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2013 Volume 29 Issue 11
2013, 29(11): 2265-2275
doi: 10.3969/j.issn.1001-4861.2013.00.352
Abstract:
The cleavage of C-C bond is one sort of important and challenging reactions, and much attention has been focused upon the catalytic reactions of the C-C bond cleavage of nitriles during the last few decades. As a commonly used organic solvent, acetonitrile is the smallest one among nitriles. Based on the recent investigations, this paper summarizes the related research advancements of the cleavage of C-C bond in acetonitrile catalyzed by transition-metal complexes, analyses the present problems and gives the researching prospects of this type of reactions.
The cleavage of C-C bond is one sort of important and challenging reactions, and much attention has been focused upon the catalytic reactions of the C-C bond cleavage of nitriles during the last few decades. As a commonly used organic solvent, acetonitrile is the smallest one among nitriles. Based on the recent investigations, this paper summarizes the related research advancements of the cleavage of C-C bond in acetonitrile catalyzed by transition-metal complexes, analyses the present problems and gives the researching prospects of this type of reactions.
2013, 29(11): 2276-2282
doi: 10.3969/j.issn.1001-4861.2013.00.359
Abstract:
The study on the preparation of a series of silicon carbide nanomaterials, including 1D nanowires, nanobelts, nanorods, 2D nanosheets, hollow spheres, and so on, via solvothermal technique is summarized in this article. Meanwhile, SiC@C composite materials can be produced in the case of excess carbon sources. Silicon carbide nanomaterials can also be prepared by using waste plastics as carbon source, which provides a new route to the recycling and reutilization of waste plastics. Moreover, the synthesis temperature can be effectively decreased by using iodine and sulfur as additives, indicating the unique advantage of solvothermal technique in the preparation of silicon carbide nanomaterials.
The study on the preparation of a series of silicon carbide nanomaterials, including 1D nanowires, nanobelts, nanorods, 2D nanosheets, hollow spheres, and so on, via solvothermal technique is summarized in this article. Meanwhile, SiC@C composite materials can be produced in the case of excess carbon sources. Silicon carbide nanomaterials can also be prepared by using waste plastics as carbon source, which provides a new route to the recycling and reutilization of waste plastics. Moreover, the synthesis temperature can be effectively decreased by using iodine and sulfur as additives, indicating the unique advantage of solvothermal technique in the preparation of silicon carbide nanomaterials.
2013, 29(11): 2283-2288
doi: 10.3969/j.issn.1001-4861.2013.00.347
Abstract:
As the third gasotransmitter after NOand CO, hydrogen sulfide plays essential biological roles in living systems, and developing sensitive fluorescent probe for the rapid tracking of endogenous H2S is attracting much attention. Anew H2S fluorescent probe was constructed in this study based on a copper complex formed by a new NBD fluorescent ligand, in which a Cu2+ chelator was incorporated. This probe displays very weak emission owing to the emission quenching effect of Cu2+, and it is able to sense H2S by exhibiting distinct emission enhancement upon H2S addition. The S2-induced Cu2+ removal from this complex was proposed as the sensing mechanism of this Cu2+ complex-based probe. Besides the quick response, the high sensing selectivity over other anion of this probe has also been confirmed, and its detection limit was estimated to be ~0.2 μmol·L-1, and the linear range is 1~20 μmol·L-1.
As the third gasotransmitter after NOand CO, hydrogen sulfide plays essential biological roles in living systems, and developing sensitive fluorescent probe for the rapid tracking of endogenous H2S is attracting much attention. Anew H2S fluorescent probe was constructed in this study based on a copper complex formed by a new NBD fluorescent ligand, in which a Cu2+ chelator was incorporated. This probe displays very weak emission owing to the emission quenching effect of Cu2+, and it is able to sense H2S by exhibiting distinct emission enhancement upon H2S addition. The S2-induced Cu2+ removal from this complex was proposed as the sensing mechanism of this Cu2+ complex-based probe. Besides the quick response, the high sensing selectivity over other anion of this probe has also been confirmed, and its detection limit was estimated to be ~0.2 μmol·L-1, and the linear range is 1~20 μmol·L-1.
2013, 29(11): 2289-2296
doi: 10.3969/j.issn.1001-4861.2013.00.367
Abstract:
Porous silicon/carbon composite was prepared via a mechanochemical reaction between Li13Si4 and SiCl4 under ball milling. Specific surface area of silicon/carbon composite can be adjusted by controlling the particle size distribution of Li13Si4. Effects of the carbon weight, specific surface area and active mass loading on the electrochemical performance were investigated. The results indicated that the composite material which combined specific surface area of 100.9 m2·g-1 and chemical vapor deposition method (CVD) carbon coating with 25.3wt% (ca.6 nm in thickness), exhibited a considerably high reversible capacity of 1900 mAh·g-1 and an excellent cycling stability with only 7.6% capacity decay after 50 cycles at a current density of 300 mA·g-1.
Porous silicon/carbon composite was prepared via a mechanochemical reaction between Li13Si4 and SiCl4 under ball milling. Specific surface area of silicon/carbon composite can be adjusted by controlling the particle size distribution of Li13Si4. Effects of the carbon weight, specific surface area and active mass loading on the electrochemical performance were investigated. The results indicated that the composite material which combined specific surface area of 100.9 m2·g-1 and chemical vapor deposition method (CVD) carbon coating with 25.3wt% (ca.6 nm in thickness), exhibited a considerably high reversible capacity of 1900 mAh·g-1 and an excellent cycling stability with only 7.6% capacity decay after 50 cycles at a current density of 300 mA·g-1.
