176-2182
doi: 10.3969/j.issn.1001-4861.2013.00.331
Abstract:
Three dinuclear Cu+ complexes [Cu2(μ-X)2(deebq)2] (where deebq=4,4'-diethylester-2,2'-biquinoline; X=Cl (1), Br (2) or I (3)), have been synthesized and characterized spectroscopically. The isostructural 1～3 crystallize in triclinic system with space group Pl, and show quite similar lattice parameters and packing structures. Two Cu+ ions in a dinuclear unit are related to each other via an inversion center; each Cu+ ion are coordinated by two Natoms form one deebq ligand and two X- anions, which act as a μ2-bridge mode to link two Cu+ ions, to form a distorted tetrahedral coordination geometry. The dinuclear units are aligned into a supramolecular chain via the intermolecular π…π interactions between the neighboring phenyl rings in deebq ligands, and the supramolecular chains are held together through weakly intermolecular van der Waals forces. Three complexes exhibit a broad and asymmetric absorption band in the 500～630 nm range in CH2Cl2, this band is almost independent on the bridged X- ligand and not observed in the absorption spectrum of deebq in CH2Cl2, thus, it is assigned to MLCTfrom Cu+ center to deebq ligand. Complexes 1～3 emitted intense fluorescence with the center around 400 nm, this emission band is attributed to the π-π* electronic transition of deebq ligand. No MLCTemission was observed in the CH2Cl2 solution and the solid state for three complexes. CCDC: 888543, 1; 888542, 2; 888541, 3.
Three dinuclear Cu+ complexes [Cu2(μ-X)2(deebq)2] (where deebq=4,4'-diethylester-2,2'-biquinoline; X=Cl (1), Br (2) or I (3)), have been synthesized and characterized spectroscopically. The isostructural 1～3 crystallize in triclinic system with space group Pl, and show quite similar lattice parameters and packing structures. Two Cu+ ions in a dinuclear unit are related to each other via an inversion center; each Cu+ ion are coordinated by two Natoms form one deebq ligand and two X- anions, which act as a μ2-bridge mode to link two Cu+ ions, to form a distorted tetrahedral coordination geometry. The dinuclear units are aligned into a supramolecular chain via the intermolecular π…π interactions between the neighboring phenyl rings in deebq ligands, and the supramolecular chains are held together through weakly intermolecular van der Waals forces. Three complexes exhibit a broad and asymmetric absorption band in the 500～630 nm range in CH2Cl2, this band is almost independent on the bridged X- ligand and not observed in the absorption spectrum of deebq in CH2Cl2, thus, it is assigned to MLCTfrom Cu+ center to deebq ligand. Complexes 1～3 emitted intense fluorescence with the center around 400 nm, this emission band is attributed to the π-π* electronic transition of deebq ligand. No MLCTemission was observed in the CH2Cl2 solution and the solid state for three complexes. CCDC: 888543, 1; 888542, 2; 888541, 3.
2013, 29(10): 2183-2187
doi: 10.3969/j.issn.1001-4861.2013.00.242
Abstract:
Acoordination polymer, [PbL2]n (1) (HL=2-(2-carboxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) has been hydrothermally synthesized and characterized by IRspectrum, elemental analysis and X-ray single-crystal diffraction. Complex 1 crystallizes in monoclinic, space group P21/c with a=1.34585(9) nm, b=0.70943(5) nm, c=3.2655(2) nm, β=99.6260(10)°, V=3.0740(4) nm3, Z=4, C40H22N8O4Pb, Mr=885.85, Dc=1.914 g·cm-3, μ(Mo Kα)=5.551 mm-1, F(000)=1728, GOOF=1.038, the final R=0.0270 and wR=0.0581 for 5067 observed reflections (I>2σ(I)). Structural analysis shows that the complex 1 presents a two dimensional layer structure. Thermal stability and luminescent property were also investigated. CCDC: 900402.
Acoordination polymer, [PbL2]n (1) (HL=2-(2-carboxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) has been hydrothermally synthesized and characterized by IRspectrum, elemental analysis and X-ray single-crystal diffraction. Complex 1 crystallizes in monoclinic, space group P21/c with a=1.34585(9) nm, b=0.70943(5) nm, c=3.2655(2) nm, β=99.6260(10)°, V=3.0740(4) nm3, Z=4, C40H22N8O4Pb, Mr=885.85, Dc=1.914 g·cm-3, μ(Mo Kα)=5.551 mm-1, F(000)=1728, GOOF=1.038, the final R=0.0270 and wR=0.0581 for 5067 observed reflections (I>2σ(I)). Structural analysis shows that the complex 1 presents a two dimensional layer structure. Thermal stability and luminescent property were also investigated. CCDC: 900402.
