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2015 Volume 31 Issue 10
2015, 31(10): 1919-1928
doi: 10.11862/CJIC.2015.265
Abstract:
A yellow-fluorescent hydrotalcite-like composition was prepared by coprecipitation method. Under excitation with 470 nm blue-light, the hydrotalcite-like composition can exhibit yellow emission at 557 nm. The hydrotalcite-like composition was surface modified by using silane coupling agent and the influence of the surface modification was discussed. Additionally, a white LED device was fabricated by coating hydrotalcite-like compound onto GaN-based LED chip. The results indicate that yellow-emitting fluorescent hydrotalcite-like compound is a promising candidate for white LED. One kind of metal-organic complexes/inorganic nanocomposite, which was prepared by low-temperature one step method, was successfully applied in WLED device in this paper. It may expand the selection range of phosphors for light emitting diodes.
A yellow-fluorescent hydrotalcite-like composition was prepared by coprecipitation method. Under excitation with 470 nm blue-light, the hydrotalcite-like composition can exhibit yellow emission at 557 nm. The hydrotalcite-like composition was surface modified by using silane coupling agent and the influence of the surface modification was discussed. Additionally, a white LED device was fabricated by coating hydrotalcite-like compound onto GaN-based LED chip. The results indicate that yellow-emitting fluorescent hydrotalcite-like compound is a promising candidate for white LED. One kind of metal-organic complexes/inorganic nanocomposite, which was prepared by low-temperature one step method, was successfully applied in WLED device in this paper. It may expand the selection range of phosphors for light emitting diodes.
2015, 31(10): 1929-1937
doi: 10.11862/CJIC.2015.231
Abstract:
By controllable syntheses, two low dimensional Cd(Ⅱ) complexes with the newly zwitterionic dicarboxylate ligand 1-(4-carboxylatobenzyl)pyridinium-4-carboxylate (HL), {Cd(L)2·4H2O}n(1), and {[Cd(L)(N3)]·3H2O}n(2) have been synthesized and structurally characterized by IR, elemental analyses, single-crystal X-ray diffraction. In compound 1, the eight-coordinated Cd(Ⅱ) ions are chelated by four equivalent L in a bis(chelating) mode, forming a one-dimensional coordination polymer structure. In 2, six-coordinated Cd(Ⅱ) ions are triple bridged by two carboxylate groups and an azide ion into 1D uniform [Cd(N3)(OCO)2]n chains, which are further interlinked through the cationic N-benzylpyridinium backbones of the L ligands into 2D sheet. Interestingly, the fluorescence measurements show that all compounds exhibit intense blue emission in the solid state, and the emission bands are correlated to the coordination modes of the L ligand. CCDC:1031439, HL; 1031440, 1; 1031441, 2.
By controllable syntheses, two low dimensional Cd(Ⅱ) complexes with the newly zwitterionic dicarboxylate ligand 1-(4-carboxylatobenzyl)pyridinium-4-carboxylate (HL), {Cd(L)2·4H2O}n(1), and {[Cd(L)(N3)]·3H2O}n(2) have been synthesized and structurally characterized by IR, elemental analyses, single-crystal X-ray diffraction. In compound 1, the eight-coordinated Cd(Ⅱ) ions are chelated by four equivalent L in a bis(chelating) mode, forming a one-dimensional coordination polymer structure. In 2, six-coordinated Cd(Ⅱ) ions are triple bridged by two carboxylate groups and an azide ion into 1D uniform [Cd(N3)(OCO)2]n chains, which are further interlinked through the cationic N-benzylpyridinium backbones of the L ligands into 2D sheet. Interestingly, the fluorescence measurements show that all compounds exhibit intense blue emission in the solid state, and the emission bands are correlated to the coordination modes of the L ligand. CCDC:1031439, HL; 1031440, 1; 1031441, 2.
2015, 31(10): 1938-1945
doi: 10.11862/CJIC.2015.270
Abstract:
A one step method of synthesis of iron-nitrogen doped carbon nanoparticles (Fe/NCNPs) is developed by pyrolysis using citric acid and ammonium oxalate as carbon source and FeCl3 as iron source. The solution of as-prepared Fe/NCNPs emits blue fluorescent under 365 nm UV. As-prepared Fe/NCNPs are investigated by XRD, TEM, FTIR, FL and XPS. The result indicates that as-prepared Fe/NCNPs are well- dispersed with an average diameter of about 3~5 nm. Its fluorescence spectra show that the particles have excellent fluorescence performance, and with increasing excitation wavelength, the fluorescence spectra shift to longer wavelengths, which is multicolor. In addition, the solution of as-prepared Fe/NCNPs has good short wavelength optical emission with long wavelength visible and infrared light excitation, which is the up-converting function. When as-prepared Fe/NCNPs are applied to photocatalytic degradation of methylene blue (20 mg·L-1) irradiated by visible light, when the H2O2 is absent, the decolorization rate is over 90% in 15 hours; when H2O2 is present as oxidant, the decolorization rate is over 97% in 15 min, revealing excellent photocatalytic activity. The redox reaction mechanism of the photocatalytic degradation is evaluated by electrochemical method, and the result is consistent with the theory.
A one step method of synthesis of iron-nitrogen doped carbon nanoparticles (Fe/NCNPs) is developed by pyrolysis using citric acid and ammonium oxalate as carbon source and FeCl3 as iron source. The solution of as-prepared Fe/NCNPs emits blue fluorescent under 365 nm UV. As-prepared Fe/NCNPs are investigated by XRD, TEM, FTIR, FL and XPS. The result indicates that as-prepared Fe/NCNPs are well- dispersed with an average diameter of about 3~5 nm. Its fluorescence spectra show that the particles have excellent fluorescence performance, and with increasing excitation wavelength, the fluorescence spectra shift to longer wavelengths, which is multicolor. In addition, the solution of as-prepared Fe/NCNPs has good short wavelength optical emission with long wavelength visible and infrared light excitation, which is the up-converting function. When as-prepared Fe/NCNPs are applied to photocatalytic degradation of methylene blue (20 mg·L-1) irradiated by visible light, when the H2O2 is absent, the decolorization rate is over 90% in 15 hours; when H2O2 is present as oxidant, the decolorization rate is over 97% in 15 min, revealing excellent photocatalytic activity. The redox reaction mechanism of the photocatalytic degradation is evaluated by electrochemical method, and the result is consistent with the theory.
