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2013 Volume 29 Issue 5
2013, 29(5): 889-895
doi: 10.3969/j.issn.1001-4861.2013.00.141
Abstract:
The expanded graphite oxides were prepared by modified Hummers method. The expanded graphite oxide/sulfur (E-GO/S) composites have been successfully prepared by a new chemical reaction method based on comproportionation in the acidic aqueous solution. FT-IR, XPS were characterized the existence of functional groups on the surface of expanded graphite oxide. XRD results showed that the as-prepared sulfur belongs to orthorhombic system. SEM and TEM results indicated the uniform distribution of the sulfur in the composite. The electrochemical test showed that the expanded graphite oxide/sulfur (E-GO/S) composites can deliver the highest discharge capacity of 1 020 mAh·g-1 at the first cycle, after 100 cycles of charge-discharge, the discharge capacity of the composites keep the capacity of ca. 650 mAh·g-1, and have the excellent rate performance and coulombic efficiency that may be attributed to the homogeneous distribution of sulfur in the composites and the chemical approach to fix sulfur and the lithium polysulfides via the chemical bonds with the functional groups on the surface of expanded graphite oxide.
The expanded graphite oxides were prepared by modified Hummers method. The expanded graphite oxide/sulfur (E-GO/S) composites have been successfully prepared by a new chemical reaction method based on comproportionation in the acidic aqueous solution. FT-IR, XPS were characterized the existence of functional groups on the surface of expanded graphite oxide. XRD results showed that the as-prepared sulfur belongs to orthorhombic system. SEM and TEM results indicated the uniform distribution of the sulfur in the composite. The electrochemical test showed that the expanded graphite oxide/sulfur (E-GO/S) composites can deliver the highest discharge capacity of 1 020 mAh·g-1 at the first cycle, after 100 cycles of charge-discharge, the discharge capacity of the composites keep the capacity of ca. 650 mAh·g-1, and have the excellent rate performance and coulombic efficiency that may be attributed to the homogeneous distribution of sulfur in the composites and the chemical approach to fix sulfur and the lithium polysulfides via the chemical bonds with the functional groups on the surface of expanded graphite oxide.
2013, 29(5): 896-902
doi: 10.3969/j.issn.1001-4861.2013.00.160
Abstract:
Ordered mesoporous aluminum silicates with strong acid sites were synthesized by sol-gel method. The resulted materials' structures were characterized by XRD, TEM, 27Al NMR, NH3-TPD and Py-FT-IR. The amount of surfactant and the Si/Al mole ratio would both affect the materials' meso-structure; while, the amount of HAc has little effect on the structure. TEM analysis confirmed that these aluminum silicates with different Si/Al mole ratios have an ordered 2D hexagonal regularity. Friedel-Crafts alkylation reaction of anisole and benzyl alcohol was used as the probe reaction to detect the acidic properties of these aluminum silicates. The Si/Al mole ratio played an important role in catalytic activity and the aluminum silicates with nSi/nAl=10 showed the best acid catalytic activity. NH3-TPD and Py-FT-IR suggested that the aluminum silicates with nSi/nAl=10 had much more Brönsted acidic sites than that of other Si/Al ratios.
Ordered mesoporous aluminum silicates with strong acid sites were synthesized by sol-gel method. The resulted materials' structures were characterized by XRD, TEM, 27Al NMR, NH3-TPD and Py-FT-IR. The amount of surfactant and the Si/Al mole ratio would both affect the materials' meso-structure; while, the amount of HAc has little effect on the structure. TEM analysis confirmed that these aluminum silicates with different Si/Al mole ratios have an ordered 2D hexagonal regularity. Friedel-Crafts alkylation reaction of anisole and benzyl alcohol was used as the probe reaction to detect the acidic properties of these aluminum silicates. The Si/Al mole ratio played an important role in catalytic activity and the aluminum silicates with nSi/nAl=10 showed the best acid catalytic activity. NH3-TPD and Py-FT-IR suggested that the aluminum silicates with nSi/nAl=10 had much more Brönsted acidic sites than that of other Si/Al ratios.
2013, 29(5): 903-909
doi: 10.3969/j.issn.1001-4861.2013.00.093
Abstract:
The differences in growth kinetics of urinary crystallites from 5 patients with renal stones and 5 healthy subjects were compared by using scanning electron microscopy (SEM) and X-ray diffractometer (XRD). With the increase of crystal growth time (t), the size of urinary crystallites from patients with renal stones increased constantly from (6±4) μm at t=1 h to (29±17) μm at t=48 h, but the density of crystallites decreased gradually from (1 400±300) mm-2 at t=1 h to (450±140) mm-2 at t=48 h. It indicated that the formation process of crystallites in lithogenic urine was dominated by growth control. In contrast, for healthy subjects, the density of urinary crystallites dereased from (850±260) mm-2 at t=1 h to (610±210) mm-2 at t=48 h, and the crystal size was increased only from 6±5 μm at t=1 h to (15±9) μm at t=48 h. It indicated that the growth process of crystallites in healthy urine was growth control and nucleation-control simultaneously. The differences mentioned above are mainly attributed to that both the concentration and activity of the inhibitors in healthy urine were higher than those in lithogenic urine, and thus can inhibit the growth and aggregation of urinary crystallites more effectively.
The differences in growth kinetics of urinary crystallites from 5 patients with renal stones and 5 healthy subjects were compared by using scanning electron microscopy (SEM) and X-ray diffractometer (XRD). With the increase of crystal growth time (t), the size of urinary crystallites from patients with renal stones increased constantly from (6±4) μm at t=1 h to (29±17) μm at t=48 h, but the density of crystallites decreased gradually from (1 400±300) mm-2 at t=1 h to (450±140) mm-2 at t=48 h. It indicated that the formation process of crystallites in lithogenic urine was dominated by growth control. In contrast, for healthy subjects, the density of urinary crystallites dereased from (850±260) mm-2 at t=1 h to (610±210) mm-2 at t=48 h, and the crystal size was increased only from 6±5 μm at t=1 h to (15±9) μm at t=48 h. It indicated that the growth process of crystallites in healthy urine was growth control and nucleation-control simultaneously. The differences mentioned above are mainly attributed to that both the concentration and activity of the inhibitors in healthy urine were higher than those in lithogenic urine, and thus can inhibit the growth and aggregation of urinary crystallites more effectively.
2013, 29(5): 910-914
doi: 10.3969/j.issn.1001-4861.2013.00.168
Abstract:
The reactions of o-carborane [P,P] ligand L1 with NiCl2(PPh3)2 and [IrCl(COD)]2 under an open atmosphere lead to two nido-carborane species 1 and 2 containing [O,P] or [O,O] ligands. All these complexes have been characterized by NMR, MS, IR and X-ray diffraction analyses. Complex 1 with solvent CHCl3 formed the normal Cl…H interaction and novel CH…π interaction. Complex 2 is the first Ir(Ⅰ) compound containing [O,P] o-carborane ligand. However, due to the difference of metal (Ni and Ir), the [P,P] ligand L1 was oxizided to novel [P,O] ligand and [O,O] ligand, respectively. CCDC: 927419, 1; 927420, 2.
The reactions of o-carborane [P,P] ligand L1 with NiCl2(PPh3)2 and [IrCl(COD)]2 under an open atmosphere lead to two nido-carborane species 1 and 2 containing [O,P] or [O,O] ligands. All these complexes have been characterized by NMR, MS, IR and X-ray diffraction analyses. Complex 1 with solvent CHCl3 formed the normal Cl…H interaction and novel CH…π interaction. Complex 2 is the first Ir(Ⅰ) compound containing [O,P] o-carborane ligand. However, due to the difference of metal (Ni and Ir), the [P,P] ligand L1 was oxizided to novel [P,O] ligand and [O,O] ligand, respectively. CCDC: 927419, 1; 927420, 2.
Synthesis and Electrochemical Performance of Nano-Structure Li3V2(PO4)3/C by Sol-Spray Drying Method
2013, 29(5): 915-921
doi: 10.3969/j.issn.1001-4861.2013.00.070
Abstract:
Li3V2(PO4)3/C samples were successfully synthesized by sol-spray drying method, with LiOH·H2O, NH4VO3, H3PO4 and critic acid as raw materials, comparing the effect of mechamicalactivation before calcinations and direct calcination on the structure, morphology and electrochemical properties of the samples. The structure and morphology were characterized by XRD, SEM, BET and tap density test, and the electrochemical performance was studied by galvanostatic charge-discharge test, CV and EIS. The results show the samples are hollow spherical shell shape, which is composed of nano-sheet about 100nm and still keep the structure after mechamicalactivation. However, the crystallinity and tap density have improved a lot, so is the electrochemical performance. The discharge capacity is 123.6 mAh·g-1 at 0.1C, maintaining 107.8 and 106.0 mAh·g-1 even at high discharge rate of 10C and 20C. The EIS results indicate the samples prepared by the method have a smaller charge transfer resistance.