2013, 29(10): 2188-2194
doi: 10.3969/j.issn.1001-4861.2013.00.337
Abstract:
Two novel metal-organic frameworks (MOFs), [Cd(bdc)(Imphen)(H2O)]n·nH2O (1) and [Zn(bdc)(Imphen)(H2O)]n·nH2O (2) based on 1,4-benzenedicarboxylic acid (H2bdc) and imidazo[4,5-f][1,10]phenanthroline (Imphen) ligands, have been constructed under hydrothermal conditions. The complexes are characterized by elemental analyse, single crystal X-ray diffraction. Structural analyses show that the complexes1 and b>2 all present one dimensional chain and bdc2- ligands display different coordination modes. Furthermore, the adjacent chains are further connected by the hydrogen-bonding and π-π stacking interactions generating three-dimensional supramolecular structures. In addition, thermal stability and luminescent properties of two complexes were also investigated. CCDC: 947287, 1; 947288, 2.
Two novel metal-organic frameworks (MOFs), [Cd(bdc)(Imphen)(H2O)]n·nH2O (1) and [Zn(bdc)(Imphen)(H2O)]n·nH2O (2) based on 1,4-benzenedicarboxylic acid (H2bdc) and imidazo[4,5-f][1,10]phenanthroline (Imphen) ligands, have been constructed under hydrothermal conditions. The complexes are characterized by elemental analyse, single crystal X-ray diffraction. Structural analyses show that the complexes1 and b>2 all present one dimensional chain and bdc2- ligands display different coordination modes. Furthermore, the adjacent chains are further connected by the hydrogen-bonding and π-π stacking interactions generating three-dimensional supramolecular structures. In addition, thermal stability and luminescent properties of two complexes were also investigated. CCDC: 947287, 1; 947288, 2.
2013, 29(10): 2195-2199
doi: 10.3969/j.issn.1001-4861.2013.00.365
Abstract:
Anew 2D Zn(Ⅱ) metal-organic framework, [Zn2(dib)(1,3-BDC)2(H2O)] (1), has been synthesized by the hydrothermal reaction of 1,3-benzenedicarboxylate with ZnSO4·7H2Oin the presence of 1,4-di(1-imidazoly)benzene (dib=1,4-di(1-imidazoly)benzene, 1,3-H2BDC=1,3-benzenedicarboxylate). The crystal is of monoclinic system, space group P21/n, with a=0.80367(12) nm, b=1.3327(2) nm, c=2.3725(4) nm, β=97.394(3)°, V=2.5199(7) nm3, Z=4, F(000)=1392, R=0.0520 and wR=0.0994 (I>2σ(I)). The two central zinc(Ⅱ) ions in the complex locate in a different coordination geometry, one is a distorted tetrahedral and the other is a distorted square-pyramidal coordination geometry, respectively. The dib ligand acts as a bridging ligand, which links the 1D double-chain into 2D layer structure. The net is linked into three-dimensional supramolecular network by O-H…Ohydrogen bonds. CCDC: 895702.
Anew 2D Zn(Ⅱ) metal-organic framework, [Zn2(dib)(1,3-BDC)2(H2O)] (1), has been synthesized by the hydrothermal reaction of 1,3-benzenedicarboxylate with ZnSO4·7H2Oin the presence of 1,4-di(1-imidazoly)benzene (dib=1,4-di(1-imidazoly)benzene, 1,3-H2BDC=1,3-benzenedicarboxylate). The crystal is of monoclinic system, space group P21/n, with a=0.80367(12) nm, b=1.3327(2) nm, c=2.3725(4) nm, β=97.394(3)°, V=2.5199(7) nm3, Z=4, F(000)=1392, R=0.0520 and wR=0.0994 (I>2σ(I)). The two central zinc(Ⅱ) ions in the complex locate in a different coordination geometry, one is a distorted tetrahedral and the other is a distorted square-pyramidal coordination geometry, respectively. The dib ligand acts as a bridging ligand, which links the 1D double-chain into 2D layer structure. The net is linked into three-dimensional supramolecular network by O-H…Ohydrogen bonds. CCDC: 895702.