2015, 31(10): 1946-1952
doi: 10.11862/CJIC.2015.261
Abstract:
A new fluorescent ratio chemosensor (Dansyl-Cys-Pro-Pro-Cys-Trp-NH2) for metal ions has been synthesized via Fmoc solid-phase peptide synthesis. The interactions of the peptide with metal ions were investigated by fluorescence spectroscopy. Results showed that it showed high selectivity toward Cd2+ over other commonly coexistent metal ions. The peptide has the advantages of specific recognition to Cd2+, a good water-soluble and a fast response. The peptide tightly binds to Cd2+ with the binding constant of 3.0×1011 L2·mol-2 and the detection limit of 11.5 nmol·L-1.
A new fluorescent ratio chemosensor (Dansyl-Cys-Pro-Pro-Cys-Trp-NH2) for metal ions has been synthesized via Fmoc solid-phase peptide synthesis. The interactions of the peptide with metal ions were investigated by fluorescence spectroscopy. Results showed that it showed high selectivity toward Cd2+ over other commonly coexistent metal ions. The peptide has the advantages of specific recognition to Cd2+, a good water-soluble and a fast response. The peptide tightly binds to Cd2+ with the binding constant of 3.0×1011 L2·mol-2 and the detection limit of 11.5 nmol·L-1.
2015, 31(10): 1953-1958
doi: 10.11862/CJIC.2015.175
Abstract:
In2TiO5 nanobelts were fabricated by means of electrospinning using Ti(OC4H9)4、In(NO3)3 and polyvinyl pyrrolidone(PVP-K30) as raw materials. The nanobelts calcined at different temperature were characterized by XRD, SEM, UV-Vis DRS and N2 adsorption-desorption isotherms. The influences of the calcination temperatures on the crystallite size, morphology, BET specific surface area and pore size of In2TiO5 nanobelts was studied. The photocatalytic activity of the as-prepared In2TiO5 nanobelts was evaluated by the photocatalytic degradation of levofloxacin (LEV) of fluoroquinolone antibiotics under the irradiation of the high pressure mercury lamp (125 W). The results show the significant effect of calcination temperature on the morphology and photocatalytic activity of In2TiO5 nanobelts. When the calcination temperature is 800℃, the In2TiO5 nanobelts prepared exhibit the best photocatalytic activity with smooth surface, the width of (552±58) nm and thickness of 140 nm. The degradation rate of LEV can be up to 95% after 60 min of irradiation.
In2TiO5 nanobelts were fabricated by means of electrospinning using Ti(OC4H9)4、In(NO3)3 and polyvinyl pyrrolidone(PVP-K30) as raw materials. The nanobelts calcined at different temperature were characterized by XRD, SEM, UV-Vis DRS and N2 adsorption-desorption isotherms. The influences of the calcination temperatures on the crystallite size, morphology, BET specific surface area and pore size of In2TiO5 nanobelts was studied. The photocatalytic activity of the as-prepared In2TiO5 nanobelts was evaluated by the photocatalytic degradation of levofloxacin (LEV) of fluoroquinolone antibiotics under the irradiation of the high pressure mercury lamp (125 W). The results show the significant effect of calcination temperature on the morphology and photocatalytic activity of In2TiO5 nanobelts. When the calcination temperature is 800℃, the In2TiO5 nanobelts prepared exhibit the best photocatalytic activity with smooth surface, the width of (552±58) nm and thickness of 140 nm. The degradation rate of LEV can be up to 95% after 60 min of irradiation.
2015, 31(10): 1959-1965
doi: 10.11862/CJIC.2015.263
Abstract:
The cuboid-shaped WO3 nanoparticles were prepared by the hydrothermal method with controlling the amount of reactant and reaction time, then the as-prepared particles were characterized by X-ray powder diffraction (XRD), transmission electron microscope (TEM), and scanning electron microscope-energy dispersive spectrometry (SEM-EDS). The Effects of WO3 powders on the thermal decomposition of hexanitrohexaazaisowur-tzitane (CL-20) were investigated by differential scanning calorimetry (DSC). The results show that the peak temperature of the decomposition and the activation energy of WO3/CL-20 have 2.95℃ and 7.74 kJ·mol-1 lower than that of CL-20, indicating that nano-WO3 could accelerate the thermal decomposition of CL-20.
The cuboid-shaped WO3 nanoparticles were prepared by the hydrothermal method with controlling the amount of reactant and reaction time, then the as-prepared particles were characterized by X-ray powder diffraction (XRD), transmission electron microscope (TEM), and scanning electron microscope-energy dispersive spectrometry (SEM-EDS). The Effects of WO3 powders on the thermal decomposition of hexanitrohexaazaisowur-tzitane (CL-20) were investigated by differential scanning calorimetry (DSC). The results show that the peak temperature of the decomposition and the activation energy of WO3/CL-20 have 2.95℃ and 7.74 kJ·mol-1 lower than that of CL-20, indicating that nano-WO3 could accelerate the thermal decomposition of CL-20.
