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2013 Volume 29 Issue 6
2013, 29(6): 1103-1108
doi: 10.3969/j.issn.1001-4861.2013.00.177
Abstract:
The Chevrel Phase materials Cu2Mo6S8-nSen (n=0,0.5,1.5) were synthesized by molten salt methods. Their crystal structures and the electrochemical properties were studied by a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammetry test (CV), galvanostatic charge-discharge test and electrochemical impedance spectroscopy (EIS). XRD analysis showed that Se-substituted Cu2Mo6S8-nSen was still Chevrel Phase, however the lattice parameters became larger, and SEM pictures viewed the particle size was small. The studies of the electrochemical properties suggested that the shape of voltammetric peaks in the region 0.5～0.8 V changed, the steady specific capacity increased to 103.5 mAh·g-1 and the cycling performance were improved because of Se substituted in Cu2Mo6S8. All these proved the reversible intercalation of Mg ions into these hosts were facilitated.
The Chevrel Phase materials Cu2Mo6S8-nSen (n=0,0.5,1.5) were synthesized by molten salt methods. Their crystal structures and the electrochemical properties were studied by a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammetry test (CV), galvanostatic charge-discharge test and electrochemical impedance spectroscopy (EIS). XRD analysis showed that Se-substituted Cu2Mo6S8-nSen was still Chevrel Phase, however the lattice parameters became larger, and SEM pictures viewed the particle size was small. The studies of the electrochemical properties suggested that the shape of voltammetric peaks in the region 0.5～0.8 V changed, the steady specific capacity increased to 103.5 mAh·g-1 and the cycling performance were improved because of Se substituted in Cu2Mo6S8. All these proved the reversible intercalation of Mg ions into these hosts were facilitated.
2013, 29(6): 1109-1114
doi: 10.3969/j.issn.1001-4861.2013.00.191
Abstract:
The 2,2'-bipyridine-based ruthenium complex with sulfobenzoate ligand was synthesized, [Ru(2,2'-bipy)3](3-Hsb)(3-sb)·5H2O (1), where 2,2'-bipy is 2,2'-bipyridine and 3-sb2- is 3-sulfobenzoate dianion, and characterized by elemental analysis, IR, UV-Vis, fluorescence spectrum, DTA-TG and single crystal X-ray analysis. The structural analysis showed that 1 is a cation-anion complex and the anions and water molecules form the three-dimensional hydrogen-bonding network with cavities occupied by cations. Cyclic voltammetry of 1 shows a one electron Ru(Ⅳ)/Ru(Ⅲ) reversible couple with E1/2 of 1.350 V. The oxidation of thioanisol catalyzed by 1 together with the acid produced high yield and selectivity for the sulfoxide. CCDC: 910779.
The 2,2'-bipyridine-based ruthenium complex with sulfobenzoate ligand was synthesized, [Ru(2,2'-bipy)3](3-Hsb)(3-sb)·5H2O (1), where 2,2'-bipy is 2,2'-bipyridine and 3-sb2- is 3-sulfobenzoate dianion, and characterized by elemental analysis, IR, UV-Vis, fluorescence spectrum, DTA-TG and single crystal X-ray analysis. The structural analysis showed that 1 is a cation-anion complex and the anions and water molecules form the three-dimensional hydrogen-bonding network with cavities occupied by cations. Cyclic voltammetry of 1 shows a one electron Ru(Ⅳ)/Ru(Ⅲ) reversible couple with E1/2 of 1.350 V. The oxidation of thioanisol catalyzed by 1 together with the acid produced high yield and selectivity for the sulfoxide. CCDC: 910779.
2013, 29(6): 1115-1122
doi: 10.3969/j.issn.1001-4861.2013.00.193
Abstract:
Transition metal oxide (MO) can obviously influence the thermal decomposition process of ammonium polyphosphate (APP) to improve the flame retardant efficiency of intumescent flame retardant composites based on APP in polymer. ZnO, Fe2O3 and TiO2, in same amount were added into APP to study the influence of MO on thermal decomposition behavior of APP, and to analyze the evolution of chemical state of metallic atoms and phosphorus atom and crystal structure in the interaction processes by thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) respectively. TGA and XPS spectra showed that MO could catalyze the releasing of NH3 and H2O of APP in the earlier period, and increase the high temperature residue in the later period due to the formation of metallic phosphate. The sequence of catalytic activity for the process of releasing of NH3 and H2O was as follows: ZnO>Fe2O3>TiO2, and that of cross-linking ability for thermal decomposition product P-O of APP was as follows: Fe2O3>ZnO>TiO2. XRD showed that APP could react with ZnO, Fe2O3 and TiO2 to produce Zn(PO3)2, Fe4(P2O7)3 and TiP2O7, respectively, at high temperature.
Transition metal oxide (MO) can obviously influence the thermal decomposition process of ammonium polyphosphate (APP) to improve the flame retardant efficiency of intumescent flame retardant composites based on APP in polymer. ZnO, Fe2O3 and TiO2, in same amount were added into APP to study the influence of MO on thermal decomposition behavior of APP, and to analyze the evolution of chemical state of metallic atoms and phosphorus atom and crystal structure in the interaction processes by thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) respectively. TGA and XPS spectra showed that MO could catalyze the releasing of NH3 and H2O of APP in the earlier period, and increase the high temperature residue in the later period due to the formation of metallic phosphate. The sequence of catalytic activity for the process of releasing of NH3 and H2O was as follows: ZnO>Fe2O3>TiO2, and that of cross-linking ability for thermal decomposition product P-O of APP was as follows: Fe2O3>ZnO>TiO2. XRD showed that APP could react with ZnO, Fe2O3 and TiO2 to produce Zn(PO3)2, Fe4(P2O7)3 and TiP2O7, respectively, at high temperature.
2013, 29(6): 1123-1128
doi: 10.3969/j.issn.1001-4861.2013.00.166
Abstract:
In this paper, the CdWO4 nano-crystal co-doping with Yb3+/Tm3+ ions was synthetized by hydrothermal method. The luminescence properties and structure of the sample were measured by X-ray powder diffractions(XRD)、field emission scanning environmental electron microscope (ESEM) and spectral analysis .And the CWO was monoclinic system with the mean size of 30 nm. It could be obtained from the image of ESEM that the structure of CWO was nano-rod with the diameter of 30 nm and the length-diameter ratio was between 5 and 8. The emission spectra were obtained when it was excited by 980 nm semi-conductor laser. There was a strong blue emission peak and the value was 481nm which was due to the transition 1G4→3H6 of Tm3+. The mechanism of Tm3+/Yb3+ co-doped system was also studied. The concentration of rare earths could influence the intensity of the blue emission. The strongest peak was obtained when the concentration of Tm3+ was 2mol% and the concentration ratio of Yb3+/Tm3+ was 10:1. According to the relationship between pump power and luminescence intensity, the emission of blue peak was three photons absorption process. It can be determined from the curve of lg(I/C)-lg(C) that the strong emission band at 481 nm belongs to electric dipole transition.
In this paper, the CdWO4 nano-crystal co-doping with Yb3+/Tm3+ ions was synthetized by hydrothermal method. The luminescence properties and structure of the sample were measured by X-ray powder diffractions(XRD)、field emission scanning environmental electron microscope (ESEM) and spectral analysis .And the CWO was monoclinic system with the mean size of 30 nm. It could be obtained from the image of ESEM that the structure of CWO was nano-rod with the diameter of 30 nm and the length-diameter ratio was between 5 and 8. The emission spectra were obtained when it was excited by 980 nm semi-conductor laser. There was a strong blue emission peak and the value was 481nm which was due to the transition 1G4→3H6 of Tm3+. The mechanism of Tm3+/Yb3+ co-doped system was also studied. The concentration of rare earths could influence the intensity of the blue emission. The strongest peak was obtained when the concentration of Tm3+ was 2mol% and the concentration ratio of Yb3+/Tm3+ was 10:1. According to the relationship between pump power and luminescence intensity, the emission of blue peak was three photons absorption process. It can be determined from the curve of lg(I/C)-lg(C) that the strong emission band at 481 nm belongs to electric dipole transition.