2013, 29(10): 2200-2204
doi: 10.3969/j.issn.1001-4861.2013.00.272
Abstract:
Colourless crystals of 1Dcoordination polymer, [Ca(L)2(H2O)2(CH3CH2OH)]n (L=N-benzenesulphonyl-L-phenylalanine), were obtained by the reaction of calcium perchlorate and N-benzenesulphonyl-L-phenylalanine in the 95% CH3CH2OH solution, and characterized by elemental analysis, IRand X-ray single crystal diffraction analysis. The single-crystal X-ray analysis of the title complex reveals that each Ca(Ⅱ) atom is seven-coordinated in a distorted pentagonal bipyramid coordination environment by seven oxygen atoms from the N-benzenesulphonyl-L-phenylalanine ligand, the coordinated water molecule and the coordinated CH3CH2OH molecule, respectively. The molecular structure is 1D coordination polymer by the interaction of bridged carboxylato groups. The antitumor activity against SMMC-7721, A549, WiDr and P388 cancer cells of the Ca(Ⅱ) complex also was investigated. CCDC: 890991.
Colourless crystals of 1Dcoordination polymer, [Ca(L)2(H2O)2(CH3CH2OH)]n (L=N-benzenesulphonyl-L-phenylalanine), were obtained by the reaction of calcium perchlorate and N-benzenesulphonyl-L-phenylalanine in the 95% CH3CH2OH solution, and characterized by elemental analysis, IRand X-ray single crystal diffraction analysis. The single-crystal X-ray analysis of the title complex reveals that each Ca(Ⅱ) atom is seven-coordinated in a distorted pentagonal bipyramid coordination environment by seven oxygen atoms from the N-benzenesulphonyl-L-phenylalanine ligand, the coordinated water molecule and the coordinated CH3CH2OH molecule, respectively. The molecular structure is 1D coordination polymer by the interaction of bridged carboxylato groups. The antitumor activity against SMMC-7721, A549, WiDr and P388 cancer cells of the Ca(Ⅱ) complex also was investigated. CCDC: 890991.
2013, 29(10): 2205-2214
doi: 10.3969/j.issn.1001-4861.2013.00.327
Abstract:
Micro/nano silica gel was functionalised with pyridinylthioether moiety. Two functionalised materials, FeC@L-NSiGand FeS@L-NSiG, were obtained by the coordination of the surface organic molecules with iron (Ⅱ) using FeCl2 and FeSO4 as the precursor, respectively. Both materials were characterised using FTIRand UV-Vis spectroscopies, TGAand SEMtechniques. Possible coordination chemistry of the iron(Ⅱ) on the surface functionalised materials and the catalytic performance of the title materials on the catalytic degradation of 1,2-dihydroxybenzene (catechol) by hydrogen peroxide were investigated. Aligand L, 2-(ethylthiomethyl)pyridine with “NS” donor set analogous to the organic functional group immobilised on the surface micro/nano silica gel, was synthesised for the study of the coordination chemistry around the iron (Ⅱ) centre of the two materials. The control complex, [Fe(L)2Cl2], used in the investigation was obtained by the reaction of the ligand Lwith FeCl2. The structure of the complex was determined by using X-ray single crystal diffraction analysis. The results suggest that the material FeS@L-NSiGshows higher catalytic efficiency by about one-fold than that of FeC@L-NSiG. This better catalytic efficiency is because that the FeS@L-NSiGhas more labile ligand(s) around the metal centre compared to its analogue (FeC@L-NSiG) and hence makes the substrate easier accessed upon binding to the metal centre. CCDC: 866526.
Micro/nano silica gel was functionalised with pyridinylthioether moiety. Two functionalised materials, FeC@L-NSiGand FeS@L-NSiG, were obtained by the coordination of the surface organic molecules with iron (Ⅱ) using FeCl2 and FeSO4 as the precursor, respectively. Both materials were characterised using FTIRand UV-Vis spectroscopies, TGAand SEMtechniques. Possible coordination chemistry of the iron(Ⅱ) on the surface functionalised materials and the catalytic performance of the title materials on the catalytic degradation of 1,2-dihydroxybenzene (catechol) by hydrogen peroxide were investigated. Aligand L, 2-(ethylthiomethyl)pyridine with “NS” donor set analogous to the organic functional group immobilised on the surface micro/nano silica gel, was synthesised for the study of the coordination chemistry around the iron (Ⅱ) centre of the two materials. The control complex, [Fe(L)2Cl2], used in the investigation was obtained by the reaction of the ligand Lwith FeCl2. The structure of the complex was determined by using X-ray single crystal diffraction analysis. The results suggest that the material FeS@L-NSiGshows higher catalytic efficiency by about one-fold than that of FeC@L-NSiG. This better catalytic efficiency is because that the FeS@L-NSiGhas more labile ligand(s) around the metal centre compared to its analogue (FeC@L-NSiG) and hence makes the substrate easier accessed upon binding to the metal centre. CCDC: 866526.