2015, 31(10): 1966-1970
doi: 10.11862/CJIC.2015.271
Abstract:
Li-rich layered cathode materials Li1.2Mn0.54Ni0.13Co0.13O2 with different second particle size distribution were prepared by carbonate based co-precipitation. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), laser particle size analyze and electrochemical performance tests. The results showed that there were no significant differences in structures between the Li1.2Mn0.54Ni0.13Co0.13O2 materials with different second particle size, and the three samples had similar discharge capacities (281 mAh·g-1) for the first cycle. However, the sample with smaller second particle size showed a much superior rate capability to the sample with bigger particle size. When the D50 of second particle size reduced to 4.59 μm, the sample delivered a discharge capacity of 199 mAh·g-1 at 3C-rate. The improvement in rate capability could be attributed to the smaller particle size, which gives a better contact between the active material and the electrolyte/conductive agent, at the same time a shorter diffusion path.
Li-rich layered cathode materials Li1.2Mn0.54Ni0.13Co0.13O2 with different second particle size distribution were prepared by carbonate based co-precipitation. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), laser particle size analyze and electrochemical performance tests. The results showed that there were no significant differences in structures between the Li1.2Mn0.54Ni0.13Co0.13O2 materials with different second particle size, and the three samples had similar discharge capacities (281 mAh·g-1) for the first cycle. However, the sample with smaller second particle size showed a much superior rate capability to the sample with bigger particle size. When the D50 of second particle size reduced to 4.59 μm, the sample delivered a discharge capacity of 199 mAh·g-1 at 3C-rate. The improvement in rate capability could be attributed to the smaller particle size, which gives a better contact between the active material and the electrolyte/conductive agent, at the same time a shorter diffusion path.
2015, 31(10): 1971-1980
doi: 10.11862/CJIC.2015.269
Abstract:
Under different synthetic condition, the Ag2S/ZnO photocatalyst with visible-light response was prepared by microwave hydrothermal two-step method. The phase structures, physicochemical properties and morphologies were well-characterized via X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance absorption (UV-Vis/DRS), Scanning electron microscopy (SEM) and N2 adsorption-desorption tests. Results indicate that the synthetic product is mainly hexagonal wurtzite ZnO, of which phase structure has been changed with the temperature of reaction and the nAg2S/nZnO increased. The presence of Ag2S enhances the light absorption of the photocatalyst under the visible-light region, redshifting the absorption band, and suppresses the growth of ZnO along the (001) crystal plane. In addition, with the nAg2S/nZnO increased, the morphology of synthetic Ag2S/ZnO realizes a transformation from the shape of popcorn to cylinder, moreover, the BET values reduce obviously. Compared to pure ZnO, when the nAg2S/nZnO was 1:10, the composite performs the highest photocatalytic activity to degrade Rhodamine B under the irradiation of ultraviolet, visible and simulated sunlight, far superior than P25 which was the most widely used at present. Moreover, there is no significant change in the degradation efficiency of Ag2S/ZnO 200° 1-10 after four times of recycling, which shows the photocatalytic stability to a certain extent. In addition, the capture experiments proved that holes brought out main effect on the photocatalytic reaction of Ag2S/ZnO. Accordingly, a potential reaction mechanism was proposed.
Under different synthetic condition, the Ag2S/ZnO photocatalyst with visible-light response was prepared by microwave hydrothermal two-step method. The phase structures, physicochemical properties and morphologies were well-characterized via X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance absorption (UV-Vis/DRS), Scanning electron microscopy (SEM) and N2 adsorption-desorption tests. Results indicate that the synthetic product is mainly hexagonal wurtzite ZnO, of which phase structure has been changed with the temperature of reaction and the nAg2S/nZnO increased. The presence of Ag2S enhances the light absorption of the photocatalyst under the visible-light region, redshifting the absorption band, and suppresses the growth of ZnO along the (001) crystal plane. In addition, with the nAg2S/nZnO increased, the morphology of synthetic Ag2S/ZnO realizes a transformation from the shape of popcorn to cylinder, moreover, the BET values reduce obviously. Compared to pure ZnO, when the nAg2S/nZnO was 1:10, the composite performs the highest photocatalytic activity to degrade Rhodamine B under the irradiation of ultraviolet, visible and simulated sunlight, far superior than P25 which was the most widely used at present. Moreover, there is no significant change in the degradation efficiency of Ag2S/ZnO 200° 1-10 after four times of recycling, which shows the photocatalytic stability to a certain extent. In addition, the capture experiments proved that holes brought out main effect on the photocatalytic reaction of Ag2S/ZnO. Accordingly, a potential reaction mechanism was proposed.
2015, 31(10): 1981-1986
doi: 10.11862/CJIC.2015.235
Abstract:
In this study, a simple low-temperature solution-impregnation method was developed for the fabrication of highly efficient AgBr photocatalyst with cooperation effect of Cu(Ⅱ) cocatalyst and graphene. Photocatalytic experimental results for the depolarization of methyl orange (MO) aqueous solution indicated that the AgBr with cooperation effect of Cu(Ⅱ) cocatalyst and graphene displayed very good photocatalytic activity. Especially, Cu(Ⅱ)(0.5 mol·L-1)/AgBr-rGO(0.5wt%) (rGO, reduced graphene oxide) showed the highest photocatalytic activity with a rate constant 0.027 31 min-1, while this value is higher than that of the pure AgBr (0.008 07 min-1), AgBr-rGO (0.5%)(0.015 98 min-1) and Cu(Ⅱ) (0.5 mol·L-1)/AgBr (0.015 19 min-1) by a factor of 3.38, 1.7 and 1.8, respectively. The reason for enhanced photocatalytic performance is that Cu(Ⅱ) can quickly catch the photogenerated electrons from AgBr and graphene has large specific surface which may provide a lot reduction active sites for Cu(Ⅱ), resulting in a rapid separation of photogenerated electrons and holes. This work may provide the new insights for the preparation of high performance AgBr photocatalyst.