2013, 29(6): 1129-1134
doi: 10.3969/j.issn.1001-4861.2013.00.152
Abstract:
A series of CexZr1-xO2(0≤x≤1) solid solutions were prepared by uniformity precipitation using urea as the precipitant. Supported Pd catalyst was prepared by using the above solid solution as the carrier. The effect of the carriers surface basicity on the sintering behavior of Pd in Pd/CexZr1-xO2 catalyst was investigated by XRD, low temperature nitrogen adsorption-desorption, CO pulse chemisorption, CO2-TPD and in situ Diffuse Reflectance IR Fourier-Transform Spectroscopy(in situ DRIFTS). The results show that the sintering inhibition of palladium relates to the weaker basic site. Owing to its relative larger amount of weak basic site,the prepared Pd/Ce0.75Zr0.25O2 catalyst exhibits higher Pd dispersion and better thermal stability.
A series of CexZr1-xO2(0≤x≤1) solid solutions were prepared by uniformity precipitation using urea as the precipitant. Supported Pd catalyst was prepared by using the above solid solution as the carrier. The effect of the carriers surface basicity on the sintering behavior of Pd in Pd/CexZr1-xO2 catalyst was investigated by XRD, low temperature nitrogen adsorption-desorption, CO pulse chemisorption, CO2-TPD and in situ Diffuse Reflectance IR Fourier-Transform Spectroscopy(in situ DRIFTS). The results show that the sintering inhibition of palladium relates to the weaker basic site. Owing to its relative larger amount of weak basic site,the prepared Pd/Ce0.75Zr0.25O2 catalyst exhibits higher Pd dispersion and better thermal stability.
2013, 29(6): 1135-1140
doi: 10.3969/j.issn.1001-4861.2013.00.157
Abstract:
Composite material CuO-Co3O4 was prepared by a co-precipitation method. A catalytic combustion CO sensor was fabricated by using CuO-Co3O4 as the sensing material and NTCT (Negative Temperature Coefficient Thermistor) as the heating resistance. The limit of quantification for the sensor is 0.034 9 mg·L-1. The phase composition and surface morphology of the composite material were characterized by X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM). When the calcination temperature of CuO-Co3O4 is 400 ℃, the sensor' s sensitivity to CO reaches maximum. The sensor shows good linear relationship between response signals and CO concentration from 0.034 9 to 0.582 mg·L-1 at the operating voltage of 9 V and the linear correlation coefficient is 0.979. The 90% response and recovery time to 0.582 mg·L-1 CO is 24 s and 68 s, respectively.
Composite material CuO-Co3O4 was prepared by a co-precipitation method. A catalytic combustion CO sensor was fabricated by using CuO-Co3O4 as the sensing material and NTCT (Negative Temperature Coefficient Thermistor) as the heating resistance. The limit of quantification for the sensor is 0.034 9 mg·L-1. The phase composition and surface morphology of the composite material were characterized by X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM). When the calcination temperature of CuO-Co3O4 is 400 ℃, the sensor' s sensitivity to CO reaches maximum. The sensor shows good linear relationship between response signals and CO concentration from 0.034 9 to 0.582 mg·L-1 at the operating voltage of 9 V and the linear correlation coefficient is 0.979. The 90% response and recovery time to 0.582 mg·L-1 CO is 24 s and 68 s, respectively.
2013, 29(6): 1141-1148
doi: 10.3969/j.issn.1001-4861.2013.00.186
Abstract:
Different anionic surfactant was empolyed as additive for the seed-mediated synthesis of gold nanorods and effect of the kind of anionic surfactant on the morphology and optical property of gold nanorods were also investigated. In the presence of sodium dodecyl benzene sulfonate (SDBS), the yield of gold nanorods is obviously higher that of the reaction system using sodium dodecyl sulfate. The reaction conditions of the seed-mediated synthesis of gold nanorods added SDBS were optimized, and the optimal concentrations of hexadecyltrimethylammonium bromide, SDBS, ascorbic acid and silver nitrate were found to be 0.04 mol·L-1, 2.4 mmol·L-1, 1.2 mmol·L-1 and 0.08 mmol·L-1, respectively. Under the condition, the growth of gold nanorods can complete within 30 minutes, the as-prepared gold nanorods offer a surface plasmon resonance absorption with a maximum absorption peak at 823 nm and aspect ratio of (5±0.03). When changing silver nitrate concentration in the growth solution, the size of gold nanorods also changed. In addition, we also discussed the action mechanism of SDBS. In comparsion with classical seed-mediated synthesis method, proposed method for synthesis of gold nanorods shows an obvious improvement of size adjustable, monodispersity and biological toxicity, and it can be widely applied to a variety of optical and biological analysis.
Different anionic surfactant was empolyed as additive for the seed-mediated synthesis of gold nanorods and effect of the kind of anionic surfactant on the morphology and optical property of gold nanorods were also investigated. In the presence of sodium dodecyl benzene sulfonate (SDBS), the yield of gold nanorods is obviously higher that of the reaction system using sodium dodecyl sulfate. The reaction conditions of the seed-mediated synthesis of gold nanorods added SDBS were optimized, and the optimal concentrations of hexadecyltrimethylammonium bromide, SDBS, ascorbic acid and silver nitrate were found to be 0.04 mol·L-1, 2.4 mmol·L-1, 1.2 mmol·L-1 and 0.08 mmol·L-1, respectively. Under the condition, the growth of gold nanorods can complete within 30 minutes, the as-prepared gold nanorods offer a surface plasmon resonance absorption with a maximum absorption peak at 823 nm and aspect ratio of (5±0.03). When changing silver nitrate concentration in the growth solution, the size of gold nanorods also changed. In addition, we also discussed the action mechanism of SDBS. In comparsion with classical seed-mediated synthesis method, proposed method for synthesis of gold nanorods shows an obvious improvement of size adjustable, monodispersity and biological toxicity, and it can be widely applied to a variety of optical and biological analysis.
2013, 29(6): 1149-1156
doi: 10.3969/j.issn.1001-4861.2013.00.198
Abstract:
Two coordination polymers {[Cd(btaa)(phen)(CH3COO)]·H2O}n (1), and {[Ag2(btaa)(4,4-bpy)2](NO3)·2H2O}n(2) (Hbtaa=1H-benzotriazole-1-acetic acid, phen=1,10-phenanthroline, 4,4-bpy=4,4-bipyridine) were prepared and characterized by IR spectrum, elemental analysis, TG and single-crystal X-ray analyses. The cadmium ion in complex 1 is linked by btaa ligands into one-dimensional helical chain coordination polymer motif. A ladder type of structure was observed in 2 in which two of the [Ag(4,4'-bpy)]n linear chains are bridged by btaa ligands and paired by Ag…Ag interactions and π-π stacking interactions. Moreover, the luminescent property of complex 1 has been investigated in the solid state. CCDC: 901938, 1; 901939, 2.
Two coordination polymers {[Cd(btaa)(phen)(CH3COO)]·H2O}n (1), and {[Ag2(btaa)(4,4-bpy)2](NO3)·2H2O}n(2) (Hbtaa=1H-benzotriazole-1-acetic acid, phen=1,10-phenanthroline, 4,4-bpy=4,4-bipyridine) were prepared and characterized by IR spectrum, elemental analysis, TG and single-crystal X-ray analyses. The cadmium ion in complex 1 is linked by btaa ligands into one-dimensional helical chain coordination polymer motif. A ladder type of structure was observed in 2 in which two of the [Ag(4,4'-bpy)]n linear chains are bridged by btaa ligands and paired by Ag…Ag interactions and π-π stacking interactions. Moreover, the luminescent property of complex 1 has been investigated in the solid state. CCDC: 901938, 1; 901939, 2.
Preparation of TNP Electrochemical Sensor Based on Silver Nanoparticles/Graphene Oxide Nanocomposite
2013, 29(6): 1157-1164
doi: 10.3969/j.issn.1001-4861.2013.00.220
Abstract:
Graphene oxide (GO) was prepared by a modified Hummers process, and then silver nanoparticles (AgNPs) were directly deposited on the surface of GO using glucose as reducing agent; finally nanocomposite of AgNPs/GO with good stability was obtained. A novel 2,4,6-trinitrophenol (TNP) electrochemical sensor was fabricated based on the prepared nanocomposite modified electrode. The nanocomposite was characterized by atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), UV-Vis spectroscopy (UV-Vis) and alternating current impedance (EIS), and the electrochemical behaviors and kinetic properties of TNP on the modified electrode were also investigated. The experimental results showed that a sensitive oxidation peak and three reduction peaks of TNP appeared at the nanocomposite modified electrode. The oxidation peak can be used for quantitative analysis of TNP. Moreover, the whole electrode process was obviously irreversible, and electrode reaction was controlled by the adsorption step. The surface coverage of nanocomposite modified electrode was 5.617×10-8 mol·cm-2, and the rate constant was 9.745×10-5 cm·s-1 at the fixed potential. In pH 6.8 phosphate buffer, the oxidation peak currents of TNP were linearly dependent on its concentrations in the range of 5.0×10-9～1.0×10-7 mol·L-1 with accumulation time of 60 s at -0.70 V. The correlation coefficient was 0.995 8 and the detection limit was 1.0×10-9 mol·L-1. The prepared electrochemical sensor had preferable stability and selectivity, and it could be applied to the quick determination of TNP in real water samples, and the recovery was from 97.6% to 103.9%.