Li3V2(PO4)3/C samples were successfully synthesized by sol-spray drying method, with LiOH·H2O, NH4VO3, H3PO4 and critic acid as raw materials, comparing the effect of mechamicalactivation before calcinations and direct calcination on the structure, morphology and electrochemical properties of the samples. The structure and morphology were characterized by XRD, SEM, BET and tap density test, and the electrochemical performance was studied by galvanostatic charge-discharge test, CV and EIS. The results show the samples are hollow spherical shell shape, which is composed of nano-sheet about 100nm and still keep the structure after mechamicalactivation. However, the crystallinity and tap density have improved a lot, so is the electrochemical performance. The discharge capacity is 123.6 mAh·g-1 at 0.1C, maintaining 107.8 and 106.0 mAh·g-1 even at high discharge rate of 10C and 20C. The EIS results indicate the samples prepared by the method have a smaller charge transfer resistance.
2013, 29(5): 922-928
doi: 10.3969/j.issn.1001-4861.2013.00.084
Abstract:
Graphene oxide(GO) was prepared by the modified Hummers method,and modified by dodecyl dimethyl benzyl ammonium chloride (1227) to produce 1227 non-covalent modified graphene oxide(GO-1227). Raman spectrum, Diffuse reflection infrared spectroscopy and X-ray photoelectron spectroscopy were used to characterize the chemical structure of GO-1227. X-ray diffraction was used to observe the exfoliated morphology of GO-1227. It is found that the layers of GO became more complete disordered and exfoliated after modified by 1227. Scanning electron microscope and Transmission electron microscope was used to characterize the micro structure of GO-1227. The results show that GO-1227 presented curling and folded layer structure. The disperse property of GO-1227 was measured and thermal stability of GO and GO-1227 was compared by thermogravimetry analysis. The solubility of GO-1227 was enhanced in the relatively weak polar solvent since the 1227 cations surround the layers of GO, and thermal stability of GO was improved due to the thermolysis of oxidation group was prevented by 1227 cations. Finally, nano-filler of the GO-1227 was mixed with gel polyelectrolyte based on polymethylmethacrylate and polystyrene block copolymer(PMMA-b-PS) to prepare the nanocomposited gel polymer electrolytes (NGPE). The result of alternating-current impedance shows that the improvement of ionic conductivity is 8.6 times when the mixed ratio of GO-1227 is two over one thousand.
Graphene oxide(GO) was prepared by the modified Hummers method,and modified by dodecyl dimethyl benzyl ammonium chloride (1227) to produce 1227 non-covalent modified graphene oxide(GO-1227). Raman spectrum, Diffuse reflection infrared spectroscopy and X-ray photoelectron spectroscopy were used to characterize the chemical structure of GO-1227. X-ray diffraction was used to observe the exfoliated morphology of GO-1227. It is found that the layers of GO became more complete disordered and exfoliated after modified by 1227. Scanning electron microscope and Transmission electron microscope was used to characterize the micro structure of GO-1227. The results show that GO-1227 presented curling and folded layer structure. The disperse property of GO-1227 was measured and thermal stability of GO and GO-1227 was compared by thermogravimetry analysis. The solubility of GO-1227 was enhanced in the relatively weak polar solvent since the 1227 cations surround the layers of GO, and thermal stability of GO was improved due to the thermolysis of oxidation group was prevented by 1227 cations. Finally, nano-filler of the GO-1227 was mixed with gel polyelectrolyte based on polymethylmethacrylate and polystyrene block copolymer(PMMA-b-PS) to prepare the nanocomposited gel polymer electrolytes (NGPE). The result of alternating-current impedance shows that the improvement of ionic conductivity is 8.6 times when the mixed ratio of GO-1227 is two over one thousand.
2013, 29(5): 929-935
doi: 10.3969/j.issn.1001-4861.2013.00.126
Abstract:
A graphene-polypyrrole nanotube hybrid is fabricated by chemical hybridization method. Scanning electron microscopy, transmission electron microscopy, fourier-transmission infrared spectroscopy, X-ray photoelectron spectroscopy and electrochemical workstation are used out to characterize the morphology, structure and properties of graphene-polypyrrole nanotube hybrid. The electron microscopy images show that graphene sheets and polypyrrole nanotubes distribute well in the hybrid. The results of spectroscopy analysis confirm the existence of amide group which connects graphene and polypyrrole nanotube in the hybrid. The specific capacitance of the hybrid is 1368 F·g-1 at a current density of 0.3 A·g-1 as well as the specific capacitance of 759 F·g-1 at a current density of 1.5 A·g-1. In long-term cyclic voltammetry tests, after 1000 cycles, the preserved specific capacitance of the hybrid is 85.5% of its initial specific capacitance, demonstrating a good electrochemical stability. The Nyquist plot of the graphene-polypyrrole nanotube hybrid reveals its good pseudo-capacitance performance.
A graphene-polypyrrole nanotube hybrid is fabricated by chemical hybridization method. Scanning electron microscopy, transmission electron microscopy, fourier-transmission infrared spectroscopy, X-ray photoelectron spectroscopy and electrochemical workstation are used out to characterize the morphology, structure and properties of graphene-polypyrrole nanotube hybrid. The electron microscopy images show that graphene sheets and polypyrrole nanotubes distribute well in the hybrid. The results of spectroscopy analysis confirm the existence of amide group which connects graphene and polypyrrole nanotube in the hybrid. The specific capacitance of the hybrid is 1368 F·g-1 at a current density of 0.3 A·g-1 as well as the specific capacitance of 759 F·g-1 at a current density of 1.5 A·g-1. In long-term cyclic voltammetry tests, after 1000 cycles, the preserved specific capacitance of the hybrid is 85.5% of its initial specific capacitance, demonstrating a good electrochemical stability. The Nyquist plot of the graphene-polypyrrole nanotube hybrid reveals its good pseudo-capacitance performance.
2013, 29(5): 936-940
doi: 10.3969/j.issn.1001-4861.2013.00.131
Abstract:
BaZr1-xAlxO3 (x=0～0.08) hollow microspheres with different Al contents were synthesized by hydrothermal method. The samples were characterized by XRD, SEM, TEM, PL, FTIR. XRD data indicated that Al3+ was successfully introduced into the lattice and replaced the Zr4+ cation at B position. Replacing Zr4+ by Al3+ aroused the decrease of cell parameters. TEM observations confirmed the hollow feature and gave a mean particle size of 150 nm. When excited by 355 nm laser, all of the hollow microspheres emitted 423 nm violet light at room temperature. Compared with that of pure BaZrO3, the cell shrinkage that stemmed from Al3+ doping directed to weakened photoluminescence. The non-equivalent doping also led to the variation of oxygen vacancies, which directed to a slightly enhanced photoluminescence with Al3+ doping contents in the range of 1% to 2%.
BaZr1-xAlxO3 (x=0～0.08) hollow microspheres with different Al contents were synthesized by hydrothermal method. The samples were characterized by XRD, SEM, TEM, PL, FTIR. XRD data indicated that Al3+ was successfully introduced into the lattice and replaced the Zr4+ cation at B position. Replacing Zr4+ by Al3+ aroused the decrease of cell parameters. TEM observations confirmed the hollow feature and gave a mean particle size of 150 nm. When excited by 355 nm laser, all of the hollow microspheres emitted 423 nm violet light at room temperature. Compared with that of pure BaZrO3, the cell shrinkage that stemmed from Al3+ doping directed to weakened photoluminescence. The non-equivalent doping also led to the variation of oxygen vacancies, which directed to a slightly enhanced photoluminescence with Al3+ doping contents in the range of 1% to 2%.