2013, 29(11): 2297-2304
doi: 10.3969/j.issn.1001-4861.2013.00.338
Abstract:
Using modified bauxite with large surface area and mesoporous structure as the support, a series of Cu-Fe/Bauxite catalysts were synthesized with co-precipitation method. The catalysts were characterized by means of X-ray fluorescence spectrometry (XRF), X-ray diffraction (XRD), SBET, H2-temperature-programmed reduction (H2-TPR) and CO temperature-programmed desorption (CO-TPD) and X-ray photoelectron spectroscopy (XPS). Their catalytic activity in water gas shift (WGS) reaction has also been studied. The results indicate that the WGS reaction activity increases markedly with increasing the content of supported Fe2O3 and when the content of Fe2O3 is to 20%, the catalyst exhibits the highest activity. Because there exists obvious interaction between supported Fe2O3 and CuO to form composite oxide like CuFe2O4 and it enhances with increase in Fe2O3 content. The interaction promotes the reduction of Fe2O3 and CuO and restrains the clotting of CuO, and then the catalytic activity increases.
Using modified bauxite with large surface area and mesoporous structure as the support, a series of Cu-Fe/Bauxite catalysts were synthesized with co-precipitation method. The catalysts were characterized by means of X-ray fluorescence spectrometry (XRF), X-ray diffraction (XRD), SBET, H2-temperature-programmed reduction (H2-TPR) and CO temperature-programmed desorption (CO-TPD) and X-ray photoelectron spectroscopy (XPS). Their catalytic activity in water gas shift (WGS) reaction has also been studied. The results indicate that the WGS reaction activity increases markedly with increasing the content of supported Fe2O3 and when the content of Fe2O3 is to 20%, the catalyst exhibits the highest activity. Because there exists obvious interaction between supported Fe2O3 and CuO to form composite oxide like CuFe2O4 and it enhances with increase in Fe2O3 content. The interaction promotes the reduction of Fe2O3 and CuO and restrains the clotting of CuO, and then the catalytic activity increases.
2013, 29(11): 2305-2314
doi: 10.3969/j.issn.1001-4861.2013.00.342
Abstract:
Graphene oxides and graphene by using redox method were synthesized and characterized. The properties of graphene obtained by chemical reduction method of NaBH4 and thermal reduction method in ethylene amine solvent were further compared. It was demonstrated that thermal reduction of graphene oxides in ethylene amine solvent could introduce nitrogen functional groups to the surface of obtained graphene, increase the distance between the film layers and enhance its dispersity. The results demonstrated that graphene oxides were reduced, CdSe quantum dots were loaded simultaneously, and oxygen content as significantly decreased. The change of reaction temperature showed little effects on the reduction of graphene oxides, and longer the reaction time, higher the reduction rate of graphene oxides. With the increase of reaction time, the CdSe quantum dots loaded on the surface of graphene grew into nanorods, nanowires, and even branch-shaped nano structures. By controlling the reaction time and temperature, we can easily control the reduction level of graphene oxides and the morphology of CdSe quantum dots supported on the surface of graphene. In conclusion, an effective method is established to control the properties and morphology of nano-composites based on graphene and CdSe quantum dots by hydro-thermal methods.
Graphene oxides and graphene by using redox method were synthesized and characterized. The properties of graphene obtained by chemical reduction method of NaBH4 and thermal reduction method in ethylene amine solvent were further compared. It was demonstrated that thermal reduction of graphene oxides in ethylene amine solvent could introduce nitrogen functional groups to the surface of obtained graphene, increase the distance between the film layers and enhance its dispersity. The results demonstrated that graphene oxides were reduced, CdSe quantum dots were loaded simultaneously, and oxygen content as significantly decreased. The change of reaction temperature showed little effects on the reduction of graphene oxides, and longer the reaction time, higher the reduction rate of graphene oxides. With the increase of reaction time, the CdSe quantum dots loaded on the surface of graphene grew into nanorods, nanowires, and even branch-shaped nano structures. By controlling the reaction time and temperature, we can easily control the reduction level of graphene oxides and the morphology of CdSe quantum dots supported on the surface of graphene. In conclusion, an effective method is established to control the properties and morphology of nano-composites based on graphene and CdSe quantum dots by hydro-thermal methods.
2013, 29(11): 2315-2322
doi: 10.3969/j.issn.1001-4861.2013.00.225
Abstract:
The compound [Ni(Hlact)2(phen)]·2H2O is synthesized in the solution and fully characterized by elemental analysis, IRand X-ray structural analyses. The interaction of Bovine Serum Albumin (BSA) and [Ni(Hlact)2(phen)]·2H2O at different temperatures are investigated with fluorescence spectra. The binding constant, binding sites and thermodynamic functions are calculated at different temperatures. The binding force and distance are discussed for BSA with complex 1. In the result, the model of fluorescence quenching is considered as static quenching process based on Stern-Volmer equation. The binding constant and binding sites are calculated for BSA and [Ni(Hlact)2(phen)]·2H2O as 5.06×105 L·mol-1 and 2.35nm respectively. Parameters of thermodynamic functions are calculated and the interaction is determined as hydrogen bonding and van der Waal interactions between BSA and complex. CCDC: 897985.
