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2013 Volume 29 Issue 9
2013, 29(9): 1777-1786
doi: 10.3969/j.issn.1001-4861.2013.00.269
Abstract:
Zeolite LTA with intracrystal mesopores was built using four different organic functionized SiO2 as configuration units. The effects of the synthesis conditions, including that of the alkalinity, the Si/Al molar ratio of synthesis mixture and crystallization time, on the growth process of the mesostructured zeolite crystals were investigated. Phenylaminopropyl-trimethoxysilane is the best candidate to create intracrystal mesopores in zeolite LTA crystals. The growth process of the mesostructured zeolite crystals was studied. Mesoporous size of the zeolite LTA can be modulated by selecting different kinds of organosilanes. Within a certain range, the external surface area and the mesoporous volume increase with the increasing organic function degree of the silica source. The results confirm that the synthesis method by the bond-blocking principle is an effective route to prepare zeolite LTA with tunable intracrystalline mesopores.
Zeolite LTA with intracrystal mesopores was built using four different organic functionized SiO2 as configuration units. The effects of the synthesis conditions, including that of the alkalinity, the Si/Al molar ratio of synthesis mixture and crystallization time, on the growth process of the mesostructured zeolite crystals were investigated. Phenylaminopropyl-trimethoxysilane is the best candidate to create intracrystal mesopores in zeolite LTA crystals. The growth process of the mesostructured zeolite crystals was studied. Mesoporous size of the zeolite LTA can be modulated by selecting different kinds of organosilanes. Within a certain range, the external surface area and the mesoporous volume increase with the increasing organic function degree of the silica source. The results confirm that the synthesis method by the bond-blocking principle is an effective route to prepare zeolite LTA with tunable intracrystalline mesopores.
2013, 29(9): 1787-1792
doi: 10.3969/j.issn.1001-4861.2013.00.231
Abstract:
Active carbons with more micropores were prepared with wooden active carbon particles and KOH used as raw material and active agent respectively. The optimized weight ratio between wooden active carbon and KOH was obtained. The low-temperature N2 adsorption, SEM and XRD methods were employed to investigate the specific surface area, pore-structure, pore size distribution, morphology of particle surface and crystal structure of the as-made samples. The xylene-removal abilities of the samples were assessed with adsorbing experiments on gas streams containing 1,3-xylene (50 mg·L-1). It was revealed by the results that re-active operation with KOH upon the wooden active carbon obviously enlarge the 1,3-xylene adsorption capacity of the samples which might be resulted by the newly formed micro-pores.
Active carbons with more micropores were prepared with wooden active carbon particles and KOH used as raw material and active agent respectively. The optimized weight ratio between wooden active carbon and KOH was obtained. The low-temperature N2 adsorption, SEM and XRD methods were employed to investigate the specific surface area, pore-structure, pore size distribution, morphology of particle surface and crystal structure of the as-made samples. The xylene-removal abilities of the samples were assessed with adsorbing experiments on gas streams containing 1,3-xylene (50 mg·L-1). It was revealed by the results that re-active operation with KOH upon the wooden active carbon obviously enlarge the 1,3-xylene adsorption capacity of the samples which might be resulted by the newly formed micro-pores.
2013, 29(9): 1793-1798
doi: 10.3969/j.issn.1001-4861.2013.00.250
Abstract:
A novel adsorbent of flower-like magnesium oxide has been prepared via hydrothermal method using CTAB as a structure director. Experiment results showed that the precursor of flower-like MgO is basic magnesium carbonate, and MgO with large surface area was obtained after calcination at 600℃. The adsorption performance of flower-like MgO was also studied in lead solution. The results of adsorption are conformed to Langmuir model, and maximum adsorption is 320 mg·g-1, which means the novel flower-like MgO has a high adsorption performance.
A novel adsorbent of flower-like magnesium oxide has been prepared via hydrothermal method using CTAB as a structure director. Experiment results showed that the precursor of flower-like MgO is basic magnesium carbonate, and MgO with large surface area was obtained after calcination at 600℃. The adsorption performance of flower-like MgO was also studied in lead solution. The results of adsorption are conformed to Langmuir model, and maximum adsorption is 320 mg·g-1, which means the novel flower-like MgO has a high adsorption performance.
2013, 29(9): 1799-1804
doi: 10.3969/j.issn.1001-4861.2013.00.228
Abstract:
Copper oxide nanoflower and iron oxide nanoring were prepared by membrane templating and hydrothermal, respectively. Copper oxide nanoflower and aluminum composite were self-assembled, so did iron oxide nanoring and aluminum. The connection between different materials were enhanced by self-assembly. The heat release and pressure of copper oxide nanoflower and aluminum were increased from 523 J·g-1, 1 858 kPa to 1 069 J·g-1, 4 389 kPa. Iron oxide nanoring and aluminum were increased from 1 448 J·g-1, 749 kPa to 2 039 J·g-1, 2 280 kPa. There are great difference between the two thermit, and the static-electric sensitivity of copper oxide nanoflower and aluminum is higher than that of most energetic materials, while the impact sensitivity of iron oxide nanoring and aluminum is lower. Thus different thermit can be used in different fields based on their performance.
Copper oxide nanoflower and iron oxide nanoring were prepared by membrane templating and hydrothermal, respectively. Copper oxide nanoflower and aluminum composite were self-assembled, so did iron oxide nanoring and aluminum. The connection between different materials were enhanced by self-assembly. The heat release and pressure of copper oxide nanoflower and aluminum were increased from 523 J·g-1, 1 858 kPa to 1 069 J·g-1, 4 389 kPa. Iron oxide nanoring and aluminum were increased from 1 448 J·g-1, 749 kPa to 2 039 J·g-1, 2 280 kPa. There are great difference between the two thermit, and the static-electric sensitivity of copper oxide nanoflower and aluminum is higher than that of most energetic materials, while the impact sensitivity of iron oxide nanoring and aluminum is lower. Thus different thermit can be used in different fields based on their performance.
2013, 29(9): 1805-1812
doi: 10.3969/j.issn.1001-4861.2013.00.254
Abstract:
A novel 8-hydroxyquinoline derivative ligand containing trifluoromethylbenzene Group: (E)-2-[2-(2-trifluromethylphenyl)vinyl]-8-hydroxyquinoline(4) and its zinc complex(5) have been synthesized and identified by 1H NMR, FFIR, MS techniques and elemental analyses. The crystal structure of ligand 4 was determined by X-ray single crystal diffraction, and its network structure is special spiral. The aggregation behavior of Zn(AcO)2·2H2O and the ligand 4 in solvents was investigated by UV-Vis, fluorescence spectrum and 1H NMR spectra titration. Fluorescence emission results showed that the λmax of ligand 4 and complex 5 were 474 nm and 601 nm, respectively. The fluorescence lifetime of ligand 4 and complex 5 were investigated in the solid state, their values are 15.6 ms and 18.1 ms, respectively. CCDC: 910120.
A novel 8-hydroxyquinoline derivative ligand containing trifluoromethylbenzene Group: (E)-2-[2-(2-trifluromethylphenyl)vinyl]-8-hydroxyquinoline(4) and its zinc complex(5) have been synthesized and identified by 1H NMR, FFIR, MS techniques and elemental analyses. The crystal structure of ligand 4 was determined by X-ray single crystal diffraction, and its network structure is special spiral. The aggregation behavior of Zn(AcO)2·2H2O and the ligand 4 in solvents was investigated by UV-Vis, fluorescence spectrum and 1H NMR spectra titration. Fluorescence emission results showed that the λmax of ligand 4 and complex 5 were 474 nm and 601 nm, respectively. The fluorescence lifetime of ligand 4 and complex 5 were investigated in the solid state, their values are 15.6 ms and 18.1 ms, respectively. CCDC: 910120.
2013, 29(9): 1813-1818
doi: 10.3969/j.issn.1001-4861.2013.00.258
Abstract:
ZnWO4 nanoparticles were synthesized by a facile solvothermal method. ZnWO4 nanoparticles were utilized as the catalyst for the formation of 5-phenyl-1H-tetrazoles from cyclo-addition reaction. The results show that the yield reaches 81% when 0.2 mmol catalyst is used at 110℃ for 10 h. However, the yield only reaches 43% and 65% for amorphous and nanorods ZnWO4, respectively. Clearly, ZnWO4 nanoparticles display superior catalytic performance. This high activity might be attributed to the larger surface area and more active sites that originate from the small size and good dispersibility of ZnWO4 nanoparticles. The unsaturated W atoms on the surface of ZnWO4 nanoparticles can activate the nitriles and enhance the reactivity for azides.
ZnWO4 nanoparticles were synthesized by a facile solvothermal method. ZnWO4 nanoparticles were utilized as the catalyst for the formation of 5-phenyl-1H-tetrazoles from cyclo-addition reaction. The results show that the yield reaches 81% when 0.2 mmol catalyst is used at 110℃ for 10 h. However, the yield only reaches 43% and 65% for amorphous and nanorods ZnWO4, respectively. Clearly, ZnWO4 nanoparticles display superior catalytic performance. This high activity might be attributed to the larger surface area and more active sites that originate from the small size and good dispersibility of ZnWO4 nanoparticles. The unsaturated W atoms on the surface of ZnWO4 nanoparticles can activate the nitriles and enhance the reactivity for azides.