Graphene oxide (GO) was prepared by a modified Hummers process, and then silver nanoparticles (AgNPs) were directly deposited on the surface of GO using glucose as reducing agent; finally nanocomposite of AgNPs/GO with good stability was obtained. A novel 2,4,6-trinitrophenol (TNP) electrochemical sensor was fabricated based on the prepared nanocomposite modified electrode. The nanocomposite was characterized by atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), UV-Vis spectroscopy (UV-Vis) and alternating current impedance (EIS), and the electrochemical behaviors and kinetic properties of TNP on the modified electrode were also investigated. The experimental results showed that a sensitive oxidation peak and three reduction peaks of TNP appeared at the nanocomposite modified electrode. The oxidation peak can be used for quantitative analysis of TNP. Moreover, the whole electrode process was obviously irreversible, and electrode reaction was controlled by the adsorption step. The surface coverage of nanocomposite modified electrode was 5.617×10-8 mol·cm-2, and the rate constant was 9.745×10-5 cm·s-1 at the fixed potential. In pH 6.8 phosphate buffer, the oxidation peak currents of TNP were linearly dependent on its concentrations in the range of 5.0×10-9～1.0×10-7 mol·L-1 with accumulation time of 60 s at -0.70 V. The correlation coefficient was 0.995 8 and the detection limit was 1.0×10-9 mol·L-1. The prepared electrochemical sensor had preferable stability and selectivity, and it could be applied to the quick determination of TNP in real water samples, and the recovery was from 97.6% to 103.9%.
2013, 29(6): 1165-1170
doi: 10.3969/j.issn.1001-4861.2013.00.201
Abstract:
A new coordination polymer [Fe(phen)(bdc)(H2O)]n has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, UV-Vis, TG and single crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1, C20H14N2FeO5, with a=0.9308(6) nm, b=1.022 6(7) nm, c=1.134 1(5) nm,α=112.790(15)°, β=94.720(14)°, γ=113.417(10)°, V=0.876 9(9) nm3, Z=2, the final R1=0.0346, wR2=0.078 8. The Fe(Ⅱ) is coordinated with two nitrogen atoms and three oxygen atoms making a highly distorted trigonal bipyramidal. A 1D chain structure is constructed and further extended into a 3D structure through O-H…O intermolecular hydrogen bonding interactions. The polymer shows a fluorescence-emission at around 368 nm. CCDC: 894820.
A new coordination polymer [Fe(phen)(bdc)(H2O)]n has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, UV-Vis, TG and single crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1, C20H14N2FeO5, with a=0.9308(6) nm, b=1.022 6(7) nm, c=1.134 1(5) nm,α=112.790(15)°, β=94.720(14)°, γ=113.417(10)°, V=0.876 9(9) nm3, Z=2, the final R1=0.0346, wR2=0.078 8. The Fe(Ⅱ) is coordinated with two nitrogen atoms and three oxygen atoms making a highly distorted trigonal bipyramidal. A 1D chain structure is constructed and further extended into a 3D structure through O-H…O intermolecular hydrogen bonding interactions. The polymer shows a fluorescence-emission at around 368 nm. CCDC: 894820.
2013, 29(6): 1171-1175
doi: 10.3969/j.issn.1001-4861.2013.00.148
Abstract:
In this paper, the yttrium doped Eu(TTA)3 probe molecule were prepared, which the EuCl3, YCl3 and 2-Thenoyltrifluoroacetone(TTA) were used as raw materials, and then the yttrium doped Eu(TTA)3/Polymethyl-methacrylate(PMMA) temperature-sensitive paint (TSP) was obtained when the yttrium doped Eu(TTA)3 probe molecule were doped into the PMMA. The structure of the probe molecule and the properties of the TSP were characterized by IR, absorption spectra, excitation and emission spectra. IR analysis indicate that the coordinate bond between Eu(Y) and TTA was formed, and the structure of Eu(TTA)3 was not destroyed when the yttrium was doped into Eu(TTA)3. UV absorption spectra show that the absorption band of the probe molecule is 290～376 nm. Excitation and emission spectra illustrate that the strongest emission peak is 614 nm when the TSP was excited by 340 nm, and the emission of Eu(TTA)3 will be enhanced for the doping of yttrium, and the gain function was the strongest when the ratio between Eu and Y was 0.5:0.5. The emission spectra of the TSP at different temperatures illustrate that the emission strength of the TSP was decreased with the increasing of temperature, it shows that the TSP has good temperature quenching property, Furthermore, the temperature measure sensitivity was also enhanced for the doping of yttrium.
In this paper, the yttrium doped Eu(TTA)3 probe molecule were prepared, which the EuCl3, YCl3 and 2-Thenoyltrifluoroacetone(TTA) were used as raw materials, and then the yttrium doped Eu(TTA)3/Polymethyl-methacrylate(PMMA) temperature-sensitive paint (TSP) was obtained when the yttrium doped Eu(TTA)3 probe molecule were doped into the PMMA. The structure of the probe molecule and the properties of the TSP were characterized by IR, absorption spectra, excitation and emission spectra. IR analysis indicate that the coordinate bond between Eu(Y) and TTA was formed, and the structure of Eu(TTA)3 was not destroyed when the yttrium was doped into Eu(TTA)3. UV absorption spectra show that the absorption band of the probe molecule is 290～376 nm. Excitation and emission spectra illustrate that the strongest emission peak is 614 nm when the TSP was excited by 340 nm, and the emission of Eu(TTA)3 will be enhanced for the doping of yttrium, and the gain function was the strongest when the ratio between Eu and Y was 0.5:0.5. The emission spectra of the TSP at different temperatures illustrate that the emission strength of the TSP was decreased with the increasing of temperature, it shows that the TSP has good temperature quenching property, Furthermore, the temperature measure sensitivity was also enhanced for the doping of yttrium.
2013, 29(6): 1176-1184
doi: 10.3969/j.issn.1001-4861.2013.00.169
Abstract:
The copper(Ⅱ)-tuned photoluminescence of [Ru(bpy)2(dppz)]2+ (bpy=2,2'-bipyridine and dppz=dipyrido[3,2-a:2',3'-c]phenazine) enhanced by DNA and sodium dodecylsulfate (SDS) has been investigated in ethanol and water mixtures by means of fluorescence spectroscopy, fluorescence microscopic imaging and voltammetry. The photoluminescence of [Ru(bpy)2(dppz)]2+ in the ethanol/Tris-water mixed system (VEthanol:VTris=1:5) is enhanced by DNA and anionic surfactant SDS, whose binding constants with the Ru(Ⅱ) complex are 5.5×105 and 4.2×102 L·mol-1, respectively. The presence of Cu(Ⅱ) ions can quench the photoluminescence of [Ru(bpy)2(dppz)]2+ in the DNA-containing mixed system via the DNA-mediated photoinduced electron transfer, in which the Stern-Volmer constant is 2.0×105 L·mol-1, being far larger than that in the SDS-containing system (9.0×103 L·mol-1). In addition, combined with the effects of SDS, DNA and Cu(Ⅱ) ions on the redox reactions of [Ru(bpy)2(dppz)]2+ on an indium-tin oxide (ITO) electrode, the copper(Ⅱ)-tuned mechanism for the photoluminescence of [Ru(bpy)2(dppz)]2+ enhanced by DNA and SDS is further explored. This study not only helps us better understand the luminescence and quenching mechanisms of DNA intercalators, but also provides a new idea for the fabrication of biomolecular light switches.