The compound [Ni(Hlact)2(phen)]·2H2O is synthesized in the solution and fully characterized by elemental analysis, IRand X-ray structural analyses. The interaction of Bovine Serum Albumin (BSA) and [Ni(Hlact)2(phen)]·2H2O at different temperatures are investigated with fluorescence spectra. The binding constant, binding sites and thermodynamic functions are calculated at different temperatures. The binding force and distance are discussed for BSA with complex 1. In the result, the model of fluorescence quenching is considered as static quenching process based on Stern-Volmer equation. The binding constant and binding sites are calculated for BSA and [Ni(Hlact)2(phen)]·2H2O as 5.06×105 L·mol-1 and 2.35nm respectively. Parameters of thermodynamic functions are calculated and the interaction is determined as hydrogen bonding and van der Waal interactions between BSA and complex. CCDC: 897985.
2013, 29(11): 2323-2326
doi: 10.3969/j.issn.1001-4861.2013.00.374
Abstract:
Helical mesoporous silica nanorods were prepared through a so-gel approach using cetyltrimethylammonium bromide (CTAB) as the template and phosphatidylcholine (PC) as a chiral additive. The molar ratio of PC and CTAB is 1:21. The morphologies and pore architectures were characterized using field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), N2 sorptions and X-ray diffraction. It was found that the mesoporous silica nanorods were about 30~50 nm in diameter and about 50~200 nm in length. The TEM images and the small-angle X-diffraction indicated that the pore channels arranged in a two-dimensional hexagonal structure. The FESEM images indicated that the ratio of the left-and right-handed nanorods is almost 1:1. However, the circular dichroism spectrum (CD) indicated that the nanorods tended to form a structure with homochirality at angstrom level. It seems that the chirality of PC has been successfully transferred to the walls of the helical mesoporous silica nanorods.
Helical mesoporous silica nanorods were prepared through a so-gel approach using cetyltrimethylammonium bromide (CTAB) as the template and phosphatidylcholine (PC) as a chiral additive. The molar ratio of PC and CTAB is 1:21. The morphologies and pore architectures were characterized using field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), N2 sorptions and X-ray diffraction. It was found that the mesoporous silica nanorods were about 30~50 nm in diameter and about 50~200 nm in length. The TEM images and the small-angle X-diffraction indicated that the pore channels arranged in a two-dimensional hexagonal structure. The FESEM images indicated that the ratio of the left-and right-handed nanorods is almost 1:1. However, the circular dichroism spectrum (CD) indicated that the nanorods tended to form a structure with homochirality at angstrom level. It seems that the chirality of PC has been successfully transferred to the walls of the helical mesoporous silica nanorods.
2013, 29(11): 2327-2332
doi: 10.3969/j.issn.1001-4861.2013.00.369
Abstract:
Abi-crystalline (monocline and anatase) titanium dioxide/multi-walled carbon nanotubes (TiO2/MWNTs) composite was prepared through the hydrothermal reaction of tetrabutyl titanate and sodium hydroxide with butyl end-capped fatty alcohol ethoxylates as phase regulator, and its photocatalytic property under visible light irradiation was investigated. The results show: the adding of MWNTs can affect crystalline phase and improve the photocatalytic activity of TiO2, the product with 5% MWNTs exhibits the greatest photocatalytic degradation rate;the photocatalytic activity of the products greatly increases with the increase of calcination temperature. The effect of doping MWNTs originates from (1) facilitating the formation of bi-crystalline phase with monocline and anatase, and (2) excellent conductivity of MWNTs, or (3) the carbon doping effect rooting in the breaking down of MWNTs under higher temperature.
Abi-crystalline (monocline and anatase) titanium dioxide/multi-walled carbon nanotubes (TiO2/MWNTs) composite was prepared through the hydrothermal reaction of tetrabutyl titanate and sodium hydroxide with butyl end-capped fatty alcohol ethoxylates as phase regulator, and its photocatalytic property under visible light irradiation was investigated. The results show: the adding of MWNTs can affect crystalline phase and improve the photocatalytic activity of TiO2, the product with 5% MWNTs exhibits the greatest photocatalytic degradation rate;the photocatalytic activity of the products greatly increases with the increase of calcination temperature. The effect of doping MWNTs originates from (1) facilitating the formation of bi-crystalline phase with monocline and anatase, and (2) excellent conductivity of MWNTs, or (3) the carbon doping effect rooting in the breaking down of MWNTs under higher temperature.
2013, 29(11): 2333-2338
doi: 10.3969/j.issn.1001-4861.2013.00.383
Abstract:
The graphite oxide (GO) samples were prepared from flake graphite via modified Hummers method. Aseries of quaternary alkylammonium-graphite oxide intercalation composites (CnTAB/GO) were synthesized by changing the alkyl chain length and surfactant concentration, respectively. The structure and intercalated amount of CnTAB for intercalation composites were characterized by using XRDand elemental analysis. The results suggest that the interlayer spacing of CnTAB/GO composites increases with the increase of alkyl chain length or surfactant concentration. It is also found that the experimental data obtained from surfactants in GO spacing have been fitted well into the Modified Langmuir adsorption isotherm equations,indicating that the CnTAB molecules are adsorbed on the surface of GO within a monomolecular layer. The result of elemental analysis also suggests that surfactant is intercalated into GO spacing via electrovalent and hydrophobic interaction. Finally, the arrangement models of the surfactant in the layer of GO include lateral monolayer, lateral bilayer, paraffin-type monolayer and vertical monolayer.