2013, 29(5): 941-947
doi: 10.3969/j.issn.1001-4861.2013.00.161
Abstract:
Trifluoropropyl-modified silica membranes were prepared by sol-gel technique using tetraethyl orthosilicate (TEOS) and (trifluoropropyl)trimethoxysilane (TFPTMS) as precursors. The effect of trifluoropropyl modification on the hydrophobic pore structure, properties, hydrogen permeation and separation properties and long-term hydrothermal stability of the modified silica membranes were investigated in detail. The results show that the modified membranes retain a desirable microporous structure with a pore size distributed from 0.45 to 0.7 nm. The hydrophobic property of silica membranes has been considerably enhanced after modification, with a water contact angle of (102.7°±0.1°) at a TFPTMS/TEOS molar ratio of 0.6. The hydrogen transport in the modified silica membranes complies with a micropore diffusion mechanism, with a single H2 permeance of 4.77×10-7 mol·m-2·s-1·Pa-1, a H2/CO2 permselectivity of 6.99 and a H2/CO2 binary gas mixture separation factor of 6.93 at 300 ℃, higher than Knudsen permselectivity (4.69). Under a humid condition with a temperature of 200 ℃ and a water vapor molar ratio of 5%, the single H2 permeance slightly decrease in the first 3 hours and then almost remain constant for at least 220 hours, indicating that the modified membranes are more hydrothermally stable than pure SiO2 membranes.
Trifluoropropyl-modified silica membranes were prepared by sol-gel technique using tetraethyl orthosilicate (TEOS) and (trifluoropropyl)trimethoxysilane (TFPTMS) as precursors. The effect of trifluoropropyl modification on the hydrophobic pore structure, properties, hydrogen permeation and separation properties and long-term hydrothermal stability of the modified silica membranes were investigated in detail. The results show that the modified membranes retain a desirable microporous structure with a pore size distributed from 0.45 to 0.7 nm. The hydrophobic property of silica membranes has been considerably enhanced after modification, with a water contact angle of (102.7°±0.1°) at a TFPTMS/TEOS molar ratio of 0.6. The hydrogen transport in the modified silica membranes complies with a micropore diffusion mechanism, with a single H2 permeance of 4.77×10-7 mol·m-2·s-1·Pa-1, a H2/CO2 permselectivity of 6.99 and a H2/CO2 binary gas mixture separation factor of 6.93 at 300 ℃, higher than Knudsen permselectivity (4.69). Under a humid condition with a temperature of 200 ℃ and a water vapor molar ratio of 5%, the single H2 permeance slightly decrease in the first 3 hours and then almost remain constant for at least 220 hours, indicating that the modified membranes are more hydrothermally stable than pure SiO2 membranes.
2013, 29(5): 948-952
doi: 10.3969/j.issn.1001-4861.2013.00.147
Abstract:
In this work, a kind of silane coupling agent was prepared by condensation reaction of the glutamic acid and silane coupling agent (KH-792). The Glutamic acid was attached to the surface of Apatite-wollastonite bioactive glass-ceramic (A-W GC) by the bifunctional cross-linking agent. To evaluate in vitro cytocompatibility, the surface modified material was co-cultured with the 5th generation human osteosarcoma cell MG63. Fourier Transform infrared spectroscopy (FTIR), Scanning Electron Microscope (SEM), and X-ray Photoelectron Spectroscopy (XPS) were used to character the structure and performance of the synthetic coupling agent and the surface modified A-W GC, respectively. The results show that the Glutamic acid and KH-792 were connected by amide groups, and A-W GC is effectively modified by the synthetic coupling agent. The MG63 cell experiments show that cells adhered to the surface of the material, and the cell proliferation on the surface of the material was promoted. It is an effective method to improve the cell compatibility of A-W GC by surface modification.
In this work, a kind of silane coupling agent was prepared by condensation reaction of the glutamic acid and silane coupling agent (KH-792). The Glutamic acid was attached to the surface of Apatite-wollastonite bioactive glass-ceramic (A-W GC) by the bifunctional cross-linking agent. To evaluate in vitro cytocompatibility, the surface modified material was co-cultured with the 5th generation human osteosarcoma cell MG63. Fourier Transform infrared spectroscopy (FTIR), Scanning Electron Microscope (SEM), and X-ray Photoelectron Spectroscopy (XPS) were used to character the structure and performance of the synthetic coupling agent and the surface modified A-W GC, respectively. The results show that the Glutamic acid and KH-792 were connected by amide groups, and A-W GC is effectively modified by the synthetic coupling agent. The MG63 cell experiments show that cells adhered to the surface of the material, and the cell proliferation on the surface of the material was promoted. It is an effective method to improve the cell compatibility of A-W GC by surface modification.
2013, 29(5): 953-957
doi: 10.3969/j.issn.1001-4861.2013.00.162
Abstract:
[IPrH]+[tBuN=TaCl4(py)]- (1) (IPr=1,3-bis(2,6-diisoproylphenyl)imidazol-2-ylidene) was obtained unexpe-ctedly by the reaction of tBuN=TaCl3(py)2 and IPr. Complex 1 was structurally characterized by NMR, IR, fluores-cence spectra, elemental analysis and single-crystal X-ray diffraction. The crystal structure of 1 shows that the Ta(Ⅴ) center is octahedrally coordinated by four chlorides and two nitrogen atoms from imido and pyridyl ligands, respectively. CCDC: 873803.
[IPrH]+[tBuN=TaCl4(py)]- (1) (IPr=1,3-bis(2,6-diisoproylphenyl)imidazol-2-ylidene) was obtained unexpe-ctedly by the reaction of tBuN=TaCl3(py)2 and IPr. Complex 1 was structurally characterized by NMR, IR, fluores-cence spectra, elemental analysis and single-crystal X-ray diffraction. The crystal structure of 1 shows that the Ta(Ⅴ) center is octahedrally coordinated by four chlorides and two nitrogen atoms from imido and pyridyl ligands, respectively. CCDC: 873803.
2013, 29(5): 958-964
doi: 10.3969/j.issn.1001-4861.2013.00.155
Abstract:
Novel Sr- and Co-codoped (Pr,Sr)(Al,Co)O3-δ perovskite oxide conducting ceramics were prepared by citrate process combined with subsequent high-temperature sintering. The phase composition, microstructure and electrical properties of the obtained ceramics were characterized by XRD, SEM and direct current four-wire method. The experimental results show that all the as-prepared Pr0.9Sr0.1Al1-yCoyO3-δ(y=0.1～0.5) ceramics are a single-phase rhombohedral perovskite structure, and their unit cell volumes, relative densities and electrical conductivities increase with increasing y in the doping range, while the increasing rate in electrical conductivity progressively decrease. Furthermore, these samples are a mixed conductor of oxygen ion and hole in air and their electrical conductivities are absolutely dominated by p-type conduction. The temperature dependence of electrical conductivity for Pr0.9Sr0.1Al1-yCoyO3-δ can be described by the small polaron hopping mechanism. For the as-prepared Pr1-xSrxAl0.5Co0.5O3-δ(x=0.1～0.4) ceramics, a second phase (Pr,Sr)CoO3 obviously precipitates when x=0.2, indicating that the solid solubility limit of Sr on A site in this system is between 10at% and 20at%, and the (Pr, Sr)CoO3 phase in samples increases gradually and finally becomes the main phase with further increase in Sr content. It is found that the electrical conductivity of Pr1-xSrxAl0.5Co0.5O3-δ ceramics roughly exhibits a trend of first increase and then decrease with increasing x in the whole examined temperature range, and reaches the maximum value at around x=0.3. Additionally, the semiconductor-to-metal transition in the conduction behavior is obviously observed for the samples with x≥0.2, and the transition temperature gradually decreases with increasing Sr content.
Novel Sr- and Co-codoped (Pr,Sr)(Al,Co)O3-δ perovskite oxide conducting ceramics were prepared by citrate process combined with subsequent high-temperature sintering. The phase composition, microstructure and electrical properties of the obtained ceramics were characterized by XRD, SEM and direct current four-wire method. The experimental results show that all the as-prepared Pr0.9Sr0.1Al1-yCoyO3-δ(y=0.1～0.5) ceramics are a single-phase rhombohedral perovskite structure, and their unit cell volumes, relative densities and electrical conductivities increase with increasing y in the doping range, while the increasing rate in electrical conductivity progressively decrease. Furthermore, these samples are a mixed conductor of oxygen ion and hole in air and their electrical conductivities are absolutely dominated by p-type conduction. The temperature dependence of electrical conductivity for Pr0.9Sr0.1Al1-yCoyO3-δ can be described by the small polaron hopping mechanism. For the as-prepared Pr1-xSrxAl0.5Co0.5O3-δ(x=0.1～0.4) ceramics, a second phase (Pr,Sr)CoO3 obviously precipitates when x=0.2, indicating that the solid solubility limit of Sr on A site in this system is between 10at% and 20at%, and the (Pr, Sr)CoO3 phase in samples increases gradually and finally becomes the main phase with further increase in Sr content. It is found that the electrical conductivity of Pr1-xSrxAl0.5Co0.5O3-δ ceramics roughly exhibits a trend of first increase and then decrease with increasing x in the whole examined temperature range, and reaches the maximum value at around x=0.3. Additionally, the semiconductor-to-metal transition in the conduction behavior is obviously observed for the samples with x≥0.2, and the transition temperature gradually decreases with increasing Sr content.