The copper(Ⅱ)-tuned photoluminescence of [Ru(bpy)2(dppz)]2+ (bpy=2,2'-bipyridine and dppz=dipyrido[3,2-a:2',3'-c]phenazine) enhanced by DNA and sodium dodecylsulfate (SDS) has been investigated in ethanol and water mixtures by means of fluorescence spectroscopy, fluorescence microscopic imaging and voltammetry. The photoluminescence of [Ru(bpy)2(dppz)]2+ in the ethanol/Tris-water mixed system (VEthanol:VTris=1:5) is enhanced by DNA and anionic surfactant SDS, whose binding constants with the Ru(Ⅱ) complex are 5.5×105 and 4.2×102 L·mol-1, respectively. The presence of Cu(Ⅱ) ions can quench the photoluminescence of [Ru(bpy)2(dppz)]2+ in the DNA-containing mixed system via the DNA-mediated photoinduced electron transfer, in which the Stern-Volmer constant is 2.0×105 L·mol-1, being far larger than that in the SDS-containing system (9.0×103 L·mol-1). In addition, combined with the effects of SDS, DNA and Cu(Ⅱ) ions on the redox reactions of [Ru(bpy)2(dppz)]2+ on an indium-tin oxide (ITO) electrode, the copper(Ⅱ)-tuned mechanism for the photoluminescence of [Ru(bpy)2(dppz)]2+ enhanced by DNA and SDS is further explored. This study not only helps us better understand the luminescence and quenching mechanisms of DNA intercalators, but also provides a new idea for the fabrication of biomolecular light switches.
2013, 29(6): 1185-1191
doi: 10.3969/j.issn.1001-4861.2013.00.181
Abstract:
Using Cu(NO3)2·3H2O as raw materials, 25% ammonia as complexing agent and NaOH as precipitant, the size tunable nano CuO was synthesized in variable alcohol-water systems. The component and the optimized calcination temperature of the precursor were determined through TG-DTA analysis. The solvent used in ammonia -water system was ethanol, butanol and octanol respectively and their effect on the product particle size was discussed. The results showed that the specific surface areas of CuO nanoparticles increased and their sizes decreased with increasing the carbon chain length of alcohol used. The surface sulphidization of CuO (CuO/CuS) was obtained by heat treatment of CuO and elemental sulfur mixture in a tube type furnace under nitrogen atmosphere at 200 ℃ for 90 minutes. Powder X-ray diffraction and infrared absorption spectroscopy analysis methods were used to characterize the physical and chemical properties of nano CuO and CuO/CuS. The adsorption of potassium ethyl xanthate at the surfaces of nano CuO and CuO/CuS was studied. The result revealed that the capability of CuO/CuS adsorbing potassium ethyl xanthate was markedly enhanced, further proving the surface sulphidization occurred on the surface of nano CuO.
Using Cu(NO3)2·3H2O as raw materials, 25% ammonia as complexing agent and NaOH as precipitant, the size tunable nano CuO was synthesized in variable alcohol-water systems. The component and the optimized calcination temperature of the precursor were determined through TG-DTA analysis. The solvent used in ammonia -water system was ethanol, butanol and octanol respectively and their effect on the product particle size was discussed. The results showed that the specific surface areas of CuO nanoparticles increased and their sizes decreased with increasing the carbon chain length of alcohol used. The surface sulphidization of CuO (CuO/CuS) was obtained by heat treatment of CuO and elemental sulfur mixture in a tube type furnace under nitrogen atmosphere at 200 ℃ for 90 minutes. Powder X-ray diffraction and infrared absorption spectroscopy analysis methods were used to characterize the physical and chemical properties of nano CuO and CuO/CuS. The adsorption of potassium ethyl xanthate at the surfaces of nano CuO and CuO/CuS was studied. The result revealed that the capability of CuO/CuS adsorbing potassium ethyl xanthate was markedly enhanced, further proving the surface sulphidization occurred on the surface of nano CuO.
2013, 29(6): 1192-1198
doi: 10.3969/j.issn.1001-4861.2013.00.153
Abstract:
A series of phosphors (Ca, Me)La4Si3O13:Eu3+ (Me=Sr, Ba) were prepared via solid-state reactions. The variations of lattice parameters and the luminescence properties were investigated based on modifying dopant concentration of Eu3+ and substitution amount of Ca2+ by Sr2+ or Ba2+ in the host. The optimal mole ratio nEu3+ to nLa3+ in the phosphor is 1:7 and the intensity ratio of emission transition 5D0-7F2 to 5D0-7F1 is 2.55 in the studied range. The lattice parameters a and c reduce linearly with concentrations of dopant Eu3+ and c is more noticeable so that a/c value increases. There are linear relationships between lattice parameters and substitution amounts of Sr2+ or Ba2+ to Ca2+ in host, but values of a and c increase and that of a/c decreases due to continuous solid solutions formed. The maximum of the luminescent intensities of Eu3+ emission appears in the sample in which the substitution amount of Sr2+ to Ca2+ is 0.4 mole per mole host, however, the intensities increase with the substitution concentrations of Ba2+ ions all the while,as well as a change in rate of grade at content 0.4 of Ba2+ ion,and the most intensity reaches till whole substitution. The CIE of the sample is (0.638 5, 0.353 0).
A series of phosphors (Ca, Me)La4Si3O13:Eu3+ (Me=Sr, Ba) were prepared via solid-state reactions. The variations of lattice parameters and the luminescence properties were investigated based on modifying dopant concentration of Eu3+ and substitution amount of Ca2+ by Sr2+ or Ba2+ in the host. The optimal mole ratio nEu3+ to nLa3+ in the phosphor is 1:7 and the intensity ratio of emission transition 5D0-7F2 to 5D0-7F1 is 2.55 in the studied range. The lattice parameters a and c reduce linearly with concentrations of dopant Eu3+ and c is more noticeable so that a/c value increases. There are linear relationships between lattice parameters and substitution amounts of Sr2+ or Ba2+ to Ca2+ in host, but values of a and c increase and that of a/c decreases due to continuous solid solutions formed. The maximum of the luminescent intensities of Eu3+ emission appears in the sample in which the substitution amount of Sr2+ to Ca2+ is 0.4 mole per mole host, however, the intensities increase with the substitution concentrations of Ba2+ ions all the while,as well as a change in rate of grade at content 0.4 of Ba2+ ion,and the most intensity reaches till whole substitution. The CIE of the sample is (0.638 5, 0.353 0).
2013, 29(6): 1199-1205
doi: 10.3969/j.issn.1001-4861.2013.00.190
Abstract:
Single-crystal MgO nanobelts were synthesized by direct current (DC) arc plasma jet chemical vapor deposition (CVD) on Mo substrates. An attempt has been made to prepare MgO nanobelts through decomposition of magnesium nitrate under argon and hydrogen flow at 950 ℃ for different durations. The MgO nanobelts were characterized by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), and powder X-ray diffraction (XRD) pattern. When reaction time was increased from 0.5 to 12 min, the initially formed “tadpole-like” MgO nanostructures transformed into “dendrite-like” structures, nanobelts, and finally nanorods. The “tadpole-like” nanostructures are mainly belts with Mo nanoparticles capped at the MgO nanobelts’ ends, and the nanostructure is covered by an amorphous layer. The nanobelts prepared after 5 min with widths ranging from 30 to 50 nm. The growth of MgO nanobelts was initiated by Mo catalyst nanoparticles via a catalyst-assisted vapor-liquid-solid (VLS) process, and a side growth along the belt width direction via a vapor-solid (VS) process was also suggested. Moreover, the MgO nanobelts exhibited strong ultraviolet-blue emission. The strong optical properties were correlated with large surface area and presence of oxide ions in low coordination (LC) OLC2- (where LC=5C, 4C and 3C for terrace, edge, corner and kink sites, respectively) along with defects, which was revealed by fourier transform Infrared (FTIR) spectrometer and photoluminescence (PL) spectroscopy studies. Our group for the first time reported the DC arc plasma jet CVD method to obtain single crystalline MgO nanobelts, which possesses the advantages of being simple, economical, fast, effective and environmentally benign.