2013, 29(9): 1819-1824
doi: 10.3969/j.issn.1001-4861.2013.00.264
Abstract:
Two new chiral oxovanadium complexes,[VO(Naph-Leu)(OMe)(CH3OH)] (1) and[VO(Naph-Phe)(OMe)(CH3OH)] (2), (Naph-Leu=Schiff base derived from 2-hydroxy-1-naphthaldehyde and L-leucine, Naph-Phe=Schiff base derived from 2-hydroxy-1-naphthaldehyde and L-phenylalanine), have been synthesized. Single crystal X-ray diffraction analysis showed that complex 1 crystallized in the orthorhombic crystal system, space group P21212 with the cell parameters: a=0.946 80(8) nm, b=3.246 3(3) nm, c=0.662 37(5) nm, V=2.035 9(3) nm3, Z=4, F(000)=864, R1=0.046 3, wR2=0.112 7, S=1.076; and complex 2, crystallized in the monoclinic crystal system, space group P21 with the cell parameters: a=1.113 41(11) nm, b=0.724 09(6) nm, c=1.342 99(12) nm, V=1.047 95(16) nm3, Z=2, F(000)=464, R1=0.035 8, wR2=0.088 8, S=1.024. The IR, UV-Vis and circular dichroism (CD) spectra of the two complexes were measured and discussed. CCDC: 885240, 1; 897188, 2.
Two new chiral oxovanadium complexes,[VO(Naph-Leu)(OMe)(CH3OH)] (1) and[VO(Naph-Phe)(OMe)(CH3OH)] (2), (Naph-Leu=Schiff base derived from 2-hydroxy-1-naphthaldehyde and L-leucine, Naph-Phe=Schiff base derived from 2-hydroxy-1-naphthaldehyde and L-phenylalanine), have been synthesized. Single crystal X-ray diffraction analysis showed that complex 1 crystallized in the orthorhombic crystal system, space group P21212 with the cell parameters: a=0.946 80(8) nm, b=3.246 3(3) nm, c=0.662 37(5) nm, V=2.035 9(3) nm3, Z=4, F(000)=864, R1=0.046 3, wR2=0.112 7, S=1.076; and complex 2, crystallized in the monoclinic crystal system, space group P21 with the cell parameters: a=1.113 41(11) nm, b=0.724 09(6) nm, c=1.342 99(12) nm, V=1.047 95(16) nm3, Z=2, F(000)=464, R1=0.035 8, wR2=0.088 8, S=1.024. The IR, UV-Vis and circular dichroism (CD) spectra of the two complexes were measured and discussed. CCDC: 885240, 1; 897188, 2.
2013, 29(9): 1825-1829
doi: 10.3969/j.issn.1001-4861.2013.00.194
Abstract:
Cyano functional groups were covalently attached to the surface of multi-walled carbon nanotubes(MWNTs) by free radical addition of AIBN, then Al-NiCl2·6H2O-THF system was used to reduce the cyano to obtain amino-functionalized carbon nanotubes. The structure and morphology of amino-functionalized MWNTs were characterized by Raman spectroscopy, thermal gravimetric analysis, X-ray photoelectron spectroscopy and transmission electron microscopy. The results showed that amino group was linked to the surface of MWNTs and approximately 17.1 of every 1 000 carbon atoms on the surface of MWNTs were grafted to amino groups.
Cyano functional groups were covalently attached to the surface of multi-walled carbon nanotubes(MWNTs) by free radical addition of AIBN, then Al-NiCl2·6H2O-THF system was used to reduce the cyano to obtain amino-functionalized carbon nanotubes. The structure and morphology of amino-functionalized MWNTs were characterized by Raman spectroscopy, thermal gravimetric analysis, X-ray photoelectron spectroscopy and transmission electron microscopy. The results showed that amino group was linked to the surface of MWNTs and approximately 17.1 of every 1 000 carbon atoms on the surface of MWNTs were grafted to amino groups.
2013, 29(9): 1830-1834
doi: 10.3969/j.issn.1001-4861.2013.00.229
Abstract:
The inhibition of PTPs which dephosphorylate the insulin receptor, resulting in prolongation of insulin signaling, is involved in the mechanism of vanadiums insulin-sensitizing effects. Here, the speicies of vanadium complexes in the solution with bioligands to oxovanadium ions of 20:1 molar ratio are investigated by UV-Vis spectra, and their inhibition over protein tyrosine phosphatases are evaluated. The results show that in the solution, amino acids are coordinated to oxovanadium ions to form 2:1 vanadium complexes, but ascorbic acid, citric acid, iminodiacetic acid and malic acid form 1:1 vanadium complexes. The inhibitions against protein tyrosine phosphatases indicate among 19 systems of 20:1 molar ratio of bioligands to VO(Ⅱ), 14 systems exhibit strong inhibition over PTP1B (protein tyrosine phosphatase 1B) with IC50 of 0.12~0.63 μmol·L-1, and[VO(Phe)2] system displays strongest inhibition with IC50 of 0.07 μmol·L-1 while[VO(Arg)2],[VO(Oxalate)],[VO(Nitrilotriacetate] and[VO(Citrate)] systems show weaker inhibition with IC50 about 1.05, 1.41, 9.90 and 21.5 μmol·L-1, respectively. The selectivity of[VO(Arg)2],[VO(Tyr)2],[VO(Phe)2],[VO(Malate)],[VO(Lactate)] and[VO(Citrate)] systems over PTP1B, TCPTP (T-cell protein tyrosine phosphatase), HePTP (Hematopoietic protein tyrosine phosphatase) and SHP-1 (Src homology phosphatase 1) show the inhibitions against four PTPs are varied with the change of the bioligands, suggesting the structures of the bioligands influence the potency of the PTPs inhibition and the selectivity.
The inhibition of PTPs which dephosphorylate the insulin receptor, resulting in prolongation of insulin signaling, is involved in the mechanism of vanadiums insulin-sensitizing effects. Here, the speicies of vanadium complexes in the solution with bioligands to oxovanadium ions of 20:1 molar ratio are investigated by UV-Vis spectra, and their inhibition over protein tyrosine phosphatases are evaluated. The results show that in the solution, amino acids are coordinated to oxovanadium ions to form 2:1 vanadium complexes, but ascorbic acid, citric acid, iminodiacetic acid and malic acid form 1:1 vanadium complexes. The inhibitions against protein tyrosine phosphatases indicate among 19 systems of 20:1 molar ratio of bioligands to VO(Ⅱ), 14 systems exhibit strong inhibition over PTP1B (protein tyrosine phosphatase 1B) with IC50 of 0.12~0.63 μmol·L-1, and[VO(Phe)2] system displays strongest inhibition with IC50 of 0.07 μmol·L-1 while[VO(Arg)2],[VO(Oxalate)],[VO(Nitrilotriacetate] and[VO(Citrate)] systems show weaker inhibition with IC50 about 1.05, 1.41, 9.90 and 21.5 μmol·L-1, respectively. The selectivity of[VO(Arg)2],[VO(Tyr)2],[VO(Phe)2],[VO(Malate)],[VO(Lactate)] and[VO(Citrate)] systems over PTP1B, TCPTP (T-cell protein tyrosine phosphatase), HePTP (Hematopoietic protein tyrosine phosphatase) and SHP-1 (Src homology phosphatase 1) show the inhibitions against four PTPs are varied with the change of the bioligands, suggesting the structures of the bioligands influence the potency of the PTPs inhibition and the selectivity.
Low Temperature Combustion Synthesis and Electrochemical Performance of xLi2MnO3-(1-x)LiNi0.7Co0.3O2
2013, 29(9): 1835-1841
doi: 10.3969/j.issn.1001-4861.2013.00.275
Abstract:
The cathode materials for lithium ion batteries xLi2MnO3-(1-x)LiNi0.7Co0.3O2 were prepared via low temperature combustion process. The structure, morphology and electrochemical performance of the synthesized materials were studied systematically. The optimal preparing conditions and the optimal ratio of Li2MnO3 for the cathode materials were studied by single factor experiment. The experimental results show that the synthesized products have α-NaFeO2 layered structure, sphere-like morphology and excellent electrochemical performance; the optimal conditions to prepare these materials are to reheat the combustion products at 850℃ for 20 h, the optimal ratio of Li2MnO3 is x=0.7. The cathode material 0.7Li2MnO3-0.3LiNi0.7Co0.3O2 synthesized under such conditions has the highest discharge capacity of 263.1 mAh·g-1, excellent cycle and rate performance.
The cathode materials for lithium ion batteries xLi2MnO3-(1-x)LiNi0.7Co0.3O2 were prepared via low temperature combustion process. The structure, morphology and electrochemical performance of the synthesized materials were studied systematically. The optimal preparing conditions and the optimal ratio of Li2MnO3 for the cathode materials were studied by single factor experiment. The experimental results show that the synthesized products have α-NaFeO2 layered structure, sphere-like morphology and excellent electrochemical performance; the optimal conditions to prepare these materials are to reheat the combustion products at 850℃ for 20 h, the optimal ratio of Li2MnO3 is x=0.7. The cathode material 0.7Li2MnO3-0.3LiNi0.7Co0.3O2 synthesized under such conditions has the highest discharge capacity of 263.1 mAh·g-1, excellent cycle and rate performance.