2013, 29(5): 965-972
doi: 10.3969/j.issn.1001-4861.2013.00.154
Abstract:
Zirconia functionalized multi-walled carbon nanotubes were successfully synthesized by hydrothermal method and their adsorption behavior for phosphate were also investigated. Characterized results showed that the BET surface areas and the total pore volumes of MWNTs decreased greatly after ZrO2 functionalization. The average particle size of zirconia that uniformly dispersed on the surface of MWNTs increased with increasing ZrO2 content. Phosphate adsorption experimental results showed that decreasing ZrO2 particle size was beneficial to improve the ZrO2 content-normalized adsorption amount and the adsorption rate. The adsorption isotherm could be well fitted by Freundlich equation which suggested a preferential adsorption, while kinetics followed the pseudo-second-order model. Lower ionic strength and pH were favorable to the removal of phosphate. And the effect of co-existing anions was in the order of F->NO3-≈SO42-.
Zirconia functionalized multi-walled carbon nanotubes were successfully synthesized by hydrothermal method and their adsorption behavior for phosphate were also investigated. Characterized results showed that the BET surface areas and the total pore volumes of MWNTs decreased greatly after ZrO2 functionalization. The average particle size of zirconia that uniformly dispersed on the surface of MWNTs increased with increasing ZrO2 content. Phosphate adsorption experimental results showed that decreasing ZrO2 particle size was beneficial to improve the ZrO2 content-normalized adsorption amount and the adsorption rate. The adsorption isotherm could be well fitted by Freundlich equation which suggested a preferential adsorption, while kinetics followed the pseudo-second-order model. Lower ionic strength and pH were favorable to the removal of phosphate. And the effect of co-existing anions was in the order of F->NO3-≈SO42-.
2013, 29(5): 973-978
doi: 10.3969/j.issn.1001-4861.2013.00.127
Abstract:
Thorned hydroxyapatite rods (THA) were synthesized on surface of commercially pure titanium specimens by two-step electrochemical method successively in electrolytes with lower and higher Ca2+ and PO43- ion concentration. The microstructural analysis showed that the main rod (100～200 nm in diameter) of the THA is of HA single crystal, while the thorn (10～50 nm in diameter) consisted of HA nanocrystals. The THAs constitute uniform micro-nano porous coating on the titanium surface. The solubility and contact angle measurement showed that, compared to the bare HA rod coating, the THA coating exhibited higher releasing rate of Ca2+ in phosphate buffered saline (PBS) and higher wettability.
Thorned hydroxyapatite rods (THA) were synthesized on surface of commercially pure titanium specimens by two-step electrochemical method successively in electrolytes with lower and higher Ca2+ and PO43- ion concentration. The microstructural analysis showed that the main rod (100～200 nm in diameter) of the THA is of HA single crystal, while the thorn (10～50 nm in diameter) consisted of HA nanocrystals. The THAs constitute uniform micro-nano porous coating on the titanium surface. The solubility and contact angle measurement showed that, compared to the bare HA rod coating, the THA coating exhibited higher releasing rate of Ca2+ in phosphate buffered saline (PBS) and higher wettability.
2013, 29(5): 979-984
doi: 10.3969/j.issn.1001-4861.2013.00.176
Abstract:
A multiple thioantimonate compound, (1,4-DABH2)Cd2Sb2S6 (1) (1,4-DAB=1,4-diaminobutane) , was solvothermally synthesized at 160 ℃ and characterized by IR and TGA. Its crystal structure analysis reveals the compound was determined by single crystal X-ray diffraction. The crystal structure is orthorhombic in the space group Cmca. Crystallographic data: Mr=750.77, a=0.860 3(5) nm, b=0.898 7(6) nm, c=2.273(2) nm, V=1.758(2) nm3, Z=4, λ=0.071 073 nm, R=0.032 0, wR=0.106 7. The compound features two-dimensional (2D) grid layer of [CdSbS3]nn- with six-membered Cd2SbS3 rings and eight-membered Cd2Sb2S4 rings. The doubly protonated organic cations are located at the interlayer spaces of [CdSbS3]nn- and form extensive N-H…S hydrogen bonds. In addition, UV-Vis diffusion reflectance spectra suggest that the compound is semiconductor with estimated band gap 2.10 eV. CCDC: 879803.
A multiple thioantimonate compound, (1,4-DABH2)Cd2Sb2S6 (1) (1,4-DAB=1,4-diaminobutane) , was solvothermally synthesized at 160 ℃ and characterized by IR and TGA. Its crystal structure analysis reveals the compound was determined by single crystal X-ray diffraction. The crystal structure is orthorhombic in the space group Cmca. Crystallographic data: Mr=750.77, a=0.860 3(5) nm, b=0.898 7(6) nm, c=2.273(2) nm, V=1.758(2) nm3, Z=4, λ=0.071 073 nm, R=0.032 0, wR=0.106 7. The compound features two-dimensional (2D) grid layer of [CdSbS3]nn- with six-membered Cd2SbS3 rings and eight-membered Cd2Sb2S4 rings. The doubly protonated organic cations are located at the interlayer spaces of [CdSbS3]nn- and form extensive N-H…S hydrogen bonds. In addition, UV-Vis diffusion reflectance spectra suggest that the compound is semiconductor with estimated band gap 2.10 eV. CCDC: 879803.
2013, 29(5): 985-990
doi: 10.3969/j.issn.1001-4861.2013.00.112
Abstract:
The kaolinite/benzamide was prepared with a direct displacement intercalation method by using kaolinite/DMSO intercalation complex as an intermediate. The XRD and FTIR results show that benzamide has inserted into kaolinite and formed new hydrogen bonds with the inner surface of kaolinite. The thermal decomposition behavior of the complex was studied by TG and DSC. The TG and DSC results indicate that the decomposition process of the complex proceeds in two steps. The first step is deintercalation of the intercalated benzamide at 231 ℃ and the second step is dehydroxylation of kaolinite. For the first step, the kinetic triplet of the complex was calculated by the Modified Iterative Iso-conversional Procedure,Malek and Dollimore methods. The activation energy Ea is 75.4 kJ·mol-1, the range of pre-exponential factor A is 4.9×1010～8.8×1010 s-1. The optimized mechanism function is nth-order chemical reaction,the mechanism function is G(α)=[1-(1-α)1-n]/(1-n), f(α)=(1-α)n.
The kaolinite/benzamide was prepared with a direct displacement intercalation method by using kaolinite/DMSO intercalation complex as an intermediate. The XRD and FTIR results show that benzamide has inserted into kaolinite and formed new hydrogen bonds with the inner surface of kaolinite. The thermal decomposition behavior of the complex was studied by TG and DSC. The TG and DSC results indicate that the decomposition process of the complex proceeds in two steps. The first step is deintercalation of the intercalated benzamide at 231 ℃ and the second step is dehydroxylation of kaolinite. For the first step, the kinetic triplet of the complex was calculated by the Modified Iterative Iso-conversional Procedure,Malek and Dollimore methods. The activation energy Ea is 75.4 kJ·mol-1, the range of pre-exponential factor A is 4.9×1010～8.8×1010 s-1. The optimized mechanism function is nth-order chemical reaction,the mechanism function is G(α)=[1-(1-α)1-n]/(1-n), f(α)=(1-α)n.