2013, 29(10): 2215-2224
doi: 10.3969/j.issn.1001-4861.2013.00.259
Abstract:
The G-quadruplex-disrupting abilities of Ag+ and Hg2+ ions were investigated by utilizing the metal ions-mediated circular dichroism (CD) spectrum changes of four representative G-quadruplexes. The results show that Ag+ ion can disrupt G-quadruplexes by chelating to Gbases and thus can be used as a general G-quadruplex-disrupting agent. The results also suggest that Hg2+ ion may disrupt G-quadruplexes by formation of T-Hg2+-Tbase pairs as well as other species. The G-quadruplexes disrupted by Ag+ and Hg2+ can be recovered by cysteine (Cys), a thiol-containing amino acid, due to the tight binding interactions between Cys and the metal ions. Thus, the system by using Ag+ (or Hg2+) and Cys as two inputs and CDsignal as output can behave as a DNA IMPLICATIONlogic gate.
The G-quadruplex-disrupting abilities of Ag+ and Hg2+ ions were investigated by utilizing the metal ions-mediated circular dichroism (CD) spectrum changes of four representative G-quadruplexes. The results show that Ag+ ion can disrupt G-quadruplexes by chelating to Gbases and thus can be used as a general G-quadruplex-disrupting agent. The results also suggest that Hg2+ ion may disrupt G-quadruplexes by formation of T-Hg2+-Tbase pairs as well as other species. The G-quadruplexes disrupted by Ag+ and Hg2+ can be recovered by cysteine (Cys), a thiol-containing amino acid, due to the tight binding interactions between Cys and the metal ions. Thus, the system by using Ag+ (or Hg2+) and Cys as two inputs and CDsignal as output can behave as a DNA IMPLICATIONlogic gate.
2013, 29(10): 2225-2230
doi: 10.3969/j.issn.1001-4861.2013.00.329
Abstract:
Monsubstituted cyclopentadienes (C5H5R) (R=n-Butyl (1), Benzyl (2), n-Propyl (3), Allyl (4)) reacted with Mo(CO)6 to give four new dinuclear cyclopentadienyl molybdenum carbonyl complexes (C5H4R)2Mo2(CO)6 (R=n-Butyl (5), Benzyl (6), n-Propyl (7), Allyl (8)), respectively. The complexes 5～8 were characterized by elemental analysis, IR, 1H NMRspectrum, and TG. The crystal structures of 5 and 6 were determined by X-ray single crystal diffraction. The structures show that complex 5 crystallizes in monoclinic system with space group P2l/c and complex 6 is triclinic crystal system with space group Pl.The TGanalysis shows that the complexes 5 and 6 are stable below 107 and 162 ℃, respectively. CCDC: 883603, 5; 881472, 6.
Monsubstituted cyclopentadienes (C5H5R) (R=n-Butyl (1), Benzyl (2), n-Propyl (3), Allyl (4)) reacted with Mo(CO)6 to give four new dinuclear cyclopentadienyl molybdenum carbonyl complexes (C5H4R)2Mo2(CO)6 (R=n-Butyl (5), Benzyl (6), n-Propyl (7), Allyl (8)), respectively. The complexes 5～8 were characterized by elemental analysis, IR, 1H NMRspectrum, and TG. The crystal structures of 5 and 6 were determined by X-ray single crystal diffraction. The structures show that complex 5 crystallizes in monoclinic system with space group P2l/c and complex 6 is triclinic crystal system with space group Pl.The TGanalysis shows that the complexes 5 and 6 are stable below 107 and 162 ℃, respectively. CCDC: 883603, 5; 881472, 6.