Single-crystal MgO nanobelts were synthesized by direct current (DC) arc plasma jet chemical vapor deposition (CVD) on Mo substrates. An attempt has been made to prepare MgO nanobelts through decomposition of magnesium nitrate under argon and hydrogen flow at 950 ℃ for different durations. The MgO nanobelts were characterized by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), and powder X-ray diffraction (XRD) pattern. When reaction time was increased from 0.5 to 12 min, the initially formed “tadpole-like” MgO nanostructures transformed into “dendrite-like” structures, nanobelts, and finally nanorods. The “tadpole-like” nanostructures are mainly belts with Mo nanoparticles capped at the MgO nanobelts’ ends, and the nanostructure is covered by an amorphous layer. The nanobelts prepared after 5 min with widths ranging from 30 to 50 nm. The growth of MgO nanobelts was initiated by Mo catalyst nanoparticles via a catalyst-assisted vapor-liquid-solid (VLS) process, and a side growth along the belt width direction via a vapor-solid (VS) process was also suggested. Moreover, the MgO nanobelts exhibited strong ultraviolet-blue emission. The strong optical properties were correlated with large surface area and presence of oxide ions in low coordination (LC) OLC2- (where LC=5C, 4C and 3C for terrace, edge, corner and kink sites, respectively) along with defects, which was revealed by fourier transform Infrared (FTIR) spectrometer and photoluminescence (PL) spectroscopy studies. Our group for the first time reported the DC arc plasma jet CVD method to obtain single crystalline MgO nanobelts, which possesses the advantages of being simple, economical, fast, effective and environmentally benign.
2013, 29(6): 1206-1214
doi: 10.3969/j.issn.1001-4861.2013.00.195
Abstract:
Ce-Ti mixed oxides (CeO2-TiO2) were prepared as the support for solid tungstophosphoric acid (H3PW12O40). FTIR, XRD, BET surface area measurement, SEM and TPD-MS were employed for characterization and mechanism analysis. CeO2-TiO2 is an excellent support for H3PW12O40. By loading on CeO2-TiO2, the NOx adsorption efficiency of H3PW12O40 increases, with a peak efficiency of 90%, which is much higher than that of H3PW12O40 (60%). With the increase of H3PW12O40 loading, the NOx adsorption efficiency tends to reach a peak value before dropping down. The mechanical grinding method is superior to the incipient impregnation method for preparing H3PW12O40/CeO2-TiO2. In NOx adsorption process, NOx reacts with H3PW12O40 to produce NOH+. The crystal water in the secondary structure of H3PW12O40 plays an important role in NOx adsorption. The lost crystal water and oxygen vacancy can be effectively compensated by adding water vapor to regenerate the catalyst. Furthermore, the adsorbed NOx is decomposed into N2, O2 and N2O, and rapid heating contributes significantly to the decomposition of NOx over the catalyst, where a yield of 30.5% is achieved for N2 with the supported catalyst at a temperature ramp of 50 ℃·min-1.
Ce-Ti mixed oxides (CeO2-TiO2) were prepared as the support for solid tungstophosphoric acid (H3PW12O40). FTIR, XRD, BET surface area measurement, SEM and TPD-MS were employed for characterization and mechanism analysis. CeO2-TiO2 is an excellent support for H3PW12O40. By loading on CeO2-TiO2, the NOx adsorption efficiency of H3PW12O40 increases, with a peak efficiency of 90%, which is much higher than that of H3PW12O40 (60%). With the increase of H3PW12O40 loading, the NOx adsorption efficiency tends to reach a peak value before dropping down. The mechanical grinding method is superior to the incipient impregnation method for preparing H3PW12O40/CeO2-TiO2. In NOx adsorption process, NOx reacts with H3PW12O40 to produce NOH+. The crystal water in the secondary structure of H3PW12O40 plays an important role in NOx adsorption. The lost crystal water and oxygen vacancy can be effectively compensated by adding water vapor to regenerate the catalyst. Furthermore, the adsorbed NOx is decomposed into N2, O2 and N2O, and rapid heating contributes significantly to the decomposition of NOx over the catalyst, where a yield of 30.5% is achieved for N2 with the supported catalyst at a temperature ramp of 50 ℃·min-1.
2013, 29(6): 1215-1221
doi: 10.3969/j.issn.1001-4861.2013.00.167
Abstract:
CdS nanoparticles were deposited directly into the anodic TiO2 nanotubes via a simple hydrothermal method. The morphology and the structures were characterized by field-emission scanning electron microscopy(FESEM), X-ray diffraction(XRD), energy dispersive spectrometer(EDS) and ultraviolet-visible spectroscopy(UV-Vis). The photoelectrochemical properties of TiO2 and CdS/TiO2 catalysts were studied which indicates that compared with pure TiO2 nanotube catalyst, the photocatalytic activity of CdS/TiO2 composite photocatalyst was improved markedly both under ultraviolet and visible light.
CdS nanoparticles were deposited directly into the anodic TiO2 nanotubes via a simple hydrothermal method. The morphology and the structures were characterized by field-emission scanning electron microscopy(FESEM), X-ray diffraction(XRD), energy dispersive spectrometer(EDS) and ultraviolet-visible spectroscopy(UV-Vis). The photoelectrochemical properties of TiO2 and CdS/TiO2 catalysts were studied which indicates that compared with pure TiO2 nanotube catalyst, the photocatalytic activity of CdS/TiO2 composite photocatalyst was improved markedly both under ultraviolet and visible light.
2013, 29(6): 1222-1226
doi: 10.3969/j.issn.1001-4861.2013.00.174
Abstract:
Two chiral Salen-type Schiff base enantiomers, 1R-(2-hydroxy benzimine)-2R-(2-hydroxy naphthylmethylenimine) cyclohexane (1a) and 1S-(2-hydroxy benzimine)-2S-(2-hydroxy naphthylmethylenimine) cyclohexane (1b), synthesized though the solution reactions of phenyl salicylate, trans-1, 2-diaminocyclohexane and 2-hydroxynaphthalene-1-carbaldehyde in 2-propanol, have been characterized by EA, IR, X-ray crystallography, Circular Dichroism (CD) spectrum and biological tests. X-ray crystallography and CD spectrum reveal 1a and 1b are optically chiral enantiomers. Biological tests show that 1a has inhibiting bacteria effects. CCDC: 932330, 1; 932331, 2.
Two chiral Salen-type Schiff base enantiomers, 1R-(2-hydroxy benzimine)-2R-(2-hydroxy naphthylmethylenimine) cyclohexane (1a) and 1S-(2-hydroxy benzimine)-2S-(2-hydroxy naphthylmethylenimine) cyclohexane (1b), synthesized though the solution reactions of phenyl salicylate, trans-1, 2-diaminocyclohexane and 2-hydroxynaphthalene-1-carbaldehyde in 2-propanol, have been characterized by EA, IR, X-ray crystallography, Circular Dichroism (CD) spectrum and biological tests. X-ray crystallography and CD spectrum reveal 1a and 1b are optically chiral enantiomers. Biological tests show that 1a has inhibiting bacteria effects. CCDC: 932330, 1; 932331, 2.
2013, 29(6): 1227-1234
doi: 10.3969/j.issn.1001-4861.2013.00.227
Abstract:
Three new unsymmetric diimines L, LMe and LCl were synthesized by a two-step process. Initially, the starting Schiff base 2-hydroxy-N-(5-nitrofurylidene)aniline (SB-NO2) was obtained by using 5-nitro-furfural and 2-hydroxyaniline. Nitro group of SB-NO2 was reduced into its amino derivative, SB-NH2, in solution. Diimines L, LMe and LCl were obtained with the addition of 2-hydroxybenzaldehyde, 2-hydroxy-5-methylbenzaldehyde and 2-hydroxy-5-chlorobenzaldehyde, respectively, into SB-NH2 solution. Dimeric, binuclear Fe(Ⅲ) and Ni(Ⅱ) complexes of these ligands were also synthesized. Diimines and their complexes were characterized by elemental analyses, LC-MS, IR, electronic spectra, 1H and 13C-NMR spectra, TGA, conductivity and magnetic measurements. The antibacterial activities of the ligands and the complexes were investigated against five bacteria. All of the compounds showed moderate activities against Escherichia coli, Bacillus subtilis and Yersinia enterecolitica. The highest activity values were obtained by Fe(Ⅲ) complexes against Pseudomonas aeruginosa.