2013, 29(5): 991-998
doi: 10.3969/j.issn.1001-4861.2013.00.156
Abstract:
The nano-composites Ag/ZnO-TiO2 under cetyltrimethylammonium bromide(CTAB) were prepared with molar ratio of 0.1:2:1 about Ag:Zn:Ti by the sol-gel method combined with temperature-programmed treatment. The phase composition, structures and morphologies of the nano-composite Ag/ZnO-TiO2 by post-processing methods of calcination at different temperature(500, 600, 700 ℃) and time(5 h, 7 h) were well-characterized by X-ray diffraction(XRD), and UV-visible diffuse reflectance spectrometer(UV-Vis/DRS), and X-ray photoelectron spectroscopy(XPS), and Transmission electron microscopy(TEM), and Scanning electron microscopy combined with X-ray energy dispersive spectroscopy(SEM-EDS) and N2 adsorption-desorption measurement. Results showed that a series of composites had not only the ZnO wurtzite and TiO2 anatase structures, meanwhile, part Zn2TiO4 were generated and silver species existing in the nano-composite Ag/ZnO-TiO2 was metallic Ag0. By the method changed calcination temperature and time, different nano-composites Ag/ZnO-TiO2(CTAB) showed nanowires and nano-ball morphology, moreover, which were uniformly distribution. By the photocatalytic degradation of RB, under UV light irradiation, the results showed that the activities of sample calcined at different time and temperature were obvious distinction.
The nano-composites Ag/ZnO-TiO2 under cetyltrimethylammonium bromide(CTAB) were prepared with molar ratio of 0.1:2:1 about Ag:Zn:Ti by the sol-gel method combined with temperature-programmed treatment. The phase composition, structures and morphologies of the nano-composite Ag/ZnO-TiO2 by post-processing methods of calcination at different temperature(500, 600, 700 ℃) and time(5 h, 7 h) were well-characterized by X-ray diffraction(XRD), and UV-visible diffuse reflectance spectrometer(UV-Vis/DRS), and X-ray photoelectron spectroscopy(XPS), and Transmission electron microscopy(TEM), and Scanning electron microscopy combined with X-ray energy dispersive spectroscopy(SEM-EDS) and N2 adsorption-desorption measurement. Results showed that a series of composites had not only the ZnO wurtzite and TiO2 anatase structures, meanwhile, part Zn2TiO4 were generated and silver species existing in the nano-composite Ag/ZnO-TiO2 was metallic Ag0. By the method changed calcination temperature and time, different nano-composites Ag/ZnO-TiO2(CTAB) showed nanowires and nano-ball morphology, moreover, which were uniformly distribution. By the photocatalytic degradation of RB, under UV light irradiation, the results showed that the activities of sample calcined at different time and temperature were obvious distinction.
2013, 29(5): 999-1006
doi: 10.3969/j.issn.1001-4861.2013.00.145
Abstract:
The core/shell structured ternary alloy of Cu@CoCr was synthesized by a one-step in-situ synthesis method under mild conditions. The catalytic performance of Cu@CoCr was studied for the hydrolysis of NH3BH3 (AB) aqueous solution. The TOF (turn over frequency) of 0.242 0 molH2·moLcat-1·s-1 for Cu0.4@Co0.5Cr0.1 catalyst on AB hydrolysis reaction is close to the noble-metal based catalysts, such as Pt, Pd, etc. The activation energy of this catalyst is only 35 kJ·mol-1. After 5 cycles, this catalyst still keeps 35% of its initial activity. Compared to the non-core/shell structured CuCoCr alloy, the Cu@CoCr catalyst shows great improvements in activity, stability and reusability. Furthermore, the Cu@CoCr catalysts could be recovered by a magnet based on its magnetic properties.
The core/shell structured ternary alloy of Cu@CoCr was synthesized by a one-step in-situ synthesis method under mild conditions. The catalytic performance of Cu@CoCr was studied for the hydrolysis of NH3BH3 (AB) aqueous solution. The TOF (turn over frequency) of 0.242 0 molH2·moLcat-1·s-1 for Cu0.4@Co0.5Cr0.1 catalyst on AB hydrolysis reaction is close to the noble-metal based catalysts, such as Pt, Pd, etc. The activation energy of this catalyst is only 35 kJ·mol-1. After 5 cycles, this catalyst still keeps 35% of its initial activity. Compared to the non-core/shell structured CuCoCr alloy, the Cu@CoCr catalyst shows great improvements in activity, stability and reusability. Furthermore, the Cu@CoCr catalysts could be recovered by a magnet based on its magnetic properties.
2013, 29(5): 1007-1012
doi: 10.3969/j.issn.1001-4861.2013.00.076
Abstract:
A magnetic polymer electrolyte using agarose as polymer matrix, NMP as solvent and NiO nanoparticles as modifier was investigated and employed in the dye-sensitized solar cell (DSSC) in this paper. The influence of NiO nanoparticles content on magnetic polymer electrolyte was characterized by SEM and ionic conductivity test. The photovoltaic properties of the corresponding DSSCs with different concentrations of NiO nanoparticles were studied by photovoltaic performance tests and electrochemical impedance spectra (EIS). The results showed that the optimal concentration of NiO nanoparticles was 1.0wt%, in which concentration the surface morphology of the polymer electrolyte was smooth and this magnetic polymer electrolyte showed the maximum conductivity (2.43×10-3 S·cm-1). The photoelectric efficiency and electron lifetime of DSSCs increased initially and then decreased with the increasing of the NiO nanoparticles content, the optimal photoelectric efficiency as well as the longest electron lifetime were achieved at the NiO nanoparticles content of 1.0wt%. At this optimal content, the photoelectric efficiency of DSSC was 1.63%, the voltage, current density and the filling factor of the DSSC was 0.57 V, 5.8 mA·cm-2 and 0.53, respectively.
A magnetic polymer electrolyte using agarose as polymer matrix, NMP as solvent and NiO nanoparticles as modifier was investigated and employed in the dye-sensitized solar cell (DSSC) in this paper. The influence of NiO nanoparticles content on magnetic polymer electrolyte was characterized by SEM and ionic conductivity test. The photovoltaic properties of the corresponding DSSCs with different concentrations of NiO nanoparticles were studied by photovoltaic performance tests and electrochemical impedance spectra (EIS). The results showed that the optimal concentration of NiO nanoparticles was 1.0wt%, in which concentration the surface morphology of the polymer electrolyte was smooth and this magnetic polymer electrolyte showed the maximum conductivity (2.43×10-3 S·cm-1). The photoelectric efficiency and electron lifetime of DSSCs increased initially and then decreased with the increasing of the NiO nanoparticles content, the optimal photoelectric efficiency as well as the longest electron lifetime were achieved at the NiO nanoparticles content of 1.0wt%. At this optimal content, the photoelectric efficiency of DSSC was 1.63%, the voltage, current density and the filling factor of the DSSC was 0.57 V, 5.8 mA·cm-2 and 0.53, respectively.
2013, 29(5): 1013-1018
doi: 10.3969/j.issn.1001-4861.2013.00.149
Abstract:
Li-rich solid solution cathode material Li[Li0.2Ni0.2Mn0.6]O2 was synthesized by a sol-gel method and subsequent solid-state sintering process, using LiOH·H2O, Mn(CH3COO)2·4H2O and H3COO)2·4H2O as raw materials, and citric acid (CA) and ethylene diamine tetraacetic acid (EDTA) as chelating agents, respectively. The as-synthesized materials were characterized by X-ray diffraction, scanning electron microscope and Laser Particle Size Analyzer, and the electrochemical properties of materials were investigated. The material using CA as chelating agent showed higher capacity and better rate performance than that using EDTA as chelating agent. The half-cell of Li/Li[Li0.2Ni0.2Mn0.6]O2 using CA as chelating agent delivered a charge specific capacity of 324 mAh·g-1 with an initial efficiency of 82% at a current density of 18 mA·g-1 between 2.0 and 4.8 V, and retained the reversible capacity of 120 mAh·g-1 even at a high current density of 180 mA·g-1.
Li-rich solid solution cathode material Li[Li0.2Ni0.2Mn0.6]O2 was synthesized by a sol-gel method and subsequent solid-state sintering process, using LiOH·H2O, Mn(CH3COO)2·4H2O and H3COO)2·4H2O as raw materials, and citric acid (CA) and ethylene diamine tetraacetic acid (EDTA) as chelating agents, respectively. The as-synthesized materials were characterized by X-ray diffraction, scanning electron microscope and Laser Particle Size Analyzer, and the electrochemical properties of materials were investigated. The material using CA as chelating agent showed higher capacity and better rate performance than that using EDTA as chelating agent. The half-cell of Li/Li[Li0.2Ni0.2Mn0.6]O2 using CA as chelating agent delivered a charge specific capacity of 324 mAh·g-1 with an initial efficiency of 82% at a current density of 18 mA·g-1 between 2.0 and 4.8 V, and retained the reversible capacity of 120 mAh·g-1 even at a high current density of 180 mA·g-1.