In this study, a simple low-temperature solution-impregnation method was developed for the fabrication of highly efficient AgBr photocatalyst with cooperation effect of Cu(Ⅱ) cocatalyst and graphene. Photocatalytic experimental results for the depolarization of methyl orange (MO) aqueous solution indicated that the AgBr with cooperation effect of Cu(Ⅱ) cocatalyst and graphene displayed very good photocatalytic activity. Especially, Cu(Ⅱ)(0.5 mol·L-1)/AgBr-rGO(0.5wt%) (rGO, reduced graphene oxide) showed the highest photocatalytic activity with a rate constant 0.027 31 min-1, while this value is higher than that of the pure AgBr (0.008 07 min-1), AgBr-rGO (0.5%)(0.015 98 min-1) and Cu(Ⅱ) (0.5 mol·L-1)/AgBr (0.015 19 min-1) by a factor of 3.38, 1.7 and 1.8, respectively. The reason for enhanced photocatalytic performance is that Cu(Ⅱ) can quickly catch the photogenerated electrons from AgBr and graphene has large specific surface which may provide a lot reduction active sites for Cu(Ⅱ), resulting in a rapid separation of photogenerated electrons and holes. This work may provide the new insights for the preparation of high performance AgBr photocatalyst.
Preparation and Liver MRI of Fe3O4/N-(2-Hydroxyl)propyl-3-trimethyl Ammonium Chitosan Contrast Agent
2015, 31(10): 1987-1992
doi: 10.11862/CJIC.2015.230
Abstract:
Supermagnetic Fe3O4/N-(2-hydroxyl)propyl-3-trimethyl ammonium chitosan nanoparticles were synthesized by combining Fe3O4 and CS chemically modified with glycidyl trimethyl ammonium chloride. Properties of the obtained nanoparticles were investigated by transmission electron microscopy, dynamic light scattering, magnetic resonance imaging and vibration sample magnetometer. The cytocompatibility of the nanoparticles were assessed. Then the in vivo MRI of the nanoparticles were confirmed. The results demonstrate that the nanoparticles are uniform and stable in simulated physiological environment. Also the nanoparticles show good cyto-compatibility. The in vivo results show that the parenchyma signal intensity of rats liver is significantly decreased after injection of the nanoparticles. Thus it indicates that the nanoparticles have potential application in liver MRI as a negative contrast.
Supermagnetic Fe3O4/N-(2-hydroxyl)propyl-3-trimethyl ammonium chitosan nanoparticles were synthesized by combining Fe3O4 and CS chemically modified with glycidyl trimethyl ammonium chloride. Properties of the obtained nanoparticles were investigated by transmission electron microscopy, dynamic light scattering, magnetic resonance imaging and vibration sample magnetometer. The cytocompatibility of the nanoparticles were assessed. Then the in vivo MRI of the nanoparticles were confirmed. The results demonstrate that the nanoparticles are uniform and stable in simulated physiological environment. Also the nanoparticles show good cyto-compatibility. The in vivo results show that the parenchyma signal intensity of rats liver is significantly decreased after injection of the nanoparticles. Thus it indicates that the nanoparticles have potential application in liver MRI as a negative contrast.
2015, 31(10): 1993-2000
doi: 10.11862/CJIC.2015.210
Abstract:
Two cadmium coordination polymers, [Cd6L3(DMA)3(H2O)]n (1) and {[Cd2L(H2O)4]·4H2O}n (2) (L=tetrakis[3-(carboxyphenyl)oxamethyl]methane acid) with different structures have been synthesized based on a tetrahedral ligand L. Compound 1 crystallizes in the trigonal space group R3. The tetrahedral ligand connects four Cd3 clusters through its four carboxylates and the Cd3 clusters connect six benzoic rings to form a 4,6-connected 3-dimentional framework of the toc topology. Compound 2 crystallizes in the monoclinic C2/c space group. Each ligand connects four cadmium atoms and the cadmium atoms are connected through carboxylates to form a chain along the b axis. The solid-state UV-Vis spectra and photoluminescent properties of 1 and 2 were investigated at room tempreture. CCDC: 1030076, 1; 1046165, 2.
Two cadmium coordination polymers, [Cd6L3(DMA)3(H2O)]n (1) and {[Cd2L(H2O)4]·4H2O}n (2) (L=tetrakis[3-(carboxyphenyl)oxamethyl]methane acid) with different structures have been synthesized based on a tetrahedral ligand L. Compound 1 crystallizes in the trigonal space group R3. The tetrahedral ligand connects four Cd3 clusters through its four carboxylates and the Cd3 clusters connect six benzoic rings to form a 4,6-connected 3-dimentional framework of the toc topology. Compound 2 crystallizes in the monoclinic C2/c space group. Each ligand connects four cadmium atoms and the cadmium atoms are connected through carboxylates to form a chain along the b axis. The solid-state UV-Vis spectra and photoluminescent properties of 1 and 2 were investigated at room tempreture. CCDC: 1030076, 1; 1046165, 2.
2015, 31(10): 2001-2007
doi: 10.11862/CJIC.2015.211
Abstract:
Three bis[tris(2-methyl-2-phenyl)propyltin] dicarboxylates (CH2)n[CO2Sn(CH2CMe2Ph)3]2 (n=2 (1), 3 (2), 4 (3)) have been synthesized by the reaction of succinic acid、glutaric and acid adipic acid with bis[tris(2-methyl-2-phenyl)propyltin] oxide, respectively. IR, 1H and 13C NMR, elemental analysis and X-ray diffraction for the title complexes were presented. The tin atoms of the three complexes have a distorted tetrahedral geometry. The tests showed the complexes 2 and 3 displayed strong in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460. CCDC: 1042305, 1; 1042306, 2; 1409041, 3.
Three bis[tris(2-methyl-2-phenyl)propyltin] dicarboxylates (CH2)n[CO2Sn(CH2CMe2Ph)3]2 (n=2 (1), 3 (2), 4 (3)) have been synthesized by the reaction of succinic acid、glutaric and acid adipic acid with bis[tris(2-methyl-2-phenyl)propyltin] oxide, respectively. IR, 1H and 13C NMR, elemental analysis and X-ray diffraction for the title complexes were presented. The tin atoms of the three complexes have a distorted tetrahedral geometry. The tests showed the complexes 2 and 3 displayed strong in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460. CCDC: 1042305, 1; 1042306, 2; 1409041, 3.