Three new unsymmetric diimines L, LMe and LCl were synthesized by a two-step process. Initially, the starting Schiff base 2-hydroxy-N-(5-nitrofurylidene)aniline (SB-NO2) was obtained by using 5-nitro-furfural and 2-hydroxyaniline. Nitro group of SB-NO2 was reduced into its amino derivative, SB-NH2, in solution. Diimines L, LMe and LCl were obtained with the addition of 2-hydroxybenzaldehyde, 2-hydroxy-5-methylbenzaldehyde and 2-hydroxy-5-chlorobenzaldehyde, respectively, into SB-NH2 solution. Dimeric, binuclear Fe(Ⅲ) and Ni(Ⅱ) complexes of these ligands were also synthesized. Diimines and their complexes were characterized by elemental analyses, LC-MS, IR, electronic spectra, 1H and 13C-NMR spectra, TGA, conductivity and magnetic measurements. The antibacterial activities of the ligands and the complexes were investigated against five bacteria. All of the compounds showed moderate activities against Escherichia coli, Bacillus subtilis and Yersinia enterecolitica. The highest activity values were obtained by Fe(Ⅲ) complexes against Pseudomonas aeruginosa.
2013, 29(6): 1235-1242
doi: 10.3969/j.issn.1001-4861.2013.00.180
Abstract:
The complex formation equilibria involved in the binary systems of M(Ⅱ)-Dopa in 0～60% (V/V) propylene glycol (PG)-water mixtures were studied using pH-metric titration at constant temperature of 303 K and a constant ionic strength of 0.16 mol·L-1 held by using sodium chloride as an electrolyte. The models contained MLH, ML2, ML2H and ML2H2 for Ca(Ⅱ) and Mg(Ⅱ), but ML, MLH, ML2, ML2H and ML2H2 for Zn(Ⅱ) in PG-water mixtures. The trend in the variation of stability constants with change in the dielectric constant of the medium was explained on the basis of electrostatic and non-electrostatic forces. Distributions of these species with pH value at different compositions of PG-water mixtures were also presented.
The complex formation equilibria involved in the binary systems of M(Ⅱ)-Dopa in 0～60% (V/V) propylene glycol (PG)-water mixtures were studied using pH-metric titration at constant temperature of 303 K and a constant ionic strength of 0.16 mol·L-1 held by using sodium chloride as an electrolyte. The models contained MLH, ML2, ML2H and ML2H2 for Ca(Ⅱ) and Mg(Ⅱ), but ML, MLH, ML2, ML2H and ML2H2 for Zn(Ⅱ) in PG-water mixtures. The trend in the variation of stability constants with change in the dielectric constant of the medium was explained on the basis of electrostatic and non-electrostatic forces. Distributions of these species with pH value at different compositions of PG-water mixtures were also presented.
2013, 29(6): 1243-1248
doi: 10.3969/j.issn.1001-4861.2013.00.188
Abstract:
Two new metal-organic coordination polymers [Pb(NA)L]n 1, [Pb(CH3COO)L]n·nH2O 2 (H2NA=nicotinic acid, L=2-(4-nitrophenol)-1H-imidazo[4,5-f][1,10]phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. They are further extended into a three-dimensional supramolecular network structure through hydrogen-bonding and π-π interactions. Moreover, the luminesent property of 1 and 2 have been investigated in the solid state. CCDC: 931504, 1; 931505, 2.
Two new metal-organic coordination polymers [Pb(NA)L]n 1, [Pb(CH3COO)L]n·nH2O 2 (H2NA=nicotinic acid, L=2-(4-nitrophenol)-1H-imidazo[4,5-f][1,10]phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. They are further extended into a three-dimensional supramolecular network structure through hydrogen-bonding and π-π interactions. Moreover, the luminesent property of 1 and 2 have been investigated in the solid state. CCDC: 931504, 1; 931505, 2.
2013, 29(6): 1249-1254
doi: 10.3969/j.issn.1001-4861.2013.00.189
Abstract:
Two novel cadmium coordination polymers: Cd(BrBDC)(py) (1) and Cd(NH2BDC)(H2O) (2) (BrBDC=2-bromo-1,4-benzenedicarboxylate, NH2BDC=2-amino-1,4-benzenedicarboxylate, py=pyridine), were synthesized under solvothermal conditions. The crystal structure of Cd(BrBDC)(py) is based on infinite chains of carboxylato-bridged six coordinated Cd(Ⅱ) ions that are linked via the BrBDC ligands to form a 2D structure. Cd(NH2BDC)(H2O) is based on brick-like 2D layers constructed by carboxylato that are crosslinked by the amino groups into a 3D structure. The photoluminescence of both compounds are studied. CCDC: 915674, 1; 915673, 2.
Two novel cadmium coordination polymers: Cd(BrBDC)(py) (1) and Cd(NH2BDC)(H2O) (2) (BrBDC=2-bromo-1,4-benzenedicarboxylate, NH2BDC=2-amino-1,4-benzenedicarboxylate, py=pyridine), were synthesized under solvothermal conditions. The crystal structure of Cd(BrBDC)(py) is based on infinite chains of carboxylato-bridged six coordinated Cd(Ⅱ) ions that are linked via the BrBDC ligands to form a 2D structure. Cd(NH2BDC)(H2O) is based on brick-like 2D layers constructed by carboxylato that are crosslinked by the amino groups into a 3D structure. The photoluminescence of both compounds are studied. CCDC: 915674, 1; 915673, 2.
Crystal Structures and Properties of Two Novel Copper Compounds Constructed from Bistriazole Methane
2013, 29(6): 1255-1262
doi: 10.3969/j.issn.1001-4861.2013.00.178
Abstract:
Using a flexible bis-triazole ligand bis(1,2,4-triazol-1-y1)metane (btm), two new copper(Ⅱ) coordination polymers [Cu0.5(btm)Cl]n (1) and [Cu(btm)Cl2]n (2) have been synthesized under hydrothermal conditions. The coordinating mode of chlorine anions can be tuned as a result of changing the metal/ligand ratio in the reaction system, which ultimately forms two novel structures. 1 possesses infinite 1D chain structure, and uncommonly four-fold Cl…H-C hydrogen bonds help the chains form a 3D supramolecular architecture. 2 features 2D (4.4) net framewok. Hydrogen bonds (Cl…H-C) reside among the 2D layers, which link the 2D layers to lead to a 3D supramolecular architecture. For 1 and 2, X-ray crystallography, elemental analysis, thermal stability and EPR spectra have been carried out. CCDC: 932333, 1; 932332, 2.
Using a flexible bis-triazole ligand bis(1,2,4-triazol-1-y1)metane (btm), two new copper(Ⅱ) coordination polymers [Cu0.5(btm)Cl]n (1) and [Cu(btm)Cl2]n (2) have been synthesized under hydrothermal conditions. The coordinating mode of chlorine anions can be tuned as a result of changing the metal/ligand ratio in the reaction system, which ultimately forms two novel structures. 1 possesses infinite 1D chain structure, and uncommonly four-fold Cl…H-C hydrogen bonds help the chains form a 3D supramolecular architecture. 2 features 2D (4.4) net framewok. Hydrogen bonds (Cl…H-C) reside among the 2D layers, which link the 2D layers to lead to a 3D supramolecular architecture. For 1 and 2, X-ray crystallography, elemental analysis, thermal stability and EPR spectra have been carried out. CCDC: 932333, 1; 932332, 2.
2013, 29(6): 1263-1268
doi: 10.3969/j.issn.1001-4861.2013.00.170
Abstract:
A Co(Ⅱ) coordination polymer has been synthesized hydrothermally, namely, {[Co(L)(chdc)]2H2O}n (1), (L=1,3-bis-(benzimidazole-1-yl-methylene)-benzene, H2chdc=1,4-cyclohexanedicrboxylic acid). Structure analysis indicates that complex 1 belongs to monoclinic system, space group C2/c, a=1.450 4(1) nm, b=1.834 9(2) nm, c=2.128 7(2) nm, β=94.325(1)°, V=5.649 2(9) nm3, Z=4. Compound 1 exhibits a looped-like chain structure, then the chains are connected into 2D supramolecular structure by interchain π-π satcking interaction. Complex 1 possesses a remarkable activity for degradation of Congo red in a Fenton-like process. CCDC: 892179.
A Co(Ⅱ) coordination polymer has been synthesized hydrothermally, namely, {[Co(L)(chdc)]2H2O}n (1), (L=1,3-bis-(benzimidazole-1-yl-methylene)-benzene, H2chdc=1,4-cyclohexanedicrboxylic acid). Structure analysis indicates that complex 1 belongs to monoclinic system, space group C2/c, a=1.450 4(1) nm, b=1.834 9(2) nm, c=2.128 7(2) nm, β=94.325(1)°, V=5.649 2(9) nm3, Z=4. Compound 1 exhibits a looped-like chain structure, then the chains are connected into 2D supramolecular structure by interchain π-π satcking interaction. Complex 1 possesses a remarkable activity for degradation of Congo red in a Fenton-like process. CCDC: 892179.