2013, 29(5): 1019-1024
doi: 10.3969/j.issn.1001-4861.2013.00.121
Abstract:
The GaOOH film composed of spindle-shaped GaOOH microparticles was firstly fabricated by hydrothermal method on Si substrate spun with ZnO particles, and then ammoniated at 950 ℃ by CVD method to give GaN film. The morphologies, crystal structure and optical properties of the samples before and after ammoniation were characterized by FESEM, EDS, TEM, XRD and PL analyses. The results show that the GaOOH film was composed of spindle-shaped microrods with a diameter of 600 nm and a length of about 1.5～2 μm. Ammoniation did not change the morphologies of GaOOH film but converted its crystal structure from orthorhombic phase of GaOOH into wurtzite GaN; and the position of PL peak at the green light range for GOOH films shifted to blue range with a peak at 365 nm, which may be related to the transformation of crystal structure. Finally, the formation mechanism of GaOOH film and the chemical reaction during the transformation from GaOOH film to GaN film were proposed.
The GaOOH film composed of spindle-shaped GaOOH microparticles was firstly fabricated by hydrothermal method on Si substrate spun with ZnO particles, and then ammoniated at 950 ℃ by CVD method to give GaN film. The morphologies, crystal structure and optical properties of the samples before and after ammoniation were characterized by FESEM, EDS, TEM, XRD and PL analyses. The results show that the GaOOH film was composed of spindle-shaped microrods with a diameter of 600 nm and a length of about 1.5～2 μm. Ammoniation did not change the morphologies of GaOOH film but converted its crystal structure from orthorhombic phase of GaOOH into wurtzite GaN; and the position of PL peak at the green light range for GOOH films shifted to blue range with a peak at 365 nm, which may be related to the transformation of crystal structure. Finally, the formation mechanism of GaOOH film and the chemical reaction during the transformation from GaOOH film to GaN film were proposed.
2013, 29(5): 1025-1030
doi: 10.3969/j.issn.1001-4861.2013.00.150
Abstract:
Objective:The aim of this study was to investigate the dose-effect relation of the ability that silver nanoparticles (SNPs) crossing through the blood-brain barrier (BBB) and presume its mechanism. Methods:In this study, SNPs were test samples and silver microparticles (SMPs) acted as control samples. First, an in vitro BBB model was established. Second, SNPs or SMPs were cultured in the BBB model at different dose from 25 μg·mL-1 to 400 μg·mL-1, respectively. After 4 hours of culture, the ultrastructure of BBB and the percentage of silver particles crossing through BBB were evaluated with TEM and ICP-MS respectively. Results:Results demonstrated that SNPs crossed the BBB, while the SMPs did not. When SNPS dose<100 μg·mL-1, about 2% silver particles crossed BBB, and the BBBs ultrastructures were normal. When dose>100 μg·mL-1, the higher dose is, the more silver particles crossed BBB, and the more damage occurred in the BBBs ultrastructures. When dose=400 μg·mL-1, about 15% silver particles crossed BBB. Conclusion:The results suggested that membrane-mobile transport mechanism is the main way allowing SNPs to cross the BBB in low dose. Cytotoxicity mechanism is the main way allowing SNPs to cross the BBB in higher dose. It is also suggested that SNPs could cross the BBB even in a low dose. A cautious attitude would be hold before silver nanoparticles-based medical devices were used in clinical practice.
Objective:The aim of this study was to investigate the dose-effect relation of the ability that silver nanoparticles (SNPs) crossing through the blood-brain barrier (BBB) and presume its mechanism. Methods:In this study, SNPs were test samples and silver microparticles (SMPs) acted as control samples. First, an in vitro BBB model was established. Second, SNPs or SMPs were cultured in the BBB model at different dose from 25 μg·mL-1 to 400 μg·mL-1, respectively. After 4 hours of culture, the ultrastructure of BBB and the percentage of silver particles crossing through BBB were evaluated with TEM and ICP-MS respectively. Results:Results demonstrated that SNPs crossed the BBB, while the SMPs did not. When SNPS dose<100 μg·mL-1, about 2% silver particles crossed BBB, and the BBBs ultrastructures were normal. When dose>100 μg·mL-1, the higher dose is, the more silver particles crossed BBB, and the more damage occurred in the BBBs ultrastructures. When dose=400 μg·mL-1, about 15% silver particles crossed BBB. Conclusion:The results suggested that membrane-mobile transport mechanism is the main way allowing SNPs to cross the BBB in low dose. Cytotoxicity mechanism is the main way allowing SNPs to cross the BBB in higher dose. It is also suggested that SNPs could cross the BBB even in a low dose. A cautious attitude would be hold before silver nanoparticles-based medical devices were used in clinical practice.
2013, 29(5): 1031-1036
doi: 10.3969/j.issn.1001-4861.2013.00.142
Abstract:
A new core-shell structure precursor were prepared by a co-precipitation method. A gradient concentration of Ni-Co-Mn shell layer was co-precipitated on the Ni(OH)2 core which was used as the precursor. Then, the well-ordered spherical LiNi0.92Co0.04Mn0.04O2 was synthesized by sintering the mixture of as-prepared precursor and LiOH·H2O in O2. The prepared samples were characterized by X-ray diffractometry, SEM and galvanostatic charge-discharge test. The results show that, the product has a layered hexagonal α-NaFeO2 structure and a spherical morphology. The line scan test of elements on the cross section area of coating shell show that the main elements of the materials change gradiently. The initial discharge capacity is 193.8 mAh·g-1 at 0.1C rate between 2.8 and 4.3 V and retains 96.8% after 40 cycles at 25 ℃. The capacity at 1C and 2C is 175 mAh·g-1 and 165.1 mAh·g-1. When cycled at 55 ℃, the initial discharge capacity is 236.1 mAh·g-1 and retains 77.5% after 40 cycles, indicating good electrochemical capacity and cycling stability.
A new core-shell structure precursor were prepared by a co-precipitation method. A gradient concentration of Ni-Co-Mn shell layer was co-precipitated on the Ni(OH)2 core which was used as the precursor. Then, the well-ordered spherical LiNi0.92Co0.04Mn0.04O2 was synthesized by sintering the mixture of as-prepared precursor and LiOH·H2O in O2. The prepared samples were characterized by X-ray diffractometry, SEM and galvanostatic charge-discharge test. The results show that, the product has a layered hexagonal α-NaFeO2 structure and a spherical morphology. The line scan test of elements on the cross section area of coating shell show that the main elements of the materials change gradiently. The initial discharge capacity is 193.8 mAh·g-1 at 0.1C rate between 2.8 and 4.3 V and retains 96.8% after 40 cycles at 25 ℃. The capacity at 1C and 2C is 175 mAh·g-1 and 165.1 mAh·g-1. When cycled at 55 ℃, the initial discharge capacity is 236.1 mAh·g-1 and retains 77.5% after 40 cycles, indicating good electrochemical capacity and cycling stability.
2013, 29(5): 1037-1044
doi: 10.3969/j.issn.1001-4861.2013.00.159
Abstract:
The binding reaction between heavy metal ions Cr(Ⅵ) and serum proteome was investigated using affinity capillary electrophoresis(ACE) method. Based on the site binding model, a model about the interaction between Cr(Ⅵ) as the ligand and FBS as the receptor, was established. The binding performance of heavy metal ions Cr(Ⅵ) and the serum proteome was studied under proteomic conditions, and the results showed that, Cr(Ⅵ)-protein complexes formed between Cr(Ⅵ) and the high abundance component albumin in FBS, such as albumin (bovine serum albumin, BSA), transferrin protein (Bovine apo transferrin, bATF), immunogolobulin (Bovine IgG, IgG) and so on, and the binding reactions of Cr(Ⅵ) -FBS are fast equilibrium reactions. The apparent binding constant was determined through non-linear fitting binding reaction and based on changes of the effective mobility, and KCr(Ⅵ)-bATF=1.27×104 L·mol-1, KCr(Ⅵ)-IgG=4.91×104 L·mol-1, KCr(Ⅵ)-BSA=8.98×104 L·mol-1. Dosage-dependent effect exists among the concentration of Cr(Ⅵ) and the strength of the binding reactions. This work has referential meaning for understanding deeply the binding reaction mechanism of chromium(Ⅵ) with serum proteome.