The graphite oxide (GO) samples were prepared from flake graphite via modified Hummers method. Aseries of quaternary alkylammonium-graphite oxide intercalation composites (CnTAB/GO) were synthesized by changing the alkyl chain length and surfactant concentration, respectively. The structure and intercalated amount of CnTAB for intercalation composites were characterized by using XRDand elemental analysis. The results suggest that the interlayer spacing of CnTAB/GO composites increases with the increase of alkyl chain length or surfactant concentration. It is also found that the experimental data obtained from surfactants in GO spacing have been fitted well into the Modified Langmuir adsorption isotherm equations,indicating that the CnTAB molecules are adsorbed on the surface of GO within a monomolecular layer. The result of elemental analysis also suggests that surfactant is intercalated into GO spacing via electrovalent and hydrophobic interaction. Finally, the arrangement models of the surfactant in the layer of GO include lateral monolayer, lateral bilayer, paraffin-type monolayer and vertical monolayer.
2013, 29(11): 2339-2346
doi: 10.3969/j.issn.1001-4861.2013.00.385
Abstract:
MCM-41 was first functionalized with benzyl sulphonic acid using a post-synthetic procedure and then modified with chiral Mn(salen) complex to prepare a heterogeneous chiral Mn(salen) catalyst under cheap and mild conditions. The chiral Mn(salen) complex was axially immobilized into MCM-41 via the organic benzyl sulfonic groups. The catalyst was characterized by XRD, N2 adsorption-desorption, FTIR, TG-DSC, ICP and acid capacity titration. The results show that the chiral Mn(salen) complex has been supported on MCM-41, and the mesoporous structure of MCM-41 and the chiral structure of Mn(salen) are still remained. The supported catalyst was applied to the asymmetric epoxidation of α-methylstyrene using m-chloroperbenzoic acid as an oxidant at 0 ℃, and showed excellent performance with a conversion of 77% and e.e. (enantiomeric excess) value above 99% after a rather short reaction time of 2 h in the absence of NMO (N-Methylmorpholine-N-Oxide). The benzyl sulphonic acid groups play a very good axial ligand function. By treating properly, the e.e. value was still 71% after the supported catalyst was reused 5 times.
MCM-41 was first functionalized with benzyl sulphonic acid using a post-synthetic procedure and then modified with chiral Mn(salen) complex to prepare a heterogeneous chiral Mn(salen) catalyst under cheap and mild conditions. The chiral Mn(salen) complex was axially immobilized into MCM-41 via the organic benzyl sulfonic groups. The catalyst was characterized by XRD, N2 adsorption-desorption, FTIR, TG-DSC, ICP and acid capacity titration. The results show that the chiral Mn(salen) complex has been supported on MCM-41, and the mesoporous structure of MCM-41 and the chiral structure of Mn(salen) are still remained. The supported catalyst was applied to the asymmetric epoxidation of α-methylstyrene using m-chloroperbenzoic acid as an oxidant at 0 ℃, and showed excellent performance with a conversion of 77% and e.e. (enantiomeric excess) value above 99% after a rather short reaction time of 2 h in the absence of NMO (N-Methylmorpholine-N-Oxide). The benzyl sulphonic acid groups play a very good axial ligand function. By treating properly, the e.e. value was still 71% after the supported catalyst was reused 5 times.
2013, 29(11): 2347-2350
doi: 10.3969/j.issn.1001-4861.2013.00.378
Abstract:
A 2Dcomplex [Ni(H2O)(MPA)(4,4'-bibp)]n (1), based on mixed-ligands, bibp (bibp =4,4'-bisimidazolyl-biphenyl) and H2MPA (H2MPA=m-phthalic acid), has been synthesized by hydrothermal method and characterized by elemental analysis, IRspectra, TGA, XRD, and the crystal structure was determined by single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group Pc and features a 2D layered structure. The solid UV-Vis properties of ligands and the complex 1 were studied at room temperature. CCDC: 940196.
A 2Dcomplex [Ni(H2O)(MPA)(4,4'-bibp)]n (1), based on mixed-ligands, bibp (bibp =4,4'-bisimidazolyl-biphenyl) and H2MPA (H2MPA=m-phthalic acid), has been synthesized by hydrothermal method and characterized by elemental analysis, IRspectra, TGA, XRD, and the crystal structure was determined by single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group Pc and features a 2D layered structure. The solid UV-Vis properties of ligands and the complex 1 were studied at room temperature. CCDC: 940196.
2013, 29(11): 2351-2356
doi: 10.3969/j.issn.1001-4861.2013.00.349
Abstract:
An efficient near-infrared (NIR) quantum cutting in Ca0.8-2x(YbxTb0.1Na0.1+x)2xWO4(x=0~20%) phosphors has been demonstrated, which involves the emission of two low-energy NIR photons (around 980 nm) from an absorbed ultra-violet photon via the two cooperative energy transfer processes both from (direct) the WO42- group to Yb3+ ions and (indirect) the WO42- group to Tb3+ to Yb3+ ions. The dependence of Yb3+ doping concentration on the visible and NIR emissions, decay lifetime, and quantum efficiencies have been investigated in detail. Yb3+ concentration dependent quantum efficiency has been calculated and the maximum quantum efficiency approaches up to 135.7%. The development of the near-infrared quantum cutting tungstates could open a route in achieving high efficiency silicon-based solar cells by means of downconversion in ultra-violet part of the solar spectrum to about 1000 nm photons with a two fold increase in the photon number.