2015, 31(10): 2008-2014
doi: 10.11862/CJIC.2015.243
Abstract:
Two complexes [CoLCl2] (1) and [MnLCl2] (2) (L=4-(4-pyridinemethyleneamino)-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one) were solvothermally synthesized and structurally characterized by elemental analysis, IR, XRD, TG, single-crystal X-ray diffraction and magnetic analysis. The complexes 1 and 2 are determined by X-ray structural analysis and the structure parameters are analyzed as follows: 1, monoclinic, Cc; 2, triclinic, P1. The X-ray diffraction results suggest that the complex 1 exhibits distorted tetrahedral configuration, and the complex 2 exhibits distorted octahedral configurations. CCDC: 913873, 1; 913872, 2.
Two complexes [CoLCl2] (1) and [MnLCl2] (2) (L=4-(4-pyridinemethyleneamino)-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one) were solvothermally synthesized and structurally characterized by elemental analysis, IR, XRD, TG, single-crystal X-ray diffraction and magnetic analysis. The complexes 1 and 2 are determined by X-ray structural analysis and the structure parameters are analyzed as follows: 1, monoclinic, Cc; 2, triclinic, P1. The X-ray diffraction results suggest that the complex 1 exhibits distorted tetrahedral configuration, and the complex 2 exhibits distorted octahedral configurations. CCDC: 913873, 1; 913872, 2.
2015, 31(10): 2015-2020
doi: 10.11862/CJIC.2015.222
Abstract:
Monodispersed water-soluble gold nano-clusters were prepared by using sodium borohydride to reduce tetrachloroauric acid in methanol, with water-soluble 2-mercaptosuccinic acid as the protecting agent on gold nano-cluster surface. HRTEM results show that MSA monolayer-protected gold clusters were obtained with size of about 10.2 nm by increasing the proportion of 2-mercaptosuccinic acid and concentration of tetrachloroauric acid with CAu:CS=1:30. TG, UV and XPS results show that the possible chemical formula of the synthesized gold nano-clusters is [Au38(MSANa)26] or [Au39(MSANa)27].
Monodispersed water-soluble gold nano-clusters were prepared by using sodium borohydride to reduce tetrachloroauric acid in methanol, with water-soluble 2-mercaptosuccinic acid as the protecting agent on gold nano-cluster surface. HRTEM results show that MSA monolayer-protected gold clusters were obtained with size of about 10.2 nm by increasing the proportion of 2-mercaptosuccinic acid and concentration of tetrachloroauric acid with CAu:CS=1:30. TG, UV and XPS results show that the possible chemical formula of the synthesized gold nano-clusters is [Au38(MSANa)26] or [Au39(MSANa)27].
2015, 31(10): 2021-2029
doi: 10.11862/CJIC.2015.266
Abstract:
In order to study the formation mechanism of calcium oxalate (CaOx) stones, the adsorption amount of COD and COM with different sizes to NP-40 was detected by UV-Vis spectroscopy. Crystal phase transformation before and after adsorption was analyzed by XRD and FT-IR. ζ potential of crystals after the adsorption of various concentration of NP-40(cNP-40) was measured by ζ potential analyzer. The adsorption capacity of COM and COD with different size to NP-40 was: 50 nm > 100 nm > 1 μm > > 3 μm > 10 μm. The adsorption quantity of COM was greater than COD of the same size. The adsorption curves of COM and COD with size of 3 μm and 10 μm are S-type, while the curves of COM and COD with size of 50 nm, 100 nm and 1 μm were linear-type. The absolute values of ζ potential of crystals were positively related to the adsorption density to NP-40. The molecular model of NP-40 adsorbed on CaOx crystals was proposed in this study. The smaller the crystal size is, the greater the adsorption amount of CaOx crystals to NP-40 possess. Although nonionic surfactant itself is uncharged, it can be adsorbed onto COM and COD crystals and increase the stability of crystals suspension by steric hindrance, which is conducive to inhibiting the formation of CaOx stones.
In order to study the formation mechanism of calcium oxalate (CaOx) stones, the adsorption amount of COD and COM with different sizes to NP-40 was detected by UV-Vis spectroscopy. Crystal phase transformation before and after adsorption was analyzed by XRD and FT-IR. ζ potential of crystals after the adsorption of various concentration of NP-40(cNP-40) was measured by ζ potential analyzer. The adsorption capacity of COM and COD with different size to NP-40 was: 50 nm > 100 nm > 1 μm > > 3 μm > 10 μm. The adsorption quantity of COM was greater than COD of the same size. The adsorption curves of COM and COD with size of 3 μm and 10 μm are S-type, while the curves of COM and COD with size of 50 nm, 100 nm and 1 μm were linear-type. The absolute values of ζ potential of crystals were positively related to the adsorption density to NP-40. The molecular model of NP-40 adsorbed on CaOx crystals was proposed in this study. The smaller the crystal size is, the greater the adsorption amount of CaOx crystals to NP-40 possess. Although nonionic surfactant itself is uncharged, it can be adsorbed onto COM and COD crystals and increase the stability of crystals suspension by steric hindrance, which is conducive to inhibiting the formation of CaOx stones.
2015, 31(10): 2030-2036
doi: 10.11862/CJIC.2015.267
Abstract:
Sulfur/mesoporous carbon composites were achieved by melt infiltration of sulfur into mesoporous carbon which was prepared by template method. SEM images show the Sulfur/mesoporous carbon composites are sphere with uniform diameter about 500 nm and TEM illustrate sulfur with 2 nm size is infiltrated in mesoporous carbon. XRD, BET and TG was employed to analysis the sulfur/mesoporous carbon composites. When the sulfur/mesoporous carbon composites were applied as cathode material for lithium sulfur, it exhibited high electrochemical performance. The initial discharge specific capacity of the sulfur/mesoporous carbon composites is as high as 1 519 mAh·g-1 at the current densities of 200 mA·g-1, and can remain 835 mAh·g-1 even after 200 cycles.