The binding reaction between heavy metal ions Cr(Ⅵ) and serum proteome was investigated using affinity capillary electrophoresis(ACE) method. Based on the site binding model, a model about the interaction between Cr(Ⅵ) as the ligand and FBS as the receptor, was established. The binding performance of heavy metal ions Cr(Ⅵ) and the serum proteome was studied under proteomic conditions, and the results showed that, Cr(Ⅵ)-protein complexes formed between Cr(Ⅵ) and the high abundance component albumin in FBS, such as albumin (bovine serum albumin, BSA), transferrin protein (Bovine apo transferrin, bATF), immunogolobulin (Bovine IgG, IgG) and so on, and the binding reactions of Cr(Ⅵ) -FBS are fast equilibrium reactions. The apparent binding constant was determined through non-linear fitting binding reaction and based on changes of the effective mobility, and KCr(Ⅵ)-bATF=1.27×104 L·mol-1, KCr(Ⅵ)-IgG=4.91×104 L·mol-1, KCr(Ⅵ)-BSA=8.98×104 L·mol-1. Dosage-dependent effect exists among the concentration of Cr(Ⅵ) and the strength of the binding reactions. This work has referential meaning for understanding deeply the binding reaction mechanism of chromium(Ⅵ) with serum proteome.
2013, 29(5): 1045-1050
doi: 0.3969/j.issn.1001-4861.2013.00.151
Abstract:
Flowerlike ZnO nanostructure was synthesized via a co-precipitation method by using Zn(NO3)2·6H2O, Al(NO3)3 and (CH2)6N4 as reactants, PEG400 as a surfactant. The obtained ZnO nanostructures can be tuned by the added Al3+ in the above process, resulting in an increase of gas-sensing response. The gas-sensing response of 0.3wt% Al3+-doped ZnO nanostructure reaches 28 to an ethanol concentration of 0.200 mL·L-1, with a response time of only 12 s at the working temperature of 350 ℃.
Flowerlike ZnO nanostructure was synthesized via a co-precipitation method by using Zn(NO3)2·6H2O, Al(NO3)3 and (CH2)6N4 as reactants, PEG400 as a surfactant. The obtained ZnO nanostructures can be tuned by the added Al3+ in the above process, resulting in an increase of gas-sensing response. The gas-sensing response of 0.3wt% Al3+-doped ZnO nanostructure reaches 28 to an ethanol concentration of 0.200 mL·L-1, with a response time of only 12 s at the working temperature of 350 ℃.
2013, 29(5): 1051-1056
doi: 10.3969/j.issn.1001-4861.2013.00.133
Abstract:
The graphene-Au nanocomposites were synthesized through hydrothermal route. Transmission electron microscopy (TEM) images gave direct evidence of the thin and transparent sheet structure of graphene. X-ray photoelectron spectroscopic (XPS) and X-ray diffraction (XRD) results also showed the presence of Au and the reduction of graphene oxide. As a model, myoglobin (Mb) was entrapped onto the nanocomposite modified glassy carbon electrode (GCE) and applied to construct a sensor. The immobilized Mb showed a pair of well-defined redox peaks and high catalytic activity for the reduction of H2O2. The biosensor with a linear range from 0.1 to 1.5 μmol·L-1 and a detection limit of 0.05 μmol·L-1 (S/N=3) showed good selectivity, reproducibility and stability. The graphene-Au nanocomposites provide a novel matrix for protein immobilization and the construction of biosensors via the direct electron transfer of protein.
The graphene-Au nanocomposites were synthesized through hydrothermal route. Transmission electron microscopy (TEM) images gave direct evidence of the thin and transparent sheet structure of graphene. X-ray photoelectron spectroscopic (XPS) and X-ray diffraction (XRD) results also showed the presence of Au and the reduction of graphene oxide. As a model, myoglobin (Mb) was entrapped onto the nanocomposite modified glassy carbon electrode (GCE) and applied to construct a sensor. The immobilized Mb showed a pair of well-defined redox peaks and high catalytic activity for the reduction of H2O2. The biosensor with a linear range from 0.1 to 1.5 μmol·L-1 and a detection limit of 0.05 μmol·L-1 (S/N=3) showed good selectivity, reproducibility and stability. The graphene-Au nanocomposites provide a novel matrix for protein immobilization and the construction of biosensors via the direct electron transfer of protein.
2013, 29(5): 1057-1064
doi: 10.3969/j.issn.1001-4861.2013.00.179
Abstract:
A type of double layer(array-cluster)TiO2 films were prepared with mixed solution of hydrochloric acid and tetrabutyl titanate (TBOT) by a hydrothermal method at specific reaction condition. It was found that the TiO2 films on the substrate has a two-layer structure and has the tetragonal rutile phase observed from the field emission scaning electron microscopy (FESEM) and the X-ray diffraction (XRD). Moreover, the subjacent layer of the two-layer structure were TiO2 rods array, while the supernatant layer was TiO2 rods clusters, and microscopic structure of these rods all are made of smaller TiO2 nanorods(25～65 nm). This two-layer structure of TiO2 films can favors to acquiring more light and adsorbing more dye, and could provide a fast circulation channel for photon-generated electrons. The thickness of this type of TiO2 films in supernatant layer can be varied by changing initial reactant concentration, growth time or substrate placed angles. And without any modification treatment, a light-to- electricity conversion effciency of DSSC with TiO2 nanorod array-cluster films can enhance 2.6 time in comparison with only TiO2 nanorod array films.
A type of double layer(array-cluster)TiO2 films were prepared with mixed solution of hydrochloric acid and tetrabutyl titanate (TBOT) by a hydrothermal method at specific reaction condition. It was found that the TiO2 films on the substrate has a two-layer structure and has the tetragonal rutile phase observed from the field emission scaning electron microscopy (FESEM) and the X-ray diffraction (XRD). Moreover, the subjacent layer of the two-layer structure were TiO2 rods array, while the supernatant layer was TiO2 rods clusters, and microscopic structure of these rods all are made of smaller TiO2 nanorods(25～65 nm). This two-layer structure of TiO2 films can favors to acquiring more light and adsorbing more dye, and could provide a fast circulation channel for photon-generated electrons. The thickness of this type of TiO2 films in supernatant layer can be varied by changing initial reactant concentration, growth time or substrate placed angles. And without any modification treatment, a light-to- electricity conversion effciency of DSSC with TiO2 nanorod array-cluster films can enhance 2.6 time in comparison with only TiO2 nanorod array films.
2013, 29(5): 1065-1071
doi: 10.3969/j.issn.1001-4861.2013.00.158
Abstract:
A complex Sm2(1-npac)6(dmpy)2·(H2O)3(1), (1-npac=1-naphthaleneacetate, dmpy=5,5'-dimethyl-2,2'-bipyridine) has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, powder X-ray diffraction, UV-Vis and single-crystal X-ray diffraction. Structural determination reveals that the samarium ions are bridged by two bidentate and two terdentate carboxylato groups to give centrosymmetric dimers with Sm…Sm separation of 0.3925(2) nm, which is further extended to a 3D supramolecular structure by hydrogen bonds, C-H…π and π…π stacking interactions. Solid-state 1 emits the intensive orange luminescence of Sm3+ ion with fluorescence lifetime of 0.87 μs (598 nm) at room temperature. CCDC: 898378.
A complex Sm2(1-npac)6(dmpy)2·(H2O)3(1), (1-npac=1-naphthaleneacetate, dmpy=5,5'-dimethyl-2,2'-bipyridine) has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, powder X-ray diffraction, UV-Vis and single-crystal X-ray diffraction. Structural determination reveals that the samarium ions are bridged by two bidentate and two terdentate carboxylato groups to give centrosymmetric dimers with Sm…Sm separation of 0.3925(2) nm, which is further extended to a 3D supramolecular structure by hydrogen bonds, C-H…π and π…π stacking interactions. Solid-state 1 emits the intensive orange luminescence of Sm3+ ion with fluorescence lifetime of 0.87 μs (598 nm) at room temperature. CCDC: 898378.