2013, 29(10): 2231-2238
doi: 10.3969/j.issn.1001-4861.2013.00.219
Abstract:
Two series of CeO2 materials were prepared by two different synthetic routes, i.e. the conventional ammonia precipitation route (CR) and the ammonium carbonate hydrolysis route (HA) using (NH4)2CO3 in the presence of hydrogen peroxide. The formation process and decomposition behavior of the precipitates were investigated by FTIR, Raman, thermogravimetric and differential thermal analysis (TG/DTA) and X-ray photoelectron spectroscopy (XPS). The results show that the as-prepared precipitate obtained by HAconsists of O22-, CO32- and OH- species. However, after hydrothermal digestion at 80 ℃, the CO32- species is gradually hydrolyzed into OH- species. Although the chemical components of the digested precipitates prepared by these two routes are almost the same, the agglomeration of CeO2 particles is markedly modified. The CeO2 powder produced by HAexhibits higher thermal stability and better reduction property compared to that obtained by CR. After the heat treatment at 900 ℃ for 3 h, the CeO2 powder from HAroute still remains a surface area of 27 m2·g-1.
Two series of CeO2 materials were prepared by two different synthetic routes, i.e. the conventional ammonia precipitation route (CR) and the ammonium carbonate hydrolysis route (HA) using (NH4)2CO3 in the presence of hydrogen peroxide. The formation process and decomposition behavior of the precipitates were investigated by FTIR, Raman, thermogravimetric and differential thermal analysis (TG/DTA) and X-ray photoelectron spectroscopy (XPS). The results show that the as-prepared precipitate obtained by HAconsists of O22-, CO32- and OH- species. However, after hydrothermal digestion at 80 ℃, the CO32- species is gradually hydrolyzed into OH- species. Although the chemical components of the digested precipitates prepared by these two routes are almost the same, the agglomeration of CeO2 particles is markedly modified. The CeO2 powder produced by HAexhibits higher thermal stability and better reduction property compared to that obtained by CR. After the heat treatment at 900 ℃ for 3 h, the CeO2 powder from HAroute still remains a surface area of 27 m2·g-1.
2013, 29(10): 2239-2244
doi: 10.3969/j.issn.1001-4861.2013.00.340
Abstract:
Two isostructural lanthanide complexes, [LnL2(NO3)3] (L=N,N-diphenyl-2-(quinolin-8-yloxy)acetamide, Ln=La(Ⅲ), 1; Ce(Ⅲ), 2) were synthesized and characterized by X-ray diffraction. In each complex, center metal ion is coordinated to four oxygen and two nitrogen atoms from two independent acetamide ligands and also to six oxygen atoms from three nitrate anions, possessing a coordination geometry closer to a distorted icosahedron. In CH3CNsolution, both complexes exhibit strong fluorescence emission. CCDC: 941145, 1; 941146, 2.
Two isostructural lanthanide complexes, [LnL2(NO3)3] (L=N,N-diphenyl-2-(quinolin-8-yloxy)acetamide, Ln=La(Ⅲ), 1; Ce(Ⅲ), 2) were synthesized and characterized by X-ray diffraction. In each complex, center metal ion is coordinated to four oxygen and two nitrogen atoms from two independent acetamide ligands and also to six oxygen atoms from three nitrate anions, possessing a coordination geometry closer to a distorted icosahedron. In CH3CNsolution, both complexes exhibit strong fluorescence emission. CCDC: 941145, 1; 941146, 2.
2013, 29(10): 2245-2250
doi: 10.3969/j.issn.1001-4861.2013.00.300
Abstract:
One new metal-organic framework, namely, [Co(pqba)2(biyb)](1) (2-phenyl-4-quinolinecarboxylic acid=Hpqba, 1,4-bis(imidazol-1-ylmethyl)benzene=biyb), has been synthesized under hydrothermal conditions. The compound 1 was characterized by elemental analysis, IRspectroscopy, and X-ray single-crystal diffraction. Complex 1 crystallizes in the Monoclinic system, C2/c space group. In 1, the biyb act as bidentate ligands assembling with Co(Ⅱ) ions to a one-dimensional framework, which is further expanded to form a 2D supramolecular structure by π…π stacking interactions with biyb molecules between 1D chains. Thermogravimetric analyses for 1 is discussed. Furthermore, electrochemical property of the 1 shows that electron transfer of Co(Ⅱ) between Co(Ⅲ) in electrolysis is quasi-reversible process, and magnetic susceptibility measurements indicate that compound 1 has dominating antiferromagnetic couplings between metal ions. CCDC: 919474.