Sulfur/mesoporous carbon composites were achieved by melt infiltration of sulfur into mesoporous carbon which was prepared by template method. SEM images show the Sulfur/mesoporous carbon composites are sphere with uniform diameter about 500 nm and TEM illustrate sulfur with 2 nm size is infiltrated in mesoporous carbon. XRD, BET and TG was employed to analysis the sulfur/mesoporous carbon composites. When the sulfur/mesoporous carbon composites were applied as cathode material for lithium sulfur, it exhibited high electrochemical performance. The initial discharge specific capacity of the sulfur/mesoporous carbon composites is as high as 1 519 mAh·g-1 at the current densities of 200 mA·g-1, and can remain 835 mAh·g-1 even after 200 cycles.
2015, 31(10): 2037-2043
doi: 10.11862/CJIC.2015.232
Abstract:
A PW11Cu/TiO2 composite film photocatalyst was prepared on the surface of a glass slide via the sol-gel dipping pulling method using tetrabutyl titanate Ti(OC4H9)4 as the precursor of TiO2 and the Keggin type copper substituted heteropolyanion PW11Cu as the visible light active component in this paper. Then the light absorption properties, the chemical composition, the crystal phase and the surface morphology of the as-prepared catalyst were characterized using UV-Vis DRS, IR, XRD, SEM and TEM. Meanwhile, the visible photocatalytic activity of the catalyst was assessed using the photocatalytic degradation of RhB, a model pollutant, as a probe. Influences of the calcination temperature,the PW11Cr dosage and the solution pH on the catalyst activity were also examined. In the end, a recycle test of the catalyst for RhB degradation was employed to evaluate the stability of the catalyst. Experimental results show that the PW11Cu/TiO2 photocatalyst has a good absorption to visible light. The film yielded at low calcination temperature (100℃) is amorphous and crystalline at high calcination temperature (500℃). The former has higher photocatalytic activity, and was employed to degrade RhB with a concentration of 10 μmol·L-1 under the irradiation of 200 W metal halide lamp, the degradation ratio was about 100% at 80 min and the TOC removal was 32% at 4 h. High solution acidity is favorable to enhancement of the photocatalytic activity of the PW11Cu/TiO2 film. Reaching 100% of RhB degradaion only needed 30 min at pH=2.5. The optimal PW11Cu dosage is 3.0 g under the experimental conditions. The photocatalytic activity of the PW11Cu/TiO2 film remains about 90% after 10 times recycles for RhB degradaion.
A PW11Cu/TiO2 composite film photocatalyst was prepared on the surface of a glass slide via the sol-gel dipping pulling method using tetrabutyl titanate Ti(OC4H9)4 as the precursor of TiO2 and the Keggin type copper substituted heteropolyanion PW11Cu as the visible light active component in this paper. Then the light absorption properties, the chemical composition, the crystal phase and the surface morphology of the as-prepared catalyst were characterized using UV-Vis DRS, IR, XRD, SEM and TEM. Meanwhile, the visible photocatalytic activity of the catalyst was assessed using the photocatalytic degradation of RhB, a model pollutant, as a probe. Influences of the calcination temperature,the PW11Cr dosage and the solution pH on the catalyst activity were also examined. In the end, a recycle test of the catalyst for RhB degradation was employed to evaluate the stability of the catalyst. Experimental results show that the PW11Cu/TiO2 photocatalyst has a good absorption to visible light. The film yielded at low calcination temperature (100℃) is amorphous and crystalline at high calcination temperature (500℃). The former has higher photocatalytic activity, and was employed to degrade RhB with a concentration of 10 μmol·L-1 under the irradiation of 200 W metal halide lamp, the degradation ratio was about 100% at 80 min and the TOC removal was 32% at 4 h. High solution acidity is favorable to enhancement of the photocatalytic activity of the PW11Cu/TiO2 film. Reaching 100% of RhB degradaion only needed 30 min at pH=2.5. The optimal PW11Cu dosage is 3.0 g under the experimental conditions. The photocatalytic activity of the PW11Cu/TiO2 film remains about 90% after 10 times recycles for RhB degradaion.
2015, 31(10): 2044-2050
doi: 10.11862/CJIC.2015.268
Abstract:
Two bis(tricyclohexyltin)dicarboxylate(CH2)n(CO2SnCy3)2[(n:6(1), 7(2)] have been synthesized by the reaction of suberic acid and azelaic acid with tricyclohexyltin hydroxide, respectively. The structures of the products were confirmed by IR, 1H and 13C NMR, elemental analysis and X-ray diffraction. The complexes 1 and 2 belong to monoclinic, space group P21/n and P21/c. A 2D network structure was formed by 30-membered or 32-membered macrocyclic tetratin species, which has been alternately connected through the Sn-O covalent bond or the Sn-O covalent bond and Sn...O weak interaction, respectively. The tests showed the two complexes displayed strong in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460 and has selective antibacterial property for S. Aureus, B. Subtilis, E. Coli and S. Typhi. CCDC: 1047100,11; 1047101,2.
Two bis(tricyclohexyltin)dicarboxylate(CH2)n(CO2SnCy3)2[(n:6(1), 7(2)] have been synthesized by the reaction of suberic acid and azelaic acid with tricyclohexyltin hydroxide, respectively. The structures of the products were confirmed by IR, 1H and 13C NMR, elemental analysis and X-ray diffraction. The complexes 1 and 2 belong to monoclinic, space group P21/n and P21/c. A 2D network structure was formed by 30-membered or 32-membered macrocyclic tetratin species, which has been alternately connected through the Sn-O covalent bond or the Sn-O covalent bond and Sn...O weak interaction, respectively. The tests showed the two complexes displayed strong in vitro anti-tumor activity against five human tumor cell lines, Colo205, HepG2, MCF-7, Hela and NCI-H460 and has selective antibacterial property for S. Aureus, B. Subtilis, E. Coli and S. Typhi. CCDC: 1047100,11; 1047101,2.