2013, 29(9): 1842-1848
doi: 10.3969/j.issn.1001-4861.2013.00.292
Abstract:
Carbon nanotubes (CNTs) were synthesized by direct current arc discharge using three different types of coal (Dahuangshan, Heishan, Kuche) from Xinjiang, and the effects of coal species, currents, pressures, catalysts and atmospheres on the yield and morphologies of CNTs were investigated. The starting material, i.e., coal, was investigated by thermogravimetry and X-ray diffraction. In addition, the composition of the three types of coal was tested by industrial analysis and elemental analysis. The CNT samples obtained under different synthesis conditions were studied by field-emission scanning electron microscopy, high resolution transmission electron microscopy and Raman spectroscopy. Based on the analyses of different starting coal, catalysts and synthesis atmospheres, it was found that the highest yield of CNTs was obtained using Kuche coal with 12% mixture of the nickel and ferrous sulfide, and the CNTs obtained under argon have a more uniform structure. The average diameter of CNTs obtained under argon, nitrogen and helium decrease successively. The results showed that the structure and the diameter distribution of CNTs varied with different gases used during synthesis. The mechanism on the formation of different structural CNTs was discussed.
Carbon nanotubes (CNTs) were synthesized by direct current arc discharge using three different types of coal (Dahuangshan, Heishan, Kuche) from Xinjiang, and the effects of coal species, currents, pressures, catalysts and atmospheres on the yield and morphologies of CNTs were investigated. The starting material, i.e., coal, was investigated by thermogravimetry and X-ray diffraction. In addition, the composition of the three types of coal was tested by industrial analysis and elemental analysis. The CNT samples obtained under different synthesis conditions were studied by field-emission scanning electron microscopy, high resolution transmission electron microscopy and Raman spectroscopy. Based on the analyses of different starting coal, catalysts and synthesis atmospheres, it was found that the highest yield of CNTs was obtained using Kuche coal with 12% mixture of the nickel and ferrous sulfide, and the CNTs obtained under argon have a more uniform structure. The average diameter of CNTs obtained under argon, nitrogen and helium decrease successively. The results showed that the structure and the diameter distribution of CNTs varied with different gases used during synthesis. The mechanism on the formation of different structural CNTs was discussed.
2013, 29(9): 1849-1855
doi: 10.3969/j.issn.1001-4861.2013.00.248
Abstract:
Al-SBA-15 with a rod-like morphology and well-ordered mesostructure was hydrothermally synthesized through a one-step approach in an environmentally friendly medium by using triblock copolymer Pluronic P123 as a structure-directing agent. The influence of aging temperature and silica-alumina species co-hydrolysis on the morphologies and structural properties of the resultant materials were investigated by XRD, IR, SEM, TEM and nitrogen adsorption-desorption techniques at 77 K. Compared to silica-alumina co-hydrolysis, the aging temperature plays an important role in the formation of the ordered mesostructure. The mesopores are widened and the wall thickness becomes thinner when the aging temperature is increased. The particles have well-defined rod-like morphology with the uniform particle size from 2 to 4 μm and the diameter in the range of 400~600 nm. The Si/Al molar ratio of the final Al-SBA-15 samples will be obviously higher if the time for silica-alumina co-hydrolysis is longer than 20 h.
Al-SBA-15 with a rod-like morphology and well-ordered mesostructure was hydrothermally synthesized through a one-step approach in an environmentally friendly medium by using triblock copolymer Pluronic P123 as a structure-directing agent. The influence of aging temperature and silica-alumina species co-hydrolysis on the morphologies and structural properties of the resultant materials were investigated by XRD, IR, SEM, TEM and nitrogen adsorption-desorption techniques at 77 K. Compared to silica-alumina co-hydrolysis, the aging temperature plays an important role in the formation of the ordered mesostructure. The mesopores are widened and the wall thickness becomes thinner when the aging temperature is increased. The particles have well-defined rod-like morphology with the uniform particle size from 2 to 4 μm and the diameter in the range of 400~600 nm. The Si/Al molar ratio of the final Al-SBA-15 samples will be obviously higher if the time for silica-alumina co-hydrolysis is longer than 20 h.
2013, 29(9): 1856-1862
doi: 10.3969/j.issn.1001-4861.2013.00.247
Abstract:
ZnO flower-rod ordered arrays (ZFRs) were synthesized via a liquid phase method, and the ZFRs were sensitized with Ag and Ag2Se quantum dots (AA-ZFRs) by ion exchange. Scanning electron microscopy (SEM), powder X-ray diffraction (XRD), energy dispersive X-ray spectra (EDS), and transmission electron microscopy (TEM) were used to characterize Ag and Ag2Se sensitized ZnO flower-rods (AA-ZFRs). And the photoelectrochemical properties and quantum efficiency were also investigated. The results indicate that the optical absorption of AA-ZFRs can be controllably tuned to cover almost the entire visible spectrum. The sensitization with Ag-Ag2Se restrains the recombination of photogenerated electron-hole pairs due to the heterojunction between Ag-Ag2Se and ZFRs, and enhances the incident photon-to-electron conversion efficiency. Thus, the as-prepared AA-ZFRs exhibit a higher open-circuit photovoltage (-0.77 V Ag/AgCl) and short-circuit photocurrent (0.64 mA·cm-2) under visible light.
ZnO flower-rod ordered arrays (ZFRs) were synthesized via a liquid phase method, and the ZFRs were sensitized with Ag and Ag2Se quantum dots (AA-ZFRs) by ion exchange. Scanning electron microscopy (SEM), powder X-ray diffraction (XRD), energy dispersive X-ray spectra (EDS), and transmission electron microscopy (TEM) were used to characterize Ag and Ag2Se sensitized ZnO flower-rods (AA-ZFRs). And the photoelectrochemical properties and quantum efficiency were also investigated. The results indicate that the optical absorption of AA-ZFRs can be controllably tuned to cover almost the entire visible spectrum. The sensitization with Ag-Ag2Se restrains the recombination of photogenerated electron-hole pairs due to the heterojunction between Ag-Ag2Se and ZFRs, and enhances the incident photon-to-electron conversion efficiency. Thus, the as-prepared AA-ZFRs exhibit a higher open-circuit photovoltage (-0.77 V Ag/AgCl) and short-circuit photocurrent (0.64 mA·cm-2) under visible light.
2013, 29(9): 1863-1869
doi: 10.3969/j.issn.1001-4861.2013.00.241
Abstract:
The Sb3+, Bi3+, Zr4+ and Si4+ doped YAG:Ce yellow phosphors were synthesized by high temperature solid-state method. The doping effect and the related mechanism of Sb3+, Bi3+, Zr4+ and Si4+ on the luminescence intensity of YAG:Ce were studied. The results show that the luminescence intensity firstly increases with the increases of the Sb3+, Bi3+, Zr4+ and Si4+ concentration, then decreases. The energy transfer from Sb3+ and Bi3+ to Ce3+ took the mechanism of the multipolar interactions, which leads the improvements of the emission intensity about 35.5% at 0.5 mmol for Sb3+ and 44.8% at 0.1 mmol for Bi3+, respectively. The additions of Zr4+ and Si4+ promote further reduction of Ce4+ to Ce3+, owing to spontaneous charge compensation. The highest emission intensity is obtained at the concentrations of Zr4+ and Si4+ of 0.3 mmol and 7 mmol, which is increased by 27.4% and 31.2%, respectively. With the doping of Sb3+, Bi3+, Zr4+ and Si4+ elements, the growth of phosphor particle is improved, resulting in the enhancement of phosphors emission.
The Sb3+, Bi3+, Zr4+ and Si4+ doped YAG:Ce yellow phosphors were synthesized by high temperature solid-state method. The doping effect and the related mechanism of Sb3+, Bi3+, Zr4+ and Si4+ on the luminescence intensity of YAG:Ce were studied. The results show that the luminescence intensity firstly increases with the increases of the Sb3+, Bi3+, Zr4+ and Si4+ concentration, then decreases. The energy transfer from Sb3+ and Bi3+ to Ce3+ took the mechanism of the multipolar interactions, which leads the improvements of the emission intensity about 35.5% at 0.5 mmol for Sb3+ and 44.8% at 0.1 mmol for Bi3+, respectively. The additions of Zr4+ and Si4+ promote further reduction of Ce4+ to Ce3+, owing to spontaneous charge compensation. The highest emission intensity is obtained at the concentrations of Zr4+ and Si4+ of 0.3 mmol and 7 mmol, which is increased by 27.4% and 31.2%, respectively. With the doping of Sb3+, Bi3+, Zr4+ and Si4+ elements, the growth of phosphor particle is improved, resulting in the enhancement of phosphors emission.