2013, 29(6): 1269-1276
doi: 10.3969/j.issn.1001-4861.2013.00.173
Abstract:
Two new complexes, namely {[La(pydc)(OAc)(H2O)]·2H2O}n(1) and {[Tm2Cu(pydc)4(H2O)6]·2H2O}n(2) (H2pydc=2,5-pyridinedicarboxylic acid), have been synthesized and structurally characterized. Structure analyses reveal that complex 1 has intricate 3D micropore framework with 1D square channels, which is constructed by 2,5-pyridinedicarboxylate and acetate ligands. Complex 2 shows a 3D open framework in which 2,5-pydc2- dianion ligand adopts μ2-η1-η1- and μ4-bridge coordination mode. In addition, thermal stability for 1 and 2 and temperature-dependent magnetic susceptibilities for 2 have been investigated in detail. CCDC: 884201, 1;884200, 2.
Two new complexes, namely {[La(pydc)(OAc)(H2O)]·2H2O}n(1) and {[Tm2Cu(pydc)4(H2O)6]·2H2O}n(2) (H2pydc=2,5-pyridinedicarboxylic acid), have been synthesized and structurally characterized. Structure analyses reveal that complex 1 has intricate 3D micropore framework with 1D square channels, which is constructed by 2,5-pyridinedicarboxylate and acetate ligands. Complex 2 shows a 3D open framework in which 2,5-pydc2- dianion ligand adopts μ2-η1-η1- and μ4-bridge coordination mode. In addition, thermal stability for 1 and 2 and temperature-dependent magnetic susceptibilities for 2 have been investigated in detail. CCDC: 884201, 1;884200, 2.
2013, 29(6): 1277-1282
doi: 10.3969/j.issn.1001-4861.2013.00.184
Abstract:
A new two-dimensional coordination polymer of [Mn(DSBA)(FBIX)0.5]n (1) (H2DSBA=2,2'-disulfanediyl-dibenzoic acid and FBIX=2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-yl-methyl) benzene) has been prepared and chara-cterized by elemental analysis, IR spectroscopy, TGA and single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with a=1.050 41(12) nm, b=1.160 23(13) nm, c=1.940 36(18) nm, β=116.647(3)°, V=2.113 6(4) nm3, Dc=1.617 g·cm-3, Z=4, F(000)=1 040, Goof=1.052, R1=0.057 9, wR2=0.097 0. Complex 1 shows a two-dimensional layer structure based on paddle-wheel building units. Magnetic-property studies show that antiferromagnetic exchange interactions propagate among the Mn(Ⅱ) ions. CCDC: 834854.
A new two-dimensional coordination polymer of [Mn(DSBA)(FBIX)0.5]n (1) (H2DSBA=2,2'-disulfanediyl-dibenzoic acid and FBIX=2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-yl-methyl) benzene) has been prepared and chara-cterized by elemental analysis, IR spectroscopy, TGA and single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with a=1.050 41(12) nm, b=1.160 23(13) nm, c=1.940 36(18) nm, β=116.647(3)°, V=2.113 6(4) nm3, Dc=1.617 g·cm-3, Z=4, F(000)=1 040, Goof=1.052, R1=0.057 9, wR2=0.097 0. Complex 1 shows a two-dimensional layer structure based on paddle-wheel building units. Magnetic-property studies show that antiferromagnetic exchange interactions propagate among the Mn(Ⅱ) ions. CCDC: 834854.
2013, 29(6): 1283-1288
doi: 10.3969/j.issn.1001-4861.2013.00.224
Abstract:
Two new Au(Ⅰ) complexes, namely, (ph3P)Au(mpo) (1) and [Au(mpo)2][Na(H2O)4]·H2O (2) have been synthesized via the reaction of (ph3P)AuCl with 2-mercaptopyridine-1-oxide sodium (Nampo) in dichloromethane (CH2Cl2) solution. Their crystal structures have been determined by elemental analysis and single-crystal X-ray diffraction studies. Complex 1 crystallizes in the monoclinic system, space group P21/c, and features isolated (ph3P)Au(mpo) molecules. Complex 2 crystallizes in the orthorhombic system, space group Pnma. The structure of complex 2 features three-dimensional (3D) network composed of Au(mpo)2 units, 1D Na(H2O)4 belt as well as isolated H2O molecules interlinked via weak hydrogen bonds. Complex 2 exhibits blue emission with λmax=423.5 nm by irradiation of UV light (λ=300 nm). CCDC: 932336, 1; 932337, 2.
Two new Au(Ⅰ) complexes, namely, (ph3P)Au(mpo) (1) and [Au(mpo)2][Na(H2O)4]·H2O (2) have been synthesized via the reaction of (ph3P)AuCl with 2-mercaptopyridine-1-oxide sodium (Nampo) in dichloromethane (CH2Cl2) solution. Their crystal structures have been determined by elemental analysis and single-crystal X-ray diffraction studies. Complex 1 crystallizes in the monoclinic system, space group P21/c, and features isolated (ph3P)Au(mpo) molecules. Complex 2 crystallizes in the orthorhombic system, space group Pnma. The structure of complex 2 features three-dimensional (3D) network composed of Au(mpo)2 units, 1D Na(H2O)4 belt as well as isolated H2O molecules interlinked via weak hydrogen bonds. Complex 2 exhibits blue emission with λmax=423.5 nm by irradiation of UV light (λ=300 nm). CCDC: 932336, 1; 932337, 2.
2013, 29(6): 1289-1294
doi: 10.3969/j.issn.1001-4861.2013.00.221
Abstract:
One compound [Co(AIP)(HAIP)2]·(OH)2(LH=2-(9-anthryl)-1H-imidazo[4,5-f][1,10] phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic system, space group C2/c, with a=1.152 9(2), b=3.673 6(7), c=1.584 1(3) nm, β=107.73(3), V=6.382(2) nm3, Z=4 (at 291(2) K). In the crystal structure, the Co(Ⅲ) ion is six match coordination with six nitrogen atoms which from two different HAIP ligands and one AIP ligand, assuming a slightly distorted octahedral.
One compound [Co(AIP)(HAIP)2]·(OH)2(LH=2-(9-anthryl)-1H-imidazo[4,5-f][1,10] phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic system, space group C2/c, with a=1.152 9(2), b=3.673 6(7), c=1.584 1(3) nm, β=107.73(3), V=6.382(2) nm3, Z=4 (at 291(2) K). In the crystal structure, the Co(Ⅲ) ion is six match coordination with six nitrogen atoms which from two different HAIP ligands and one AIP ligand, assuming a slightly distorted octahedral.
2013, 29(6): 1295-1301
doi: 10.3969/j.issn.1001-4861.2013.00.199
Abstract:
Two silicon(Ⅳ) compounds with α-diimine ligands, L(SiMe3)2(2) (L=[(2, 6-iPr2C6H3)NC(Me)]2), L'(SiMe3)2 (4) (L'=[(2, 6-iPr2C6H3)NCH]2) were synthesized by the reaction of corresponding sodium salts or lithium salts with chloro(trimethyl)silane. The crystal of compound 2 belongs to the monoclinic system, space group P21/n with a=0.958 5(3) nm, b=1.811 8(5) nm, c=0.982 4(3) nm, β=102.173(3), V=1.667 7(8) nm3, Z=2. The crystal of compound 4 belongs to the triclinic system, space group P1 with a=0.883 7(2) nm, b=0.967 5(2) nm, c=1.142 9(4) nm, β=88.94(2), V=0.835 8(4) nm3, Z=1. A zig-zag arrangement of the atoms N(1), C(13), C(13i), and N(1i) is the core of both of the two molecular structures. Both of the two complexes were characterized by single crystal X-ray structural analysis, 1H NMR, elemental analysis, and FTIR spectra, analyzed by UV-Vis spectrum and fluorescent spectra properties. The compounds exhibit strong fluorescence under ultraviolet light. CCDC: 896958, 2; 896957, 4.