2015, 31(10): 2051-2058
doi: 10.11862/CJIC.2015.262
Abstract:
Two complexes, [Cu(DMPM)2(Bz)][Cu(DMPM)(Bz)3]·H2O (1) and [Cu(PMA)Cl2] (2) (DMPM=4,5-dimethyl-2-(2-pyridyl)imidazole, PMA=ethyl [2-(2-pyridyl)imidazole-1-yl)]acetate, Bz=benzoate anion) were synth-esized and characterized by ultraviolet spectrophotometry (UV-Vis), thermogravimetric analysis (TG), differential scanning calorimetry (DSC), electron spin resonance (ESR) and single crystal X-ray diffraction. Results show that the crystal structure of complex 1 belongs to triclinic system, space group P1, and complex 2 belongs to monoclinic system, space group P21/c. Complex 1 assembles into a 3D structure by the intermolecular hydrogen bonding interactions, whereas a 2D layer structure of complex 2 is assembled by hydrogen bonds. CCDC: 1414243, 1; 1414242, 2.
Two complexes, [Cu(DMPM)2(Bz)][Cu(DMPM)(Bz)3]·H2O (1) and [Cu(PMA)Cl2] (2) (DMPM=4,5-dimethyl-2-(2-pyridyl)imidazole, PMA=ethyl [2-(2-pyridyl)imidazole-1-yl)]acetate, Bz=benzoate anion) were synth-esized and characterized by ultraviolet spectrophotometry (UV-Vis), thermogravimetric analysis (TG), differential scanning calorimetry (DSC), electron spin resonance (ESR) and single crystal X-ray diffraction. Results show that the crystal structure of complex 1 belongs to triclinic system, space group P1, and complex 2 belongs to monoclinic system, space group P21/c. Complex 1 assembles into a 3D structure by the intermolecular hydrogen bonding interactions, whereas a 2D layer structure of complex 2 is assembled by hydrogen bonds. CCDC: 1414243, 1; 1414242, 2.
2015, 31(10): 2059-2064
doi: 10.11862/CJIC.2015.264
Abstract:
Three transition metal complexes, namely, [Co2(H2bptc)2(H2O)4]·bpe·9H2O (1), [Ni2(H2bptc)2(H2O)4]·bpe·9H2O (2), [Ni2(H2bptc)2(H2O)4]·0.5bpp·7H2O (3) (H4bptc=2,2'-bipyridine-3,3',6,6'-tetracarboxylic acid, bpe=1,2-di(4-pyridyl)ethylene, bpp=1,2-di(4-pyridyl) ethane) have been synthesized under hydrothermal conditions and structurally characterized by infrared spectra, thermogravimetric analyses and single crystal X-ray diffraction. Compounds 1~3 are the mononuclear units and extended further to generate the three-dimensional supramol-ecular architectures by strong hydrogen-bonding interactions, respectively. CCDC: 1054309, 1; 1054310, 2; 1054311, 3.
Three transition metal complexes, namely, [Co2(H2bptc)2(H2O)4]·bpe·9H2O (1), [Ni2(H2bptc)2(H2O)4]·bpe·9H2O (2), [Ni2(H2bptc)2(H2O)4]·0.5bpp·7H2O (3) (H4bptc=2,2'-bipyridine-3,3',6,6'-tetracarboxylic acid, bpe=1,2-di(4-pyridyl)ethylene, bpp=1,2-di(4-pyridyl) ethane) have been synthesized under hydrothermal conditions and structurally characterized by infrared spectra, thermogravimetric analyses and single crystal X-ray diffraction. Compounds 1~3 are the mononuclear units and extended further to generate the three-dimensional supramol-ecular architectures by strong hydrogen-bonding interactions, respectively. CCDC: 1054309, 1; 1054310, 2; 1054311, 3.
2015, 31(10): 2065-2072
doi: 10.11862/CJIC.2015.273
Abstract:
Two metal-organic coordination polymers with novel structural based on a rigid bis(triazole) ligand, namely, [Co1.5(btb)2(nbta)(H2O)2]n (1), and [Cd(btb)0.5(nph)(H2O)]n (2) (btb=4,4'-bis(1,2,4-triazolyl-1-yl)-biphenyl, H3nbta=5-nitro-1,2,3-benzenetricarboxylic acid, H2nph=3-nitrophthalic acid) were synthesized hydrothermally and characterized by IR, elemental analysis, as well as single-crystal X-ray diffraction. Compound 1 features a 2D structure with a (3,4)-connected 3,4L90 topology, which ultimately is extended into a 3D supramolecular framework via O-H…O hydrogen bonding interactions. While complex 2 exhibits a 3D (3,4,4)-connected sqc69 network with the Schläfli symbol of (4.82)2(42.82.102)(8.104.12). Furthermore, the thermal stability and fluorescence properties of the complexes have been investigated. CCDC: 1055345, 1; 1063802, 2.
Two metal-organic coordination polymers with novel structural based on a rigid bis(triazole) ligand, namely, [Co1.5(btb)2(nbta)(H2O)2]n (1), and [Cd(btb)0.5(nph)(H2O)]n (2) (btb=4,4'-bis(1,2,4-triazolyl-1-yl)-biphenyl, H3nbta=5-nitro-1,2,3-benzenetricarboxylic acid, H2nph=3-nitrophthalic acid) were synthesized hydrothermally and characterized by IR, elemental analysis, as well as single-crystal X-ray diffraction. Compound 1 features a 2D structure with a (3,4)-connected 3,4L90 topology, which ultimately is extended into a 3D supramolecular framework via O-H…O hydrogen bonding interactions. While complex 2 exhibits a 3D (3,4,4)-connected sqc69 network with the Schläfli symbol of (4.82)2(42.82.102)(8.104.12). Furthermore, the thermal stability and fluorescence properties of the complexes have been investigated. CCDC: 1055345, 1; 1063802, 2.