2013, 29(9): 1870-1876
doi: 10.3969/j.issn.1001-4861.2013.00.288
Abstract:
Europium complexes with cinnamic acid (HL) and its para-substitued derivates R-L (R=CH3, Cl, NO2, OCH3, OH) have been synthesized, and their crystal structures have been determined. The results of single-crystal X-Ray diffraction have shown that {[Eu2(CH3-L)6(DMF)(H2O)]·2DMF·H2O}n (1) and {[Eu2(Cl-L)6(DMF)(H2O)]·2DMF·H2O}n (2) are 1D chain coordination polymers while {[Eu2(NO2-L)6(DMF)(H2O)]·2DMF·H2O}2 (3) is binuclear structured. The complexes have been characterized by FT-IR, UV-Vis and photoluminescence (PL) spectroscopy. The influence of substituted groups' electron-withdrawing effect has been discussed. The effect of coordinated solvent molecular on complexes' luminescent properties has been investigated. CCDC:856461, 1; 856460, 2; 856462, 3.
Europium complexes with cinnamic acid (HL) and its para-substitued derivates R-L (R=CH3, Cl, NO2, OCH3, OH) have been synthesized, and their crystal structures have been determined. The results of single-crystal X-Ray diffraction have shown that {[Eu2(CH3-L)6(DMF)(H2O)]·2DMF·H2O}n (1) and {[Eu2(Cl-L)6(DMF)(H2O)]·2DMF·H2O}n (2) are 1D chain coordination polymers while {[Eu2(NO2-L)6(DMF)(H2O)]·2DMF·H2O}2 (3) is binuclear structured. The complexes have been characterized by FT-IR, UV-Vis and photoluminescence (PL) spectroscopy. The influence of substituted groups' electron-withdrawing effect has been discussed. The effect of coordinated solvent molecular on complexes' luminescent properties has been investigated. CCDC:856461, 1; 856460, 2; 856462, 3.
2013, 29(9): 1877-1881
doi: 10.3969/j.issn.1001-4861.2013.00.271
Abstract:
A complex {[Cu4(PMo12O40)(H2O)5(H2bpdc)(Hbpdc)(bpdc)2]·6H2O}n was synthesized under hydrothermal condition using H3PMo12O40·xH2O,H2bpdc, CuSO4·5H2O as raw materials and characterized by elemental analysis, IR,TG and single-crystal X-ray diffraction. The title compound consists of polyoxoanion[PMo12O40]3-, cations[Cu4(H2O)5(H2bpdc)(Hbpdc)(bpdc)2]3+ and lattice water molecules. The structure refinement indicates that the title compound forms a one-dimensional chain from the polyanions and[Cu4(H2O)5(H2bpdc)(Hbpdc)(bpdc)2]3+ through O bridge. The cyclic voltammogram indicates that three couples redox waves are observed on the compound modified carbon paste electrode. CCDC: 748899.
A complex {[Cu4(PMo12O40)(H2O)5(H2bpdc)(Hbpdc)(bpdc)2]·6H2O}n was synthesized under hydrothermal condition using H3PMo12O40·xH2O,H2bpdc, CuSO4·5H2O as raw materials and characterized by elemental analysis, IR,TG and single-crystal X-ray diffraction. The title compound consists of polyoxoanion[PMo12O40]3-, cations[Cu4(H2O)5(H2bpdc)(Hbpdc)(bpdc)2]3+ and lattice water molecules. The structure refinement indicates that the title compound forms a one-dimensional chain from the polyanions and[Cu4(H2O)5(H2bpdc)(Hbpdc)(bpdc)2]3+ through O bridge. The cyclic voltammogram indicates that three couples redox waves are observed on the compound modified carbon paste electrode. CCDC: 748899.
2013, 29(9): 1882-1886
doi: 10.3969/j.issn.1001-4861.2013.00.237
Abstract:
The ligands[C5Me4HR] (R=cyclopentyl,cyclohexyl,nPr) reacted with Ru3(CO)12 in refluxing xylene to give three new substituted tetramethylcyclopentadienyl diruthenium metal carbonyl complexes[(η5-C5Me4R)Ru(CO)(μ-CO)]2 (R=cyclopentyl (1),cyclohexyl (2),nPr (3)),respectively. The three new complexes were characterized by IR,elemental analysis and 1H NMR spectra. The crystal structure of complexes 1 and 2 was determined by X-ray single crystal diffraction. CCDC: 891140, 1; 837727, 2.
The ligands[C5Me4HR] (R=cyclopentyl,cyclohexyl,nPr) reacted with Ru3(CO)12 in refluxing xylene to give three new substituted tetramethylcyclopentadienyl diruthenium metal carbonyl complexes[(η5-C5Me4R)Ru(CO)(μ-CO)]2 (R=cyclopentyl (1),cyclohexyl (2),nPr (3)),respectively. The three new complexes were characterized by IR,elemental analysis and 1H NMR spectra. The crystal structure of complexes 1 and 2 was determined by X-ray single crystal diffraction. CCDC: 891140, 1; 837727, 2.
2013, 29(9): 1887-1892
doi: 10.3969/j.issn.1001-4861.2013.00.276
Abstract:
Polyaniline (PANi) co-doped with hydrochloric acid (HCl) and sulfosalicylic acid (SSA) were synthesized by chemical oxidization polymerization with aniline as monomer and ammonium persulfate as oxidant. The structures of the polyaniline were characterized by XRD, SEM and FTIR. Effects of the molar concentration ratio (cSSA:cHCl) on the thermoelectric properties of the polyaniline co-doped with HCl and SSA in different proportions were investigated under the same condition. It was found that the electrical conductivity of the polyaniline increased as increasing of cSSA:cHCl, while the changes in Seebeck coefficient showed an opposite trend. The power factor of cSSA:cHCl=0.25:1 sample reaches 0.46 μW·m-1·K-2 at 175℃, which is 1.7 and 1.9 times than that of SSA doped and HCl doped polyaniline, respectively. This indicates that the co-doping with an appropriate ratio of organic acid and inorganic acid is more effective to improve the thermoelectric properties of polyaniline than single acid.
Polyaniline (PANi) co-doped with hydrochloric acid (HCl) and sulfosalicylic acid (SSA) were synthesized by chemical oxidization polymerization with aniline as monomer and ammonium persulfate as oxidant. The structures of the polyaniline were characterized by XRD, SEM and FTIR. Effects of the molar concentration ratio (cSSA:cHCl) on the thermoelectric properties of the polyaniline co-doped with HCl and SSA in different proportions were investigated under the same condition. It was found that the electrical conductivity of the polyaniline increased as increasing of cSSA:cHCl, while the changes in Seebeck coefficient showed an opposite trend. The power factor of cSSA:cHCl=0.25:1 sample reaches 0.46 μW·m-1·K-2 at 175℃, which is 1.7 and 1.9 times than that of SSA doped and HCl doped polyaniline, respectively. This indicates that the co-doping with an appropriate ratio of organic acid and inorganic acid is more effective to improve the thermoelectric properties of polyaniline than single acid.
2013, 29(9): 1893-1896
doi: 10.3969/j.issn.1001-4861.2013.00.222
Abstract:
A zinc polymer {[Zn(H2O)2(L)(phen)]·3H2O}n (1, H2L=1-hydroxy-8-amino-naphthahne-3,6-disulfonic acid, phen=1,10-phenanthroline) has been synthesized and structurally characterized by elemental analysis, IR, UV, PL, TG and single crystal X-ray diffraction. The title complex crystallized in orthorhombic with space group Pnma, a=1.698 90(12) nm, b=0.661 88(11) nm, c=2.480 40(14) nm, V=2.789 1(5) nm3, Z=4, Mr=634.92, Dc=1.512 g·cm-3, the final R=0.058 6, wR=0.121 4 for 1 994 observed reflections (I>2σ(I)). In 1, L2- ligands bridge the six-coordinated zinc(Ⅱ) ions forming 1D chains, which are further connected by intermolecular hydrogen-bonding interactions, generating a 2D supramolecular network. Moreover, aromatic π-π stacking interactions between phenyl rings of L2- dianion and phenanthrolines were detected. CCDC: 900913.
A zinc polymer {[Zn(H2O)2(L)(phen)]·3H2O}n (1, H2L=1-hydroxy-8-amino-naphthahne-3,6-disulfonic acid, phen=1,10-phenanthroline) has been synthesized and structurally characterized by elemental analysis, IR, UV, PL, TG and single crystal X-ray diffraction. The title complex crystallized in orthorhombic with space group Pnma, a=1.698 90(12) nm, b=0.661 88(11) nm, c=2.480 40(14) nm, V=2.789 1(5) nm3, Z=4, Mr=634.92, Dc=1.512 g·cm-3, the final R=0.058 6, wR=0.121 4 for 1 994 observed reflections (I>2σ(I)). In 1, L2- ligands bridge the six-coordinated zinc(Ⅱ) ions forming 1D chains, which are further connected by intermolecular hydrogen-bonding interactions, generating a 2D supramolecular network. Moreover, aromatic π-π stacking interactions between phenyl rings of L2- dianion and phenanthrolines were detected. CCDC: 900913.
2013, 29(9): 1897-1902
doi: 10.3969/j.issn.1001-4861.2013.00.285
Abstract:
By the reaction of 2-(p-bromophenyl)-1H-imidazole-4,5-dicarboxylic acid (p-BrPhH3IDC) with Ni(Ⅱ) ion, one coordination polymer, namely,[Ni(p-BrPhH2IDC)2]·2H2O}n (1) has been synthesized under solvothermal condition. Its molecular structure has been characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The results reveal that it is a two-dimensional polymer, and the ligand p-BrPhH3IDC shows strong coordination ability. Furthermore, the existence of intermolecular hydrogen bonds and π…π stacking interactions between the aromatic groups supplies the additional stabilization for the solid-state supramolecular structure of polymer 1. The thermal properties of 1 and its magnetic behaviors have been studied in the temperature range of 2.0~300 K. Magnetic measurement shows that the antiferromagnetic coupling between the Ni(Ⅱ) ions in complex 1 can be observed. CCDC: 913845.