Two silicon(Ⅳ) compounds with α-diimine ligands, L(SiMe3)2(2) (L=[(2, 6-iPr2C6H3)NC(Me)]2), L'(SiMe3)2 (4) (L'=[(2, 6-iPr2C6H3)NCH]2) were synthesized by the reaction of corresponding sodium salts or lithium salts with chloro(trimethyl)silane. The crystal of compound 2 belongs to the monoclinic system, space group P21/n with a=0.958 5(3) nm, b=1.811 8(5) nm, c=0.982 4(3) nm, β=102.173(3), V=1.667 7(8) nm3, Z=2. The crystal of compound 4 belongs to the triclinic system, space group P1 with a=0.883 7(2) nm, b=0.967 5(2) nm, c=1.142 9(4) nm, β=88.94(2), V=0.835 8(4) nm3, Z=1. A zig-zag arrangement of the atoms N(1), C(13), C(13i), and N(1i) is the core of both of the two molecular structures. Both of the two complexes were characterized by single crystal X-ray structural analysis, 1H NMR, elemental analysis, and FTIR spectra, analyzed by UV-Vis spectrum and fluorescent spectra properties. The compounds exhibit strong fluorescence under ultraviolet light. CCDC: 896958, 2; 896957, 4.
2013, 29(6): 1302-1306
doi: 10.3969/j.issn.1001-4861.2013.00.171
Abstract:
A new metal-organic coordination polymer [Mn(C2O4)(bimb)]n·0.25nH2O (1) (H2C2O4=oxalic acid, bimb=1,4-bis(imidazol-1-yl)-butane) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, UV spectrum, TG and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P1 with a=0.928 62(12) nm, b=0.965 61(13) nm, c=0.972 27(13) nm, α=67.992(2)°, β=87.361(2)°, γ=64.596(2)°, V=0.723 25(17) nm3, C24H29Mn2N8O8.5, Mr=675.43, Dc=1.551 g·cm-3, μ(Mo Kα)=0.936 mm-1, F(000)=347, Z=1, R=0.031 2, wR=0.074 9. In the crystalstructure, the manganese atom is six-coordinated with four carboxylate oxygen atoms from two different C2O42- ligands and two nitrogen atoms from two bimb ligands, showing a distorted octahedral geometry. CCDC: 929937.
A new metal-organic coordination polymer [Mn(C2O4)(bimb)]n·0.25nH2O (1) (H2C2O4=oxalic acid, bimb=1,4-bis(imidazol-1-yl)-butane) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, UV spectrum, TG and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P1 with a=0.928 62(12) nm, b=0.965 61(13) nm, c=0.972 27(13) nm, α=67.992(2)°, β=87.361(2)°, γ=64.596(2)°, V=0.723 25(17) nm3, C24H29Mn2N8O8.5, Mr=675.43, Dc=1.551 g·cm-3, μ(Mo Kα)=0.936 mm-1, F(000)=347, Z=1, R=0.031 2, wR=0.074 9. In the crystalstructure, the manganese atom is six-coordinated with four carboxylate oxygen atoms from two different C2O42- ligands and two nitrogen atoms from two bimb ligands, showing a distorted octahedral geometry. CCDC: 929937.
2013, 29(6): 1307-1311
doi: 10.3969/j.issn.1001-4861.2013.00.183
Abstract:
Manganese substituted ferric perovskite-type catalysts were prepared by co-precipitation method. The title catalysts were calcined at 700 ℃ and characterized by XRD, TPR and TG-DSC techniques. The catalytic activity was evaluated using methane combustion as a model reaction. The specific surface area was calculated by BET model. The values of the apparent activation energy were estimated from the Arrhenius plots based on a CH4 first-order rate equation. The samples exhibit significant catalytic activity for methane combustion at 700 ℃. With increasing the substitution of Mn2+, the activities of the catalysts are improved. Upon calcination at 700 ℃ the catalyst SrMnO3 shows an excellent activity for methane combustion (the conversion of 10% and 90% are obtained at 435 ℃ and 457 ℃, respectively).
Manganese substituted ferric perovskite-type catalysts were prepared by co-precipitation method. The title catalysts were calcined at 700 ℃ and characterized by XRD, TPR and TG-DSC techniques. The catalytic activity was evaluated using methane combustion as a model reaction. The specific surface area was calculated by BET model. The values of the apparent activation energy were estimated from the Arrhenius plots based on a CH4 first-order rate equation. The samples exhibit significant catalytic activity for methane combustion at 700 ℃. With increasing the substitution of Mn2+, the activities of the catalysts are improved. Upon calcination at 700 ℃ the catalyst SrMnO3 shows an excellent activity for methane combustion (the conversion of 10% and 90% are obtained at 435 ℃ and 457 ℃, respectively).
2013, 29(6): 1312-1318
doi: 10.3969/j.issn.1001-4861.2013.00.164
Abstract:
A new cadmium (Ⅱ) coordination polymer, {[Cd(L)(bpy)(H2O)2·2H2O]}n(1), was prepared through hydrothermal reaction of Cd(Ⅱ) acetate with H2L (H2L=4-methylphthalic acid) and 4,4'-bipyridine. The complex was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder XRD and X-ray single-crystal diffraction. Complex 1 displays a two-dimensional layer, which is further associated through hydrogen bonding to result in a three-dimensional supramolecular architecture. In addition, the luminescence property of the complex 1 was also investigated.
A new cadmium (Ⅱ) coordination polymer, {[Cd(L)(bpy)(H2O)2·2H2O]}n(1), was prepared through hydrothermal reaction of Cd(Ⅱ) acetate with H2L (H2L=4-methylphthalic acid) and 4,4'-bipyridine. The complex was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder XRD and X-ray single-crystal diffraction. Complex 1 displays a two-dimensional layer, which is further associated through hydrogen bonding to result in a three-dimensional supramolecular architecture. In addition, the luminescence property of the complex 1 was also investigated.
2013, 29(6): 1319-1327
doi: 10.3969/j.issn.1001-4861.2013.00.185
Abstract:
Four dinuclear transition metal complexes with schiff base ligand of bis-salicylaldehyde have been synthesized and structurally characterized by means of elemental analysis, IR, UV, TGA and X-ray single-crystal diffraction. The results of structural analysis indicate that complex 1, 3 and 4 belong to triclinic crystal system, space group P1 and the complex 2 belong to monoclinic crystal system, space group C2/c. In complex 1, two copper ions show different coordination environment, one of which has a five-coordinate, slightly distorted tetragonal pyramidal geometry and another has a four-coordinate squareplanar geometry. In complex 4, the binuclear units are held together to form an infinite 1D chain by bridging phenol O atoms.
Four dinuclear transition metal complexes with schiff base ligand of bis-salicylaldehyde have been synthesized and structurally characterized by means of elemental analysis, IR, UV, TGA and X-ray single-crystal diffraction. The results of structural analysis indicate that complex 1, 3 and 4 belong to triclinic crystal system, space group P1 and the complex 2 belong to monoclinic crystal system, space group C2/c. In complex 1, two copper ions show different coordination environment, one of which has a five-coordinate, slightly distorted tetragonal pyramidal geometry and another has a four-coordinate squareplanar geometry. In complex 4, the binuclear units are held together to form an infinite 1D chain by bridging phenol O atoms.
2013, 29(6): 1328-1332
doi: 10.3969/j.issn.1001-4861.2013.00.202
Abstract:
A 3D network Ca(Ⅱ) complex has been synthesized in CH3CH2OH solvent, and characterized by elemental analysis, IR spectra, molar conductivity, thermal analysis and X-ray crystal structure determination. The results of crystal structure show that that each Ca(Ⅱ) ion is coordinated with six oxygen atoms from Schiff base ligands (Schiff base derived from 2-carboxybenzaldehyde and diethylenetriamine), forming a distorted octahedral coordination geometry. The compound formed 3D network structure through hydrogen bonds and π-π interaction of benzene rings. The antitumor activity of the Ca(Ⅱ) complex also was investigated. CCDC: 709605.
A 3D network Ca(Ⅱ) complex has been synthesized in CH3CH2OH solvent, and characterized by elemental analysis, IR spectra, molar conductivity, thermal analysis and X-ray crystal structure determination. The results of crystal structure show that that each Ca(Ⅱ) ion is coordinated with six oxygen atoms from Schiff base ligands (Schiff base derived from 2-carboxybenzaldehyde and diethylenetriamine), forming a distorted octahedral coordination geometry. The compound formed 3D network structure through hydrogen bonds and π-π interaction of benzene rings. The antitumor activity of the Ca(Ⅱ) complex also was investigated. CCDC: 709605.