One new metal-organic framework, namely, [Co(pqba)2(biyb)](1) (2-phenyl-4-quinolinecarboxylic acid=Hpqba, 1,4-bis(imidazol-1-ylmethyl)benzene=biyb), has been synthesized under hydrothermal conditions. The compound 1 was characterized by elemental analysis, IRspectroscopy, and X-ray single-crystal diffraction. Complex 1 crystallizes in the Monoclinic system, C2/c space group. In 1, the biyb act as bidentate ligands assembling with Co(Ⅱ) ions to a one-dimensional framework, which is further expanded to form a 2D supramolecular structure by π…π stacking interactions with biyb molecules between 1D chains. Thermogravimetric analyses for 1 is discussed. Furthermore, electrochemical property of the 1 shows that electron transfer of Co(Ⅱ) between Co(Ⅲ) in electrolysis is quasi-reversible process, and magnetic susceptibility measurements indicate that compound 1 has dominating antiferromagnetic couplings between metal ions. CCDC: 919474.
2013, 29(10): 2251-2256
doi: 10.3969/j.issn.1001-4861.2013.00.210
Abstract:
Anew three-dimensional coordination polymer of {[Cd2(titmb)(CAM)2]·2H2O}n (1) (H2CAM=camphor acid, and titmb=1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene) has been prepared and characterized by elemental analysis, IR spectroscopy, TGAand single-crystal X-ray diffraction. The crystal is of monoclinic, space group Pl with a=1.23825(15) nm, b=1.30128(16) nm, c=1.53729(19) nm, α=91.351 (2)°, β=94.864 (3)°, γ=98.730 (2)°, V=2.4379(5) nm3, Dc=1.386 g·cm-3, Z=2, F(000)=1040, Goof=1.027, R1=0.0545, wR2=0.1210. Complex 1 displays an unusual three-dimensional (3, 4, 6)-connected network with (4.64.8)2(42.64.89)(62.8)2 topology. Moreover, their luminescent properties have been investigated in the solid state. CCDC: 834854.
Anew three-dimensional coordination polymer of {[Cd2(titmb)(CAM)2]·2H2O}n (1) (H2CAM=camphor acid, and titmb=1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene) has been prepared and characterized by elemental analysis, IR spectroscopy, TGAand single-crystal X-ray diffraction. The crystal is of monoclinic, space group Pl with a=1.23825(15) nm, b=1.30128(16) nm, c=1.53729(19) nm, α=91.351 (2)°, β=94.864 (3)°, γ=98.730 (2)°, V=2.4379(5) nm3, Dc=1.386 g·cm-3, Z=2, F(000)=1040, Goof=1.027, R1=0.0545, wR2=0.1210. Complex 1 displays an unusual three-dimensional (3, 4, 6)-connected network with (4.64.8)2(42.64.89)(62.8)2 topology. Moreover, their luminescent properties have been investigated in the solid state. CCDC: 834854.
2013, 29(10): 2257-2264
doi: 10.3969/j.issn.1001-4861.2013.00.333
Abstract:
Rod-like LiFePO4 was synthesized by hydrothermal method using ethylene diamine tetraacetic acid (EDTA) as complexing agent to control the growth of the crystal. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge test. The results show that EDTAhas great influence on the morphology and electrochemical performance. The crystal morphology develops from irregular particles to rod-like particles and the thickness of the particles decreases from 140～200 nm to 40～90 nm by adding EDTAand the obtained LiFePO4/Cwith EDTAexhibits a homogenous carbon coating layer with a thickness of ～3.5 nm. The discharge capacity is 167 mAh·g-1 (close to the theoretical capacity of 170 mAh·g-1) at 0.1C. The CVand EISresults indicate the samples prepared with EDTAhave a lower polarization and lower interfacial resistance.
Rod-like LiFePO4 was synthesized by hydrothermal method using ethylene diamine tetraacetic acid (EDTA) as complexing agent to control the growth of the crystal. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge test. The results show that EDTAhas great influence on the morphology and electrochemical performance. The crystal morphology develops from irregular particles to rod-like particles and the thickness of the particles decreases from 140～200 nm to 40～90 nm by adding EDTAand the obtained LiFePO4/Cwith EDTAexhibits a homogenous carbon coating layer with a thickness of ～3.5 nm. The discharge capacity is 167 mAh·g-1 (close to the theoretical capacity of 170 mAh·g-1) at 0.1C. The CVand EISresults indicate the samples prepared with EDTAhave a lower polarization and lower interfacial resistance.