By the reaction of 2-(p-bromophenyl)-1H-imidazole-4,5-dicarboxylic acid (p-BrPhH3IDC) with Ni(Ⅱ) ion, one coordination polymer, namely,[Ni(p-BrPhH2IDC)2]·2H2O}n (1) has been synthesized under solvothermal condition. Its molecular structure has been characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The results reveal that it is a two-dimensional polymer, and the ligand p-BrPhH3IDC shows strong coordination ability. Furthermore, the existence of intermolecular hydrogen bonds and π…π stacking interactions between the aromatic groups supplies the additional stabilization for the solid-state supramolecular structure of polymer 1. The thermal properties of 1 and its magnetic behaviors have been studied in the temperature range of 2.0~300 K. Magnetic measurement shows that the antiferromagnetic coupling between the Ni(Ⅱ) ions in complex 1 can be observed. CCDC: 913845.
2013, 29(9): 1903-1908
doi: 10.3969/j.issn.1001-4861.2013.00.246
Abstract:
Transparent 25KTiOPO4-75SiO2 (KTP@SiO2) nanocrystalline glass-ceramics were synthesized by the wet-chemical method. Morphology and nanostructure of the KTP nanocrystals embedded in the silicate glass were characterized by means of X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM). The results show that, KTP nanocrystals with the size of ~30 nm are precipitated from SiO2-based glass in the heat-treated transparent gels, forming KTiOPO4@SiO2 nanophase glass-ceramics. At the same time, a large amount of irregular mesopores were eliminated, but small amount of spherical nanopores with 30 nm-diameter form. This type of relatively dense glass-ceramic exhibits the optical transmittance of about 64% in the visible region. Based on nanostructure data, the effects of the nanostructure on the transparency of the glass-ceramics were analyzed according to Rayleigh model. It shows that the ratio of the refractive indices decreases the optical transmittance of the KTiOPO4@SiO2 nano-glass-ceramics in the visible region.
Transparent 25KTiOPO4-75SiO2 (KTP@SiO2) nanocrystalline glass-ceramics were synthesized by the wet-chemical method. Morphology and nanostructure of the KTP nanocrystals embedded in the silicate glass were characterized by means of X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM). The results show that, KTP nanocrystals with the size of ~30 nm are precipitated from SiO2-based glass in the heat-treated transparent gels, forming KTiOPO4@SiO2 nanophase glass-ceramics. At the same time, a large amount of irregular mesopores were eliminated, but small amount of spherical nanopores with 30 nm-diameter form. This type of relatively dense glass-ceramic exhibits the optical transmittance of about 64% in the visible region. Based on nanostructure data, the effects of the nanostructure on the transparency of the glass-ceramics were analyzed according to Rayleigh model. It shows that the ratio of the refractive indices decreases the optical transmittance of the KTiOPO4@SiO2 nano-glass-ceramics in the visible region.
2013, 29(9): 1909-1913
doi: 10.3969/j.issn.1001-4861.2013.00.296
Abstract:
The reaction of LAlH2 (L=(Z)-4-[(2,6-diisopropylphenyl)amino]pent-3-en-2-ylidene-2,6-diisopropylaniline) with 2-trifluoromethylphenylboronic acid resulted in the boroxine-linked organic aluminum compound LAl[OB(2-CF3C6H4)]2(μ-O). Compound is an unique example of a spiro-centered aluminum atom, showing the inorganic AlO3B2 ring fused to the organic C3N2 part. Compound was characterized by 1H NMR, IR, elemental analysis, and single crystal X-ray structural analysis. Furthermore, compound was studied by TG analysis. CCDC: 918118.
The reaction of LAlH2 (L=(Z)-4-[(2,6-diisopropylphenyl)amino]pent-3-en-2-ylidene-2,6-diisopropylaniline) with 2-trifluoromethylphenylboronic acid resulted in the boroxine-linked organic aluminum compound LAl[OB(2-CF3C6H4)]2(μ-O). Compound is an unique example of a spiro-centered aluminum atom, showing the inorganic AlO3B2 ring fused to the organic C3N2 part. Compound was characterized by 1H NMR, IR, elemental analysis, and single crystal X-ray structural analysis. Furthermore, compound was studied by TG analysis. CCDC: 918118.
2013, 29(9): 1914-1920
doi: 10.3969/j.issn.1001-4861.2013.00.290
Abstract:
A new three-dimensional (3D) coordination polymer of[Cu2(nic)4(H2O)]n (1) (Hnic=nicotinic acid) has been prepared and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with a=1.071 56(3) nm, b=1.958 79(6) nm, c=1.379 50(3) nm, β=104.498 (2)°, V=2.803 31(13) nm3, Dc=1.501 g·cm-3, Z=4, F(000)=1 280, Goof=1.014, R1=0.041 7, wR2=0.113 2. Complex 1 shows a 3D uninodal 5-connected framework with (44·66) topology. Moreover, Magnetic susceptibility measurements demonstrate that complex 1 exhibits antiferromagnetic interaction within the binuclear units. CCDC: 921590.
A new three-dimensional (3D) coordination polymer of[Cu2(nic)4(H2O)]n (1) (Hnic=nicotinic acid) has been prepared and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with a=1.071 56(3) nm, b=1.958 79(6) nm, c=1.379 50(3) nm, β=104.498 (2)°, V=2.803 31(13) nm3, Dc=1.501 g·cm-3, Z=4, F(000)=1 280, Goof=1.014, R1=0.041 7, wR2=0.113 2. Complex 1 shows a 3D uninodal 5-connected framework with (44·66) topology. Moreover, Magnetic susceptibility measurements demonstrate that complex 1 exhibits antiferromagnetic interaction within the binuclear units. CCDC: 921590.
2013, 29(9): 1921-1927
doi: 10.3969/j.issn.1001-4861.2013.00.274
Abstract:
A 2D coordination polymer, namely {[NaMn3ⅢO(sao)3(tfbdc)(H2O)4]·0.5H2O·2CH3CH2OH}n(1) (H2tfbdc=2, 3, 5, 6-tetrafluoroterephthalic acid, H2sao=salicylaldoxime), was synthesized and structurally characterized by elemental analysis, IR spectrum, thermogravimetric analysis, and single-crystal X-ray diffraction. This complex crystallizes in triclinic space group P1, and exhibits a two-dimensional polymeric structure constructing from[Mn3O] units bridged by sodium cations and tetrafluoroterephthalate. Variable-temperature magnetic susceptibility analysis indicates that antiferromagnetic interaction exists between the manganese(Ⅲ)ions in the[Mn3O] unit. CCDC: 934761.
A 2D coordination polymer, namely {[NaMn3ⅢO(sao)3(tfbdc)(H2O)4]·0.5H2O·2CH3CH2OH}n(1) (H2tfbdc=2, 3, 5, 6-tetrafluoroterephthalic acid, H2sao=salicylaldoxime), was synthesized and structurally characterized by elemental analysis, IR spectrum, thermogravimetric analysis, and single-crystal X-ray diffraction. This complex crystallizes in triclinic space group P1, and exhibits a two-dimensional polymeric structure constructing from[Mn3O] units bridged by sodium cations and tetrafluoroterephthalate. Variable-temperature magnetic susceptibility analysis indicates that antiferromagnetic interaction exists between the manganese(Ⅲ)ions in the[Mn3O] unit. CCDC: 934761.
2013, 29(9): 1928-1934
doi: 10.3969/j.issn.1001-4861.2013.00.270
Abstract:
Two novel metal-organic complexes {[Zn2(IMDN)4(H2O)3]·(H2O)3}n (1) and[Co(IMDN)2(H2O)2]n (2) (HIMDN=2H-imidazole-4,5-dicarbonitrile) based on HIMDN have been synthesized by the method of normal temperature diffusion, and characterized by elemental analysis, FTIR, thermal gravimetric analysis and X-ray diffraction single-crystal structural analysis. The coordination environment of two Zn (Ⅱ) ions is different in 1. One Zn (Ⅱ) ion is four-coordinated and the other is six-coordinated. The central Co (Ⅱ) ion is six-coordinated in 2. Both complexes show one dimensional (1D) chain structure and connected by hydrogen bonds to form three-dimensional structure. Moreover, the fluorescent property of complex 1 had been investigated in the solid state. CCDC: 889348, 1; 889349, 2.
Two novel metal-organic complexes {[Zn2(IMDN)4(H2O)3]·(H2O)3}n (1) and[Co(IMDN)2(H2O)2]n (2) (HIMDN=2H-imidazole-4,5-dicarbonitrile) based on HIMDN have been synthesized by the method of normal temperature diffusion, and characterized by elemental analysis, FTIR, thermal gravimetric analysis and X-ray diffraction single-crystal structural analysis. The coordination environment of two Zn (Ⅱ) ions is different in 1. One Zn (Ⅱ) ion is four-coordinated and the other is six-coordinated. The central Co (Ⅱ) ion is six-coordinated in 2. Both complexes show one dimensional (1D) chain structure and connected by hydrogen bonds to form three-dimensional structure. Moreover, the fluorescent property of complex 1 had been investigated in the solid state. CCDC: 889348, 1; 889349, 2.