2015, 31(10): 2073-2078
doi: 10.11862/CJIC.2015.229
Abstract:
Two complexes, {[Cd2(L1)(1,4-NDC)2]·2H2O}n (1) and {[Zn2(L2)(1,4-NDC)2]·DMF·3H2O)}n (2) (L1=tetrakis(4-pyridyloxymethylene)methane, L2=tetrakis(3-pyridyloxymethylene)methane, 1,4-NDC=naphthalene-1,4-dicarbox-ylic acid) are obtained by the self-assembly reaction of L1 or L2, 1,4-NDC, and d10 metal ions under solvothermal conditions. The X-ray analysis reveals that 1 is constructed from a 1D zigzag chain [Cd(1,4-NDC)]n which is linked by L1 ligand to yield a 3D framework. And yet in case of 2, one double helix is mutually interdigitated by another 1D chain into a 2D network. Above all, the effect of steric hindrance of the auxiliary linker on the structural diversity of CPs can be discussed in great detail by the introduction of two kinds of auxiliary linkers with different steric hindrance. Additionally, their luminescent properties are also observed. CCDC: 1019510, 1; 1019511, 2.
Two complexes, {[Cd2(L1)(1,4-NDC)2]·2H2O}n (1) and {[Zn2(L2)(1,4-NDC)2]·DMF·3H2O)}n (2) (L1=tetrakis(4-pyridyloxymethylene)methane, L2=tetrakis(3-pyridyloxymethylene)methane, 1,4-NDC=naphthalene-1,4-dicarbox-ylic acid) are obtained by the self-assembly reaction of L1 or L2, 1,4-NDC, and d10 metal ions under solvothermal conditions. The X-ray analysis reveals that 1 is constructed from a 1D zigzag chain [Cd(1,4-NDC)]n which is linked by L1 ligand to yield a 3D framework. And yet in case of 2, one double helix is mutually interdigitated by another 1D chain into a 2D network. Above all, the effect of steric hindrance of the auxiliary linker on the structural diversity of CPs can be discussed in great detail by the introduction of two kinds of auxiliary linkers with different steric hindrance. Additionally, their luminescent properties are also observed. CCDC: 1019510, 1; 1019511, 2.
2015, 31(10): 2079-2088
doi: 10.11862/CJIC.2015.272
Abstract:
A novel series of ferrocenylimine compounds (5~12) were synthesized via the same route by refluxing a mixture of corresponding ferrocenylaniline with aromatic aldehyde. Compounds 5~12 were air stable without any decomposition when exposed to air. The compounds were all characterized by 1H and 13C NMR spectroscopy, mass spectrometry, IR, UV-Visible and elemental analysis. The single crystal structure of compound 10 was also reported, which revealed that compound 10 crystallized in monoclinic system with P21/c space group. CCDC: 1010246, 10.
A novel series of ferrocenylimine compounds (5~12) were synthesized via the same route by refluxing a mixture of corresponding ferrocenylaniline with aromatic aldehyde. Compounds 5~12 were air stable without any decomposition when exposed to air. The compounds were all characterized by 1H and 13C NMR spectroscopy, mass spectrometry, IR, UV-Visible and elemental analysis. The single crystal structure of compound 10 was also reported, which revealed that compound 10 crystallized in monoclinic system with P21/c space group. CCDC: 1010246, 10.
2015, 31(10): 2089-2094
doi: 10.11862/CJIC.2015.274
Abstract:
Two novel silver(Ⅰ) complexes [Ag2Br2(DPEphos)2(dppe)](1) and [Ag(DPEphos)(dppe)]NO3(2) (DPEphos=bis[2-(diphenylphosphino)phenyl]ether, dppe=bis(diphenylphosphino)ethane) have been synthesized and characterized by IR, single-crystal X-ray diffraction, 1H NMR, 31P NMR spectroscopy and fluorescence spectra. 1 is comprised of AgBr, DPEphos and dppe in 2:2:1 molar ratio generating a binuclear complex. The dppe ligand bridges two Ag atoms through two P atoms in 1. While, 2 is obtained by the reactions of AgNO3, DPEphos and dppe in 1:1:1 molar ratio generating a sample mono-nuclear complex. The Ag(Ⅰ) atom is chelated by DPEphos and dppe ligand. In the 31P NMR spectra of 2, there are four splitting signals (doublets or triplets). The luminescent spectra show that the origin of these emissions all involves emissive state derived from ligand centered π-π* transition. CCDC: 1043375, 1; 1043376, 2.
Two novel silver(Ⅰ) complexes [Ag2Br2(DPEphos)2(dppe)](1) and [Ag(DPEphos)(dppe)]NO3(2) (DPEphos=bis[2-(diphenylphosphino)phenyl]ether, dppe=bis(diphenylphosphino)ethane) have been synthesized and characterized by IR, single-crystal X-ray diffraction, 1H NMR, 31P NMR spectroscopy and fluorescence spectra. 1 is comprised of AgBr, DPEphos and dppe in 2:2:1 molar ratio generating a binuclear complex. The dppe ligand bridges two Ag atoms through two P atoms in 1. While, 2 is obtained by the reactions of AgNO3, DPEphos and dppe in 1:1:1 molar ratio generating a sample mono-nuclear complex. The Ag(Ⅰ) atom is chelated by DPEphos and dppe ligand. In the 31P NMR spectra of 2, there are four splitting signals (doublets or triplets). The luminescent spectra show that the origin of these emissions all involves emissive state derived from ligand centered π-π* transition. CCDC: 1043375, 1; 1043376, 2.