An efficient near-infrared (NIR) quantum cutting in Ca0.8-2x(YbxTb0.1Na0.1+x)2xWO4(x=0~20%) phosphors has been demonstrated, which involves the emission of two low-energy NIR photons (around 980 nm) from an absorbed ultra-violet photon via the two cooperative energy transfer processes both from (direct) the WO42- group to Yb3+ ions and (indirect) the WO42- group to Tb3+ to Yb3+ ions. The dependence of Yb3+ doping concentration on the visible and NIR emissions, decay lifetime, and quantum efficiencies have been investigated in detail. Yb3+ concentration dependent quantum efficiency has been calculated and the maximum quantum efficiency approaches up to 135.7%. The development of the near-infrared quantum cutting tungstates could open a route in achieving high efficiency silicon-based solar cells by means of downconversion in ultra-violet part of the solar spectrum to about 1000 nm photons with a two fold increase in the photon number.
2013, 29(11): 2357-2362
doi: 10.3969/j.issn.1001-4861.2013.00.363
Abstract:
A 2D TbⅢ coordination polymer [Tb(cam)(H2O)3]n·nH2O (1) (H3cam=4-Hydroxypyridine-2,6-dicarbo-xylic acid) was synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectrum, single-crystal X-ray diffraction, UV-Vis, Fluorescence, TGA and XRD. The TbⅢ ion is eight-coordinate with a slightly distorted dodecahedron geometry. One TbⅢ ion joined with three (cam)3- ions to form a 2D layered with (4·82) topological. The neighboring layers are linked into 3D supramolecular network through hydrogen bonding interaction. The luminescence experiments show that 1 exhibits typical TbⅢ-centered emissions in the solid state, the energy level difference was well matched and the emission of terbium complex was characteristic and high. CCDC: 922429.
A 2D TbⅢ coordination polymer [Tb(cam)(H2O)3]n·nH2O (1) (H3cam=4-Hydroxypyridine-2,6-dicarbo-xylic acid) was synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectrum, single-crystal X-ray diffraction, UV-Vis, Fluorescence, TGA and XRD. The TbⅢ ion is eight-coordinate with a slightly distorted dodecahedron geometry. One TbⅢ ion joined with three (cam)3- ions to form a 2D layered with (4·82) topological. The neighboring layers are linked into 3D supramolecular network through hydrogen bonding interaction. The luminescence experiments show that 1 exhibits typical TbⅢ-centered emissions in the solid state, the energy level difference was well matched and the emission of terbium complex was characteristic and high. CCDC: 922429.
2013, 29(11): 2363-2369
doi: 10.3969/j.issn.1001-4861.2013.00.357
Abstract:
Ahighly active MnOx materials were prepared by an oxidation-reduction reaction between KMnO4 and Mn(NO3)2. The γ-Al2O3 support with large surface area was synthesized by the peptizing method. Subsequently, Pd was loaded on MnOx and γ-Al2O3 by incipient wetness impregnation, respectively. Then, the Pd/MnOx and Pd/γ-Al2O3 were mixed and coated on the cordierite. Finally, the Pd/MnOx+Pd/γ-Al2O3 monolithic catalysts were obtained. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Temperature-programmed reduction (H2-TPR) and low temperature N2 adsorption/desorption measurement, respectively. Asynergetic effect took place between Pd and MnOx when O3 was decomposed on the surface of the Pd/MnOx+Pd/γ-Al2O3 catalysts. The effect of calcination temperature on the catalytic performance for the decomposition of ground-level ozone was investigated. It revealed that the activity of catalysts was considerably influenced by the calcination temperature of MnOx. When the MnOx was calcined at 600 ℃, the catalyst had the highest activity, where ozone conversion reached 88% at 12 ℃ and it was completely decomposed at 18 ℃. The results show that catalytic activity mainly depends on the MnOx phase and oxygen species adsorbed on the surface of catalysts. The MnO2 and Mn2O3 with proper proportion can efficiently promote the decomposition of ozone. And oxygen adsorbed on the surface of catalysts is active oxygen species during ozone decomposition.
Ahighly active MnOx materials were prepared by an oxidation-reduction reaction between KMnO4 and Mn(NO3)2. The γ-Al2O3 support with large surface area was synthesized by the peptizing method. Subsequently, Pd was loaded on MnOx and γ-Al2O3 by incipient wetness impregnation, respectively. Then, the Pd/MnOx and Pd/γ-Al2O3 were mixed and coated on the cordierite. Finally, the Pd/MnOx+Pd/γ-Al2O3 monolithic catalysts were obtained. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Temperature-programmed reduction (H2-TPR) and low temperature N2 adsorption/desorption measurement, respectively. Asynergetic effect took place between Pd and MnOx when O3 was decomposed on the surface of the Pd/MnOx+Pd/γ-Al2O3 catalysts. The effect of calcination temperature on the catalytic performance for the decomposition of ground-level ozone was investigated. It revealed that the activity of catalysts was considerably influenced by the calcination temperature of MnOx. When the MnOx was calcined at 600 ℃, the catalyst had the highest activity, where ozone conversion reached 88% at 12 ℃ and it was completely decomposed at 18 ℃. The results show that catalytic activity mainly depends on the MnOx phase and oxygen species adsorbed on the surface of catalysts. The MnO2 and Mn2O3 with proper proportion can efficiently promote the decomposition of ozone. And oxygen adsorbed on the surface of catalysts is active oxygen species during ozone decomposition.