2013, 29(9): 1935-1941
doi: 10.3969/j.issn.1001-4861.2013.00.252
Abstract:
Lead sulfate/graphene nano sheets (GNS) composites were fabricated by using a simple impregnation method. The composite was used as a negative active material for lead acid battery. Compared with pure lead sulfate electrodes, the composite electrodes display higher specific capacity and rechargeable performance under high charge and discharge rates. An average discharging specific capacity of PbSO4/GNS composites reaches 110, 94 and 69 mAh·g-1 at current density of 100 mA·g-1, 200 mA·g-1 and 300 mA·g-1, respectively. However, the average discharging capacity of PbSO4 only reaches 49, 5 and 0.5 mAh·g-1 at the same condition. The electrochemical characteristic of the composites electrode was studied by cyclic voltammetry (CV) and battery tests. The cyclic voltammetry results show that capacitive effect and the hydrogen evolution of graphene nano sheets become more obvious with the increase in scanning rate resulting in 20% lower charging efficiency of PbSO4/GNS composites compared to lead sulfate. The battery charge-discharge curves confirm that graphene nano sheets improve the charging voltage about 0.1 V and can also help double the capacity of lead sulfate. The XRD and SEM results show that lead sulfate particles are well dispersed on the surface of graphene nano sheets instead of agglomerating.
Lead sulfate/graphene nano sheets (GNS) composites were fabricated by using a simple impregnation method. The composite was used as a negative active material for lead acid battery. Compared with pure lead sulfate electrodes, the composite electrodes display higher specific capacity and rechargeable performance under high charge and discharge rates. An average discharging specific capacity of PbSO4/GNS composites reaches 110, 94 and 69 mAh·g-1 at current density of 100 mA·g-1, 200 mA·g-1 and 300 mA·g-1, respectively. However, the average discharging capacity of PbSO4 only reaches 49, 5 and 0.5 mAh·g-1 at the same condition. The electrochemical characteristic of the composites electrode was studied by cyclic voltammetry (CV) and battery tests. The cyclic voltammetry results show that capacitive effect and the hydrogen evolution of graphene nano sheets become more obvious with the increase in scanning rate resulting in 20% lower charging efficiency of PbSO4/GNS composites compared to lead sulfate. The battery charge-discharge curves confirm that graphene nano sheets improve the charging voltage about 0.1 V and can also help double the capacity of lead sulfate. The XRD and SEM results show that lead sulfate particles are well dispersed on the surface of graphene nano sheets instead of agglomerating.
2013, 29(9): 1942-1946
doi: 10.3969/j.issn.1001-4861.2013.00.249
Abstract:
A coordination polymer,[Pb2(L1)2(L2)2] (1) (H2L1=succinic acid and L2=2-(4-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), has been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, TGA and single-crystal X-ray diffraction. Crystal data: C46H30F2N8O8Pb2, monoclinic, space group P21/c, a=0.795 40(10) nm, b=2.649 0(3) nm, c=1.996 9(2) nm, β=99.784(2)°, V=4.146 3(9) nm3, Z=4, R=0.038 0, wR=0.0845. In 1, each L1 anion in a bis-chelating mode bridges Pb(Ⅱ) atoms to afford a one-dimensional (1D) chain structure. Neighboring 1D chains are linked together by π-π stackings among L2 ligands to yield a 3D supramolecular architecture. Finally, the N-H…O hydrogen-bonding interactions further stabilize the 3D supramolecular structure of 1.
A coordination polymer,[Pb2(L1)2(L2)2] (1) (H2L1=succinic acid and L2=2-(4-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), has been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, TGA and single-crystal X-ray diffraction. Crystal data: C46H30F2N8O8Pb2, monoclinic, space group P21/c, a=0.795 40(10) nm, b=2.649 0(3) nm, c=1.996 9(2) nm, β=99.784(2)°, V=4.146 3(9) nm3, Z=4, R=0.038 0, wR=0.0845. In 1, each L1 anion in a bis-chelating mode bridges Pb(Ⅱ) atoms to afford a one-dimensional (1D) chain structure. Neighboring 1D chains are linked together by π-π stackings among L2 ligands to yield a 3D supramolecular architecture. Finally, the N-H…O hydrogen-bonding interactions further stabilize the 3D supramolecular structure of 1.
2013, 29(9): 1947-1951
doi: 10.3969/j.issn.1001-4861.2013.00.282
Abstract:
Direct electrochemical reduction of Sm2O3 and formation of Al-Sm alloys were investigated in LiCl-KCl melts by using additive AlCl3 at 803 K. The electrochemical behaviors of Sm2O3 and SmCl3 raw material in LiCl-KCl-AlCl3 melts were characterized by cyclic voltammetry and square wave voltammetry. Galvanostatic electrolysis was carried out to extract Sm element from LiCl-KCl-AlCl3 melts, and the deposits were characterized by X-ray diffraction (XRD). The numbers and potential regions of the peaks obtained from the two systems are almost the same, indicating that the Sm2O3 is chloridized by AlCl3 in the LiCl-KCl melt. The chronopotentiometry result indicates that the coreduction of Al and Sm occurs when the cathodic current is more negative than-139.8 mA·cm-2. Al-Sm alloys with different phases can be obtained by adjusting the concentration of AlCl3 and Sm2O3.
Direct electrochemical reduction of Sm2O3 and formation of Al-Sm alloys were investigated in LiCl-KCl melts by using additive AlCl3 at 803 K. The electrochemical behaviors of Sm2O3 and SmCl3 raw material in LiCl-KCl-AlCl3 melts were characterized by cyclic voltammetry and square wave voltammetry. Galvanostatic electrolysis was carried out to extract Sm element from LiCl-KCl-AlCl3 melts, and the deposits were characterized by X-ray diffraction (XRD). The numbers and potential regions of the peaks obtained from the two systems are almost the same, indicating that the Sm2O3 is chloridized by AlCl3 in the LiCl-KCl melt. The chronopotentiometry result indicates that the coreduction of Al and Sm occurs when the cathodic current is more negative than-139.8 mA·cm-2. Al-Sm alloys with different phases can be obtained by adjusting the concentration of AlCl3 and Sm2O3.
2013, 29(9): 1952-1956
doi: 10.3969/j.issn.1001-4861.2013.00.260
Abstract:
A new Cd(Ⅱ) complex {[CdL2(H2O)2]·2(C7H6N5)}n(C7H6N5=5-(3-aminophenyl)tetrazole ion) based on a ligand L (L=1,3-di(4-pyridy)propane) has been synthesized and structurally characterized by X-ray single crystal diffraction analysis. Structural analysis reveals that the complex is a one-dimensional complex. The Cd(Ⅱ) ion adopts a distorted octahedral coordinated geometry formed by four N atoms and two O atoms, of which four N atoms from different L ligands, two O atoms from different H2O. In the crystal, adjacent Cd(Ⅱ) centers are bridged by L ligands to generate a one-dimensional chain structure. The one-dimensional chains are further connected into a three-dimensional supramolecular network by O-H…N, N-H…N hydrogen bonding contacts. CCDC: 908806.
A new Cd(Ⅱ) complex {[CdL2(H2O)2]·2(C7H6N5)}n(C7H6N5=5-(3-aminophenyl)tetrazole ion) based on a ligand L (L=1,3-di(4-pyridy)propane) has been synthesized and structurally characterized by X-ray single crystal diffraction analysis. Structural analysis reveals that the complex is a one-dimensional complex. The Cd(Ⅱ) ion adopts a distorted octahedral coordinated geometry formed by four N atoms and two O atoms, of which four N atoms from different L ligands, two O atoms from different H2O. In the crystal, adjacent Cd(Ⅱ) centers are bridged by L ligands to generate a one-dimensional chain structure. The one-dimensional chains are further connected into a three-dimensional supramolecular network by O-H…N, N-H…N hydrogen bonding contacts. CCDC: 908806.
2013, 29(9): 1957-1961
doi: 10.3969/j.issn.1001-4861.2013.00.230
Abstract:
The title complex[Zn(PCPA)2(4,4'-bipy)(H2O)]n with p-chlorophenoxyacetic acid (PCPA), 4,4'-bipyridine (4,4'-bipy) has been hydrothermally synthesized and characterized by elemental analysis, IR spectra, UV spectra, thermal analyses, powder X-ray diffraction and single crystal X-ray diffraction. The zinc(Ⅱ) ion is six-coordinated with two nitrogen atoms from two 4,4'-bipy, three oxygen atoms from three PCPA and one water oxygen atom, forming a slightly distorted octahedral configuration. The complex molecules form a 2D layer structure through bridged PCPA and 4,4'-bipy which is consolidated by O-H…O hydrogen bonds. CCDC: 850113.