2013, 29(5): 1072-1076
doi: 10.3969/j.issn.1001-4861.2013.00.163
Abstract:
A new Sm3+ complex [Sm2(BTA)3·(H2O)10]·5H2O (1) (H2BTA=5, 5-bis(1H-tetrazoly)amine, CAS No. 127661-01-2) was synthesized by the hydrothermal reaction of SmCl3·6H2O and bis(tetrazoly)amine, and characterized by X-ray diffraction and elemental analysis. The crystal of 1 is triclinic with space group P1. In 1, two Sm3+ ions are coordinated to the chelated N atoms of BTA anions and water molecules to give two different mononuclear units with a distorted tetragonal antiprism structure. A 3D supermolecular structure is formed by three different intermolecular hydrogen bonding interactions of O-H…N, O-H…O and N-H…N in this complex. CCDC: 894688
A new Sm3+ complex [Sm2(BTA)3·(H2O)10]·5H2O (1) (H2BTA=5, 5-bis(1H-tetrazoly)amine, CAS No. 127661-01-2) was synthesized by the hydrothermal reaction of SmCl3·6H2O and bis(tetrazoly)amine, and characterized by X-ray diffraction and elemental analysis. The crystal of 1 is triclinic with space group P1. In 1, two Sm3+ ions are coordinated to the chelated N atoms of BTA anions and water molecules to give two different mononuclear units with a distorted tetragonal antiprism structure. A 3D supermolecular structure is formed by three different intermolecular hydrogen bonding interactions of O-H…N, O-H…O and N-H…N in this complex. CCDC: 894688
2013, 29(5): 1077-1083
doi: 10.3969/j.issn.1001-4861.2013.00.132
Abstract:
Cu/Co/Fe mixed oxides (Cu/Co/Fe-MOs) were prepared by calcining the precursors of Cu/Co/Fe layered double hydroxides (Cu/Co/Fe-LDHs), and were used as new catalysts for the thermal decomposition of ammonium perchlorate (AP). The catalytic activity was investigated using differential thermal analysis (DTA) and thermal gravimetric analyzer coupled with an online mass spectrometer (TG-MS). The results reveal that Cu/Co/Fe-MOs exhibit CuFe2O4 and (CoFe2)O4 phase with high specific surface area of 70～110 m2·g-1. The Cu/Co/Fe-MOs have homogenous particles with crystallite size of 20～30 nm. The thermal decomposition temperature of AP can be lowered by 139 ℃ with 4wt% of Cu/Co/Fe-MOs calcined at 400 ℃. The improvement in thermal decomposition of AP by Cu/Co/Fe-MOs catalysts is achieved via the superoxide ion (O2-) adsorbed on the surface of Cu/Co/Fe-MOs.
Cu/Co/Fe mixed oxides (Cu/Co/Fe-MOs) were prepared by calcining the precursors of Cu/Co/Fe layered double hydroxides (Cu/Co/Fe-LDHs), and were used as new catalysts for the thermal decomposition of ammonium perchlorate (AP). The catalytic activity was investigated using differential thermal analysis (DTA) and thermal gravimetric analyzer coupled with an online mass spectrometer (TG-MS). The results reveal that Cu/Co/Fe-MOs exhibit CuFe2O4 and (CoFe2)O4 phase with high specific surface area of 70～110 m2·g-1. The Cu/Co/Fe-MOs have homogenous particles with crystallite size of 20～30 nm. The thermal decomposition temperature of AP can be lowered by 139 ℃ with 4wt% of Cu/Co/Fe-MOs calcined at 400 ℃. The improvement in thermal decomposition of AP by Cu/Co/Fe-MOs catalysts is achieved via the superoxide ion (O2-) adsorbed on the surface of Cu/Co/Fe-MOs.
2013, 29(5): 1084-1088
doi: 10.3969/j.issn.1001-4861.2013.00.165
Abstract:
L-[Ni2(van)(Hvap)2(MeOH)2]ClO4·2.5MeOH·H2O (1) was prepared via the reaction of Ni(ClO4)2·H2O with o-vanillin and L-2-amino-3-phenyl-1-propanol in the presence of triethylamine. The structure of 1 was characterized by elemental analysis, IR, TGA, solid-state CD spectra and single-crystal X-ray diffraction analyses. The X-ray diffraction analyses reveal that the complex crystallizes in the monoclinic chiral space group P21 with Z=1. Two nickel (Ⅱ) ions are bridged by the deprotonated o-vanillin molecule, forming a {Ni2O} dinuclear structure. The solid-state CD spectra comfirm the chiral nature of 1. CCDC: 928211.
L-[Ni2(van)(Hvap)2(MeOH)2]ClO4·2.5MeOH·H2O (1) was prepared via the reaction of Ni(ClO4)2·H2O with o-vanillin and L-2-amino-3-phenyl-1-propanol in the presence of triethylamine. The structure of 1 was characterized by elemental analysis, IR, TGA, solid-state CD spectra and single-crystal X-ray diffraction analyses. The X-ray diffraction analyses reveal that the complex crystallizes in the monoclinic chiral space group P21 with Z=1. Two nickel (Ⅱ) ions are bridged by the deprotonated o-vanillin molecule, forming a {Ni2O} dinuclear structure. The solid-state CD spectra comfirm the chiral nature of 1. CCDC: 928211.
2013, 29(5): 1089-1095
doi: 10.3969/j.issn.1001-4861.2013.00.182
Abstract:
Heteropolyacid complex (HP2W18O62)(C6H6NO2)5·2H2O (1) with 2-picolinic acid in deionized water has been synthesized and characterized by IR, UV, cyclic voltammetry (CV) and X-ray single-crystal diffraction methods. The 2-picolinic acid was obtained by decarboxylation of pyridine-2,6-dicarboxylicacid(H2PDA). The results show that the crystal of the complex 1 belongs to monoclinic system, space group P21/n with: a=1.553 3(2)nm, b=2.006 3(3) nm, c=2.759 9(4) nm, β=103.981(2)°, Z=4, F(000)=8 816. Intermolecular hydrogen-bond and weak interactions from polyanions and 2-picolinic acid lead the complex to a 3D supramolecular architecture. CV study reveals that compound 1 exhibits four chemical processes. CCDC: 905785.
Heteropolyacid complex (HP2W18O62)(C6H6NO2)5·2H2O (1) with 2-picolinic acid in deionized water has been synthesized and characterized by IR, UV, cyclic voltammetry (CV) and X-ray single-crystal diffraction methods. The 2-picolinic acid was obtained by decarboxylation of pyridine-2,6-dicarboxylicacid(H2PDA). The results show that the crystal of the complex 1 belongs to monoclinic system, space group P21/n with: a=1.553 3(2)nm, b=2.006 3(3) nm, c=2.759 9(4) nm, β=103.981(2)°, Z=4, F(000)=8 816. Intermolecular hydrogen-bond and weak interactions from polyanions and 2-picolinic acid lead the complex to a 3D supramolecular architecture. CV study reveals that compound 1 exhibits four chemical processes. CCDC: 905785.
2013, 29(5): 1096-1102
doi: 10.3969/j.issn.1001-4861.2013.00.175
Abstract:
The complexes of [Zn(TBTA)(BPP)]n (1) and [Cd(TBTA)(BPP)2(H2O)2]n (2) based on 2,3,5,6-tetrabromo-terephthalic acid (H2TBTA) and 1,3-bis(4-pyridyl)propane (BPP) have been constructed in CH3OH/H2O solution at room temperature. The structures and properties were characterized by the single-crystal X-ray diffraction, elemental analyses, IR spectra and thermogravimetric analyses. The results indicate the complex 1 is two dimension (2D) wave-like layer network, and the complex 2 is one dimension (1D) chain structure, and the carboxyl groups in H2TBTA ligands coordinate with metal ions in monodentate mode, and the H-bonding interactions contribute to the stabilities of the structures of the complexes. CCDC: 854381, 1; 854380, 2.
The complexes of [Zn(TBTA)(BPP)]n (1) and [Cd(TBTA)(BPP)2(H2O)2]n (2) based on 2,3,5,6-tetrabromo-terephthalic acid (H2TBTA) and 1,3-bis(4-pyridyl)propane (BPP) have been constructed in CH3OH/H2O solution at room temperature. The structures and properties were characterized by the single-crystal X-ray diffraction, elemental analyses, IR spectra and thermogravimetric analyses. The results indicate the complex 1 is two dimension (2D) wave-like layer network, and the complex 2 is one dimension (1D) chain structure, and the carboxyl groups in H2TBTA ligands coordinate with metal ions in monodentate mode, and the H-bonding interactions contribute to the stabilities of the structures of the complexes. CCDC: 854381, 1; 854380, 2.