2013, 29(11): 2370-2374
doi: 10.3969/j.issn.1001-4861.2013.00.351
Abstract:
We synthesized two novel Schiff-Base ligands by modificating the aromatic aldehyde: H2L1=N,N'-bis(2-oxy-acetate-3-methoxyl)benzylpropylene diamine, H2L2=N,N'-bis(2-oxy-acetate-3-methoxyl)benzylpropylene (1,3-propane)diamine. [Zn(L1)]·7H2O (1) and [Zn(L2)]·7H2O (2) complexes were prepared by the reaction between H2L1, H2L2 and zinc salts in the solvents of water. The two complexes were structurally characterized by elemental analysis, IR, HNMR and single-crystal X-ray diffraction. The X-ray diffraction results suggest that both the two complexes contain lattice water molecules. The complex 1 exhibits distorted tri-prism geometry and the complex 2 exhibits distorted octahedron geometry. There are lattice water molecules in the complex 1 and 2. In this paper, we research the solid luminescence of these two complexes. The results suggest that they have excellent photoluminescence and will be useful in the optical material. CCDC: 783660: 1;783330: 2.
We synthesized two novel Schiff-Base ligands by modificating the aromatic aldehyde: H2L1=N,N'-bis(2-oxy-acetate-3-methoxyl)benzylpropylene diamine, H2L2=N,N'-bis(2-oxy-acetate-3-methoxyl)benzylpropylene (1,3-propane)diamine. [Zn(L1)]·7H2O (1) and [Zn(L2)]·7H2O (2) complexes were prepared by the reaction between H2L1, H2L2 and zinc salts in the solvents of water. The two complexes were structurally characterized by elemental analysis, IR, HNMR and single-crystal X-ray diffraction. The X-ray diffraction results suggest that both the two complexes contain lattice water molecules. The complex 1 exhibits distorted tri-prism geometry and the complex 2 exhibits distorted octahedron geometry. There are lattice water molecules in the complex 1 and 2. In this paper, we research the solid luminescence of these two complexes. The results suggest that they have excellent photoluminescence and will be useful in the optical material. CCDC: 783660: 1;783330: 2.
2013, 29(11): 2375-2381
doi: 10.3969/j.issn.1001-4861.2013.00.368
Abstract:
Ultrafine ZnFe2O4 nanocrystals were prepared by hydrothermal method and characterized by HRTEM, XRD and EDX techniques respectively. Protein adsorption properties and their correlations to ζ potentials between nanocrystals and protein molecules were investigated under different pH conditions using bovine serum albumin (BSA) and hemoglobin as model proteins. The hydrodynamic size of bare and protein loaded nanocrystals as well as protein conformation changes induced by nanocrystals were respectively studied by dynamic light scattering (DLS) and Fourier transform infrared (FTIR) spectroscopy techniques. Results show that adsorption between nanocrystals and hemoglobin obeys the law of electrostatistic interaction, whereas BSA adsorption behavior is not agreed with such law. After hemoglobin loading, most of nanocrystal-protein systems suspend as monomers and trimers apart from a few aggregates, whereas only aggregates exist after BSA adsorbing onto nanocrystals. FTIR spectroscopy revealed that Hemoglobin suffers more conformational changes than that of BSA. In addition, highly protein adsorption capacities exceeding380 mg·g-1 at appropriate pH conditions imply the potential applications of nanocrystals in protein separation.
Ultrafine ZnFe2O4 nanocrystals were prepared by hydrothermal method and characterized by HRTEM, XRD and EDX techniques respectively. Protein adsorption properties and their correlations to ζ potentials between nanocrystals and protein molecules were investigated under different pH conditions using bovine serum albumin (BSA) and hemoglobin as model proteins. The hydrodynamic size of bare and protein loaded nanocrystals as well as protein conformation changes induced by nanocrystals were respectively studied by dynamic light scattering (DLS) and Fourier transform infrared (FTIR) spectroscopy techniques. Results show that adsorption between nanocrystals and hemoglobin obeys the law of electrostatistic interaction, whereas BSA adsorption behavior is not agreed with such law. After hemoglobin loading, most of nanocrystal-protein systems suspend as monomers and trimers apart from a few aggregates, whereas only aggregates exist after BSA adsorbing onto nanocrystals. FTIR spectroscopy revealed that Hemoglobin suffers more conformational changes than that of BSA. In addition, highly protein adsorption capacities exceeding380 mg·g-1 at appropriate pH conditions imply the potential applications of nanocrystals in protein separation.
2013, 29(11): 2382-2386
doi: 10.3969/j.issn.1001-4861.2013.00.376
Abstract:
Quaternary kesterite Cu2ZnSnS4(CZTS) micro-particles were successfully synthesized by a facile solvothermal method in ethylene glycol with the presence of Polyvinylpyrrolidone (PVP) as surfactant, using CuCl2·2H2O、Zn(Ac)2·2H2O and SnCl4·5H2O as metal precursor and thiourea as sulfur source. Different dispersion CZTS particles were obtained by different contents of PVP. The structure, morphology and absorption spectra of the as-obtained CZTS particles were characterized by means of X-ray diffraction(XRD), Raman spectroscopy, scanning electron microscopy(SEM), transmission electron microscopy(TEM), UV-V is spectroscopy. The results revealed that the structure of as-synthesized CZTS microparticles is kesterite;the morphology of CZTS has occurred a certain change with different contents of PVP. When 0.2 g of PVP was added to the reaction system, uniform and monodisperse CZTS MCs containing nanosheets were obtained. The nanosheets was more compact than the reaction system with 0.1 g of PVP. The band gap of the CZTS is about 1.47 eV, which approaches the optimum value for solar photoelectric conversion. Finally, a possible fabrication mechanisms of uniform and monodisperse CZTS MCs containing nanosheets was also inferred.