The title complex[Zn(PCPA)2(4,4'-bipy)(H2O)]n with p-chlorophenoxyacetic acid (PCPA), 4,4'-bipyridine (4,4'-bipy) has been hydrothermally synthesized and characterized by elemental analysis, IR spectra, UV spectra, thermal analyses, powder X-ray diffraction and single crystal X-ray diffraction. The zinc(Ⅱ) ion is six-coordinated with two nitrogen atoms from two 4,4'-bipy, three oxygen atoms from three PCPA and one water oxygen atom, forming a slightly distorted octahedral configuration. The complex molecules form a 2D layer structure through bridged PCPA and 4,4'-bipy which is consolidated by O-H…O hydrogen bonds. CCDC: 850113.
2013, 29(9): 1962-1968
doi: 10.3969/j.issn.1001-4861.2013.00.208
Abstract:
The title complex {[Ca2(μ3-HMIA2-)(μ5-HMIA2-)(H2O)]·H2O}n (1, H3MIA=2-methyl-1H-imidazole-4,5-dicarboxylic acid) was synthesized by hydrothermal synthesis and characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic system, space group P21/c with a=0.860 67(11) nm, b=1.656 5(2) nm, c=1.269 24(16) nm, β=108.005 0(10)°, V=1.720 9(4) nm3, C12H10Ca2N4O10, Mr=450.40, Z=4, Dc=1.728 g·cm-3, F(000)=920, μ=0.727 mm-1, S=1.041, λ(Mo Kα)=0.071 073 nm, R=0.026 0 and wR=0.063 8 for 3 211 observed reflections (I>2σ(I)). Compound 1 is a unique binuclear Ca(Ⅱ) parallelepiped MOFs, two Ca(Ⅱ) cations are seven-coordinated, but show different coordination environments. Four μ3-HMIA2-, two μ5-HMIA2- and eight Ca(Ⅱ) ions form a molecular parallelepiped of[Ca8(μ3-HMIA)4(μ5-HMIA)2]4+. The μ5-HMIA2- ligand adopts a unique coordination mode and links the neighboring parallelepipeds to form one-dimensional chain. The μ3-HMIA2- ligand links the neighboring one-dimensional chains to yield a two-dimensional honey comb-like network layer architectures, which are further linked through two carboxlate oxygen atoms from μ3-HMIA2- ligand to generate a three-dimensional MOFs. Thermal gravimetric analysis and antibacterial activities of complex 1 were also studied. CCDC: 869134.
The title complex {[Ca2(μ3-HMIA2-)(μ5-HMIA2-)(H2O)]·H2O}n (1, H3MIA=2-methyl-1H-imidazole-4,5-dicarboxylic acid) was synthesized by hydrothermal synthesis and characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic system, space group P21/c with a=0.860 67(11) nm, b=1.656 5(2) nm, c=1.269 24(16) nm, β=108.005 0(10)°, V=1.720 9(4) nm3, C12H10Ca2N4O10, Mr=450.40, Z=4, Dc=1.728 g·cm-3, F(000)=920, μ=0.727 mm-1, S=1.041, λ(Mo Kα)=0.071 073 nm, R=0.026 0 and wR=0.063 8 for 3 211 observed reflections (I>2σ(I)). Compound 1 is a unique binuclear Ca(Ⅱ) parallelepiped MOFs, two Ca(Ⅱ) cations are seven-coordinated, but show different coordination environments. Four μ3-HMIA2-, two μ5-HMIA2- and eight Ca(Ⅱ) ions form a molecular parallelepiped of[Ca8(μ3-HMIA)4(μ5-HMIA)2]4+. The μ5-HMIA2- ligand adopts a unique coordination mode and links the neighboring parallelepipeds to form one-dimensional chain. The μ3-HMIA2- ligand links the neighboring one-dimensional chains to yield a two-dimensional honey comb-like network layer architectures, which are further linked through two carboxlate oxygen atoms from μ3-HMIA2- ligand to generate a three-dimensional MOFs. Thermal gravimetric analysis and antibacterial activities of complex 1 were also studied. CCDC: 869134.
2013, 29(9): 1969-1978
doi: 10.3969/j.issn.1001-4861.2013.00.319
Abstract:
Ternary complexes of Ni(Ⅱ), Cu(Ⅱ), and Zn(Ⅱ) with nitrilotriacetic acid HNTA2- as a primary ligand and valine or leucine as a secondary ligand were synthesized in slightly acidic medium. The new complexes were characterized by elemental analysis, FTIR, UV-Vis spectroscopy, thermal analysis, magnetic measurements and mass spectroscopy. The results indicate that the ternary complexes are isolated in M:HNTA:valine(or leucine) ratio of 1:1:1, and the molecular structures are suggested to be[M(HNTA)(valine)(H2O)2]·1.5H2O and[M(HNTA) (leucine)(H2O)2]·1.5H2O, where M=Ni(Ⅱ) or Cu(Ⅱ) and H2[Zn(NTA)(valine)(H2O)] H2O. The suggested geometry of our ternary metal complexes is an octahedral symmetry. The antimicrobial activities of prepared complexes against Escherichia coli, Staphylococcus aureus, Candida albicans and Aspergillus flavus (isolates from Microanalytical Center, Faculty of Science, Cairo University) were also investigated. The complexes were tested in vitro to assess growth inhibitory activity against the bacterial and fungal species with standard antibacterial and antifungal agents according to the recommended known method.
Ternary complexes of Ni(Ⅱ), Cu(Ⅱ), and Zn(Ⅱ) with nitrilotriacetic acid HNTA2- as a primary ligand and valine or leucine as a secondary ligand were synthesized in slightly acidic medium. The new complexes were characterized by elemental analysis, FTIR, UV-Vis spectroscopy, thermal analysis, magnetic measurements and mass spectroscopy. The results indicate that the ternary complexes are isolated in M:HNTA:valine(or leucine) ratio of 1:1:1, and the molecular structures are suggested to be[M(HNTA)(valine)(H2O)2]·1.5H2O and[M(HNTA) (leucine)(H2O)2]·1.5H2O, where M=Ni(Ⅱ) or Cu(Ⅱ) and H2[Zn(NTA)(valine)(H2O)] H2O. The suggested geometry of our ternary metal complexes is an octahedral symmetry. The antimicrobial activities of prepared complexes against Escherichia coli, Staphylococcus aureus, Candida albicans and Aspergillus flavus (isolates from Microanalytical Center, Faculty of Science, Cairo University) were also investigated. The complexes were tested in vitro to assess growth inhibitory activity against the bacterial and fungal species with standard antibacterial and antifungal agents according to the recommended known method.
2013, 29(9): 1979-1984
doi: 10.3969/j.issn.1001-4861.2013.00.291
Abstract:
Solvothermal reaction of BaCl2·2H2O with 3,4-pyridinedicarboxylic acid afforded a new inorganic-organic hybrid framework,[Ba2(pdc)2(H2O)3]n (1) (H2pdc=3,4-pyridinedicarboxylic acid). This complex has been fully characterized by single crystal X-ray diffraction, elemental analysis, and IR spectrum. X-ray analysis shows that complex 1 features a two-dimensional network (2D). Ba1 takes eight-coordinated distorted square antiprism geometry. Ba2 takes ten-coordinate distorted dicapped square prism coordination geometry. The whole pdc2- anion connects four different Ba(Ⅱ) atoms, giving rise to a 2D network structure. The three-dimensional structure is formed by O-H…N hydrogen bonding interactions. Thermal stability and luminescent property of compound 1 have also been investigated. CCDC: 887479.
Solvothermal reaction of BaCl2·2H2O with 3,4-pyridinedicarboxylic acid afforded a new inorganic-organic hybrid framework,[Ba2(pdc)2(H2O)3]n (1) (H2pdc=3,4-pyridinedicarboxylic acid). This complex has been fully characterized by single crystal X-ray diffraction, elemental analysis, and IR spectrum. X-ray analysis shows that complex 1 features a two-dimensional network (2D). Ba1 takes eight-coordinated distorted square antiprism geometry. Ba2 takes ten-coordinate distorted dicapped square prism coordination geometry. The whole pdc2- anion connects four different Ba(Ⅱ) atoms, giving rise to a 2D network structure. The three-dimensional structure is formed by O-H…N hydrogen bonding interactions. Thermal stability and luminescent property of compound 1 have also been investigated. CCDC: 887479.
2013, 29(9): 1985-1992
doi: 10.3969/j.issn.1001-4861.2013.00.278
Abstract:
In order to locate the exact chelation site, the chelation between luteolin and Cd(Ⅱ) ion was studied using theoretical methods. Various complexes, formed by natural and deprotonated luteolin chelating with Cd(Ⅱ) and hydrated Cd(Ⅱ) ion, respectively, were studied by using "Density Functional Theory"(DFT) method. The results indicate that Cd(Ⅱ) ion is connected with luteolin at the 5-hydroxy-4-keto site in the formed complexes and that deprotonated luteolin has stronger chelating power than natural luteolin. The reactivity differences between luteolin and luteolin-Cd(Ⅱ) complexes were observed through comparison of their Conceptual DFT reactivity indices. In addition to the theoretical studies, the experiments were performed to compare with the theoretical conclusions. Meanwhile, luteolin-Cd(Ⅱ) complex was synthesized, and the chelation site was analyzed using IR and UV/Vis spectroscopy. The experimental results have the same conclusions as those by theoretical studies.