Quaternary kesterite Cu2ZnSnS4(CZTS) micro-particles were successfully synthesized by a facile solvothermal method in ethylene glycol with the presence of Polyvinylpyrrolidone (PVP) as surfactant, using CuCl2·2H2O、Zn(Ac)2·2H2O and SnCl4·5H2O as metal precursor and thiourea as sulfur source. Different dispersion CZTS particles were obtained by different contents of PVP. The structure, morphology and absorption spectra of the as-obtained CZTS particles were characterized by means of X-ray diffraction(XRD), Raman spectroscopy, scanning electron microscopy(SEM), transmission electron microscopy(TEM), UV-V is spectroscopy. The results revealed that the structure of as-synthesized CZTS microparticles is kesterite;the morphology of CZTS has occurred a certain change with different contents of PVP. When 0.2 g of PVP was added to the reaction system, uniform and monodisperse CZTS MCs containing nanosheets were obtained. The nanosheets was more compact than the reaction system with 0.1 g of PVP. The band gap of the CZTS is about 1.47 eV, which approaches the optimum value for solar photoelectric conversion. Finally, a possible fabrication mechanisms of uniform and monodisperse CZTS MCs containing nanosheets was also inferred.
2013, 29(11): 2387-2393
doi: 10.3969/j.issn.1001-4861.2013.00.353
Abstract:
Oxygenation of three complexes His-Co, Hio-Co and Hit-Co were determined by UV-Vis spectrophotometry and oxygen electrode, respectively. The curve of absorption change with pHshowed that the oxygenation reactions took place after pH6.0 for all three complexes. His-Co has two oxygenated species in pH6.0~10.0, whereas, Hio-Co and Hit-Co only formed one oxygenated species. The results obtained from the equimolar ratio method showed the molar ration for Co:His and Co:Hio is 1:2,whereas Co:Hit is 1:3. Oxygenation properties and anti-aging processes of three complexes were determined by UV-V is spectrophotometry at λ=384 nm in room temperature in pH 7.0, respectively. The results revealed that all three complexes can uptake dioxygen reversibly whereas there are obvious differences in their oxygenations, especially in the deoxygenation rate. His-Co kept 5% oxygenation capacity after 560 cycles/110 h continuous oxygenation, while Hio-Co and Hit-Co sustained 59 cycles/54 h and 5 cycles /10.2 h, respectively. The order of anti-aging rate of the complexes is His-Co>>Hio-Co>Hit-Co. The results suggested that the uptaking dioxygen reversibility of the complex with a ligand of three coordinating atoms is better than the complex with a ligand of two coordinating atoms, and the uptaking dioxygen reversibility of the aminoacid complex is better than that of alkamine complex.
Oxygenation of three complexes His-Co, Hio-Co and Hit-Co were determined by UV-Vis spectrophotometry and oxygen electrode, respectively. The curve of absorption change with pHshowed that the oxygenation reactions took place after pH6.0 for all three complexes. His-Co has two oxygenated species in pH6.0~10.0, whereas, Hio-Co and Hit-Co only formed one oxygenated species. The results obtained from the equimolar ratio method showed the molar ration for Co:His and Co:Hio is 1:2,whereas Co:Hit is 1:3. Oxygenation properties and anti-aging processes of three complexes were determined by UV-V is spectrophotometry at λ=384 nm in room temperature in pH 7.0, respectively. The results revealed that all three complexes can uptake dioxygen reversibly whereas there are obvious differences in their oxygenations, especially in the deoxygenation rate. His-Co kept 5% oxygenation capacity after 560 cycles/110 h continuous oxygenation, while Hio-Co and Hit-Co sustained 59 cycles/54 h and 5 cycles /10.2 h, respectively. The order of anti-aging rate of the complexes is His-Co>>Hio-Co>Hit-Co. The results suggested that the uptaking dioxygen reversibility of the complex with a ligand of three coordinating atoms is better than the complex with a ligand of two coordinating atoms, and the uptaking dioxygen reversibility of the aminoacid complex is better than that of alkamine complex.
2013, 29(11): 2394-2398
doi: 10.3969/j.issn.1001-4861.2013.00.375
Abstract:
Anew compound, namely 2,4-di(2-thiazole)-6-[2-(4-N,N-dimethylamino)phenylethenyl]-1,3,5-s-triazine (2), was synthesized and fully characterized. Compound 2 displayed double absorption peaks at 355 and 416 nm in the acetonitrile-water mixed medium. In the presence of various metal ions, a new absorption band peaking at 520 nm was appeared for Cu2+, Hg2+ and Fe3+ ions. The binding stoichiometry of compound 2 with Cu2+, Hg2+ and Fe3+ ions was 1:1 and the association constants were 1.9×105, 6.6×103 and 2.7×103 L·mol-1, respectively. Compound 4 exhibited similar spectral response to metal ions with compound 2. The binding mode for compounds 2 with these heavy metal ions was investigated using1H NMR spectral titration as well. The results suggested that Cu2+, Hg2+ and Fe3+ ions coordinated with the Natom of the triazine and the Satom of thiophene cooperatively.
Anew compound, namely 2,4-di(2-thiazole)-6-[2-(4-N,N-dimethylamino)phenylethenyl]-1,3,5-s-triazine (2), was synthesized and fully characterized. Compound 2 displayed double absorption peaks at 355 and 416 nm in the acetonitrile-water mixed medium. In the presence of various metal ions, a new absorption band peaking at 520 nm was appeared for Cu2+, Hg2+ and Fe3+ ions. The binding stoichiometry of compound 2 with Cu2+, Hg2+ and Fe3+ ions was 1:1 and the association constants were 1.9×105, 6.6×103 and 2.7×103 L·mol-1, respectively. Compound 4 exhibited similar spectral response to metal ions with compound 2. The binding mode for compounds 2 with these heavy metal ions was investigated using1H NMR spectral titration as well. The results suggested that Cu2+, Hg2+ and Fe3+ ions coordinated with the Natom of the triazine and the Satom of thiophene cooperatively.