In order to locate the exact chelation site, the chelation between luteolin and Cd(Ⅱ) ion was studied using theoretical methods. Various complexes, formed by natural and deprotonated luteolin chelating with Cd(Ⅱ) and hydrated Cd(Ⅱ) ion, respectively, were studied by using "Density Functional Theory"(DFT) method. The results indicate that Cd(Ⅱ) ion is connected with luteolin at the 5-hydroxy-4-keto site in the formed complexes and that deprotonated luteolin has stronger chelating power than natural luteolin. The reactivity differences between luteolin and luteolin-Cd(Ⅱ) complexes were observed through comparison of their Conceptual DFT reactivity indices. In addition to the theoretical studies, the experiments were performed to compare with the theoretical conclusions. Meanwhile, luteolin-Cd(Ⅱ) complex was synthesized, and the chelation site was analyzed using IR and UV/Vis spectroscopy. The experimental results have the same conclusions as those by theoretical studies.
2013, 29(9): 1993-1998
doi: 10.3969/j.issn.1001-4861.2013.00.265
Abstract:
The reactions of tris[(benzimidazol-2-yl)methyl]amine (ntb) and 1,3-phenylenedinitrilotetraacetic acid (H4mpda) with copper nitrate can produce complex 1 from CH3COCH3/CH3OH/H2O and complex 2 from DMF/CH3OH/H2O. Complexes with the formula of[Cu(ntb)(H2mpda)]·0.5CH3COCH3·2H2O (1) and[Cu(ntb)(H2mpda)]·DMF·CH3OH·2H2O (2) both have[Cu(ntb)(H2mpda)] structural units, in which Cu(Ⅱ) centers always have a five-coordination number bound to one ntb ligand and one H2mpda anion. All these complexes possess trigonal bipyramidal coordination geometry. However, metal ions show remarkable differences in structures due to the effects of solvents. Comparing to complex 1, complex 2 possesses more distorted coordination geometry. The positions of ntb and H2mpda ligands in 1 and 2 are very different. The mononuclear coordination units are extended by hydrogen-bonding into different three dimensional networks. CCDC: 893363, 1; 893364, 2.
The reactions of tris[(benzimidazol-2-yl)methyl]amine (ntb) and 1,3-phenylenedinitrilotetraacetic acid (H4mpda) with copper nitrate can produce complex 1 from CH3COCH3/CH3OH/H2O and complex 2 from DMF/CH3OH/H2O. Complexes with the formula of[Cu(ntb)(H2mpda)]·0.5CH3COCH3·2H2O (1) and[Cu(ntb)(H2mpda)]·DMF·CH3OH·2H2O (2) both have[Cu(ntb)(H2mpda)] structural units, in which Cu(Ⅱ) centers always have a five-coordination number bound to one ntb ligand and one H2mpda anion. All these complexes possess trigonal bipyramidal coordination geometry. However, metal ions show remarkable differences in structures due to the effects of solvents. Comparing to complex 1, complex 2 possesses more distorted coordination geometry. The positions of ntb and H2mpda ligands in 1 and 2 are very different. The mononuclear coordination units are extended by hydrogen-bonding into different three dimensional networks. CCDC: 893363, 1; 893364, 2.
2013, 29(9): 1999-2006
doi: 10.3969/j.issn.1001-4861.2013.00.268
Abstract:
Two new Zinc(Ⅱ) complexes,[Zn2(bpy)4(Htfbdc)2(tfbdc)] (1) and[Zn(bpy)(H2O)2(tfbdc)] (2) (2,2'-bpy=2,2'-bipyridine, tfbdc=tetrafluoroterephthalate) have been synthesized and characterized by elemental analysis, IR spectra, thermogravimetric and X-ray single crystal structure analyses. Structure analysis reveals that 1 and 2 possess same crystal system and space group: triclinic,P1. In 1, Zn(Ⅱ) ion has distorted octahedral geometry, while in 2, Zn(Ⅱ) ion has geometry of distorted trigonal bipyramid. Complex 1 is a dinucleate structure, which is further assembled to a 2D supramolecular network through intermolecular hydrogen bonds. Complex 2 is a mononucleate zwitterion, which is further assembled to a 3D supramolecular network via hydrogen bonds interactions. Photoluminescent properties of complexes 1 and 2 in the solid state have also been investigated. CCDC: 900443, 1; 900444, 2.
Two new Zinc(Ⅱ) complexes,[Zn2(bpy)4(Htfbdc)2(tfbdc)] (1) and[Zn(bpy)(H2O)2(tfbdc)] (2) (2,2'-bpy=2,2'-bipyridine, tfbdc=tetrafluoroterephthalate) have been synthesized and characterized by elemental analysis, IR spectra, thermogravimetric and X-ray single crystal structure analyses. Structure analysis reveals that 1 and 2 possess same crystal system and space group: triclinic,P1. In 1, Zn(Ⅱ) ion has distorted octahedral geometry, while in 2, Zn(Ⅱ) ion has geometry of distorted trigonal bipyramid. Complex 1 is a dinucleate structure, which is further assembled to a 2D supramolecular network through intermolecular hydrogen bonds. Complex 2 is a mononucleate zwitterion, which is further assembled to a 3D supramolecular network via hydrogen bonds interactions. Photoluminescent properties of complexes 1 and 2 in the solid state have also been investigated. CCDC: 900443, 1; 900444, 2.
2013, 29(9): 2007-2012
doi: 10.3969/j.issn.1001-4861.2013.00.262
Abstract:
A new 1D zinc(Ⅱ) coordination polymer {[Zn(Hhbc)2(bpp)]H2O}n (1) (Hhbc=4'-Hydroxyl-biphenyl-4-carboxylate, bpp=1,3-bis(4-pyridyl)propane) has been synthesized by hydrothermal method and characterized by elemental analysis, IR, TGA, powder X-ray diffraction and single-crystal X-ray diffraction. The carboxylate oxygens of two different Hhbc ligands connect one ZnⅡ ion in bidentate-chelating and monodentate coordinated modes to form mononuclear zinc building blocks, which are further linked into a 1D infinite chain through trans-bpp ligands. These chains are further linked into a 2D supramolecular network through water-hydroxyl tetramers involving the free water molecules and hydroxyl groups of Hhbc ligands. Furthermore, the luminescent property of complex 1 was investigated at room temperature. CCDC: 919045.
A new 1D zinc(Ⅱ) coordination polymer {[Zn(Hhbc)2(bpp)]H2O}n (1) (Hhbc=4'-Hydroxyl-biphenyl-4-carboxylate, bpp=1,3-bis(4-pyridyl)propane) has been synthesized by hydrothermal method and characterized by elemental analysis, IR, TGA, powder X-ray diffraction and single-crystal X-ray diffraction. The carboxylate oxygens of two different Hhbc ligands connect one ZnⅡ ion in bidentate-chelating and monodentate coordinated modes to form mononuclear zinc building blocks, which are further linked into a 1D infinite chain through trans-bpp ligands. These chains are further linked into a 2D supramolecular network through water-hydroxyl tetramers involving the free water molecules and hydroxyl groups of Hhbc ligands. Furthermore, the luminescent property of complex 1 was investigated at room temperature. CCDC: 919045.
2013, 29(9): 2013-2020
doi: 10.3969/j.issn.1001-4861.2013.00.266
Abstract:
A copper(Ⅱ) complex[Cu2(NO3)2L(phen)2(H2O)]NO3, (HL=2-phenyl-4-selenazole carboxylic acid, phen=1,10-phenanthroline), was synthesized and characterized by elemental analysis and IR spectra. Its crystal structure was determined by single crystal X-ray diffraction method. The complex, C34H24N8Cu2O12Se, crystallized in the triclinic system, space group P1. The interaction of the complex with DNA was studied by ethidium bromide (EB) fluorescence spectroscopy. The antibacterial activities of the ligand and the complex against five species of bacteria, Escherichia coli (E. coli), Staphylococcus epidermidis (S. epidermidis), Streptococcus viridans (S. viridans), Staphylococcus aureus (S. aureus) and Acinetobacter baumanii (A. baumanii), were tested respectively. The anticancer activities of the ligand and the complex against human pancreatic cancer line PANC-28 and human hepatocarcinoma line HuH7 were also studied by employing MTT assay. The results revealed that the complex possessed significant biological activity. CCDC: 804066.
A copper(Ⅱ) complex[Cu2(NO3)2L(phen)2(H2O)]NO3, (HL=2-phenyl-4-selenazole carboxylic acid, phen=1,10-phenanthroline), was synthesized and characterized by elemental analysis and IR spectra. Its crystal structure was determined by single crystal X-ray diffraction method. The complex, C34H24N8Cu2O12Se, crystallized in the triclinic system, space group P1. The interaction of the complex with DNA was studied by ethidium bromide (EB) fluorescence spectroscopy. The antibacterial activities of the ligand and the complex against five species of bacteria, Escherichia coli (E. coli), Staphylococcus epidermidis (S. epidermidis), Streptococcus viridans (S. viridans), Staphylococcus aureus (S. aureus) and Acinetobacter baumanii (A. baumanii), were tested respectively. The anticancer activities of the ligand and the complex against human pancreatic cancer line PANC-28 and human hepatocarcinoma line HuH7 were also studied by employing MTT assay. The results revealed that the complex possessed significant biological activity. CCDC: 804066.