2013, 29(11): 2399-2404
doi: 10.3969/j.issn.1001-4861.2013.00.316
Abstract:
In-situ Diffuse Reflectance Infrared Fourier Transform (In-situ DRIFT) Spectroscopy was employed to investigate the reaction mechanism of NH3-Selective Catalytic Reduction (SCR) upon NOon CrOx-CeO2 binary oxide at 473 K. The surface adsorbed species on the CrOx-CeO2 binary oxide during the SCR reaction were analyzed. To elucidate the reaction process more precisely, we cut off the NH3 and NO flow, respectively, in the SCR reaction and collected the resulting in-situ DRIFT spectra. The results indicate that the SCR reaction process might follow the Eley-Rideal (E-R) mechanism.
In-situ Diffuse Reflectance Infrared Fourier Transform (In-situ DRIFT) Spectroscopy was employed to investigate the reaction mechanism of NH3-Selective Catalytic Reduction (SCR) upon NOon CrOx-CeO2 binary oxide at 473 K. The surface adsorbed species on the CrOx-CeO2 binary oxide during the SCR reaction were analyzed. To elucidate the reaction process more precisely, we cut off the NH3 and NO flow, respectively, in the SCR reaction and collected the resulting in-situ DRIFT spectra. The results indicate that the SCR reaction process might follow the Eley-Rideal (E-R) mechanism.
2013, 29(11): 2405-2414
doi: 10.3969/j.issn.1001-4861.2013.00.380
Abstract:
Two new Cu(Ⅱ) complexes, [Cu(phen)(H2O)(fba)(ClO4)]·H2O (1) and ∞1[Cu(bpy)(H2O)(fba)2](2)(phen=phenanthroline, bpy=2,2'-bipyridine Hfba=p-formylbenzoic acid) were synthesized by solution-based method and characterized by single-crystal, powder X-ray diffraction methods, IR spectroscopy, TG-DTAanalyses, elemental analyses, and magnetic measurements. Compound 1 is a mononuclear structure crystallizing in the space group P1 and 2 shows a 1D chain structure which belongs to the space group Pbca. Through non-covalent interactions the complex molecules are assembled into 3D supramolecular network structures. The variable temperature magnetic measurements of 1 shows a weak ferromagnetic and antiferromagnetic behavior in the range of 300~7 and 7~2 K, respectively, while the 2's suggests very weak ferromagnetic interactions between Cu(Ⅱ) ions in the experimental temperature range. CCDC: 912745, 1;CCDC: 912746, 2.
Two new Cu(Ⅱ) complexes, [Cu(phen)(H2O)(fba)(ClO4)]·H2O (1) and ∞1[Cu(bpy)(H2O)(fba)2](2)(phen=phenanthroline, bpy=2,2'-bipyridine Hfba=p-formylbenzoic acid) were synthesized by solution-based method and characterized by single-crystal, powder X-ray diffraction methods, IR spectroscopy, TG-DTAanalyses, elemental analyses, and magnetic measurements. Compound 1 is a mononuclear structure crystallizing in the space group P1 and 2 shows a 1D chain structure which belongs to the space group Pbca. Through non-covalent interactions the complex molecules are assembled into 3D supramolecular network structures. The variable temperature magnetic measurements of 1 shows a weak ferromagnetic and antiferromagnetic behavior in the range of 300~7 and 7~2 K, respectively, while the 2's suggests very weak ferromagnetic interactions between Cu(Ⅱ) ions in the experimental temperature range. CCDC: 912745, 1;CCDC: 912746, 2.
2013, 29(11): 2415-2421
doi: 10.3969/j.issn.1001-4861.2013.00.346
Abstract:
Layered, flowerlike, and rodlike bismuth titanate (Bi4Ti3O12, BIT) nanostructures were synthesized via the controllable hydrothermal method. The phase structures and morphologies were measured by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). XRD patterns demonstrate that the as-prepared samples are of layered-perovskite structure. FESEM shows that BITcrystals can be fabricated in different morphologies by simply manipulating the reaction parameters of hydrothermal process. The UV-Vis diffuse reflectance spectra (UV-Vis DRS) reveal that the band gaps of BIT photocatalysts are 2.63~2.95 eV. The as-prepared BIT photocatalysts exhibit higher photocatalytic activities in the degradation of methyl orange (MO) under visible light irradiation (λ>420 nm) compared with traditional N-doped TiO2 (N-TiO2). Layered BIT nanostructures show the highest photocatalytic activity. Up to 95.0% MO is decolorized after visible light irradiation for 360 min. In addition, the reason for the difference in the photocatalytic activities obtained at different conditions was studied based on the structures and morphologies.
Layered, flowerlike, and rodlike bismuth titanate (Bi4Ti3O12, BIT) nanostructures were synthesized via the controllable hydrothermal method. The phase structures and morphologies were measured by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). XRD patterns demonstrate that the as-prepared samples are of layered-perovskite structure. FESEM shows that BITcrystals can be fabricated in different morphologies by simply manipulating the reaction parameters of hydrothermal process. The UV-Vis diffuse reflectance spectra (UV-Vis DRS) reveal that the band gaps of BIT photocatalysts are 2.63~2.95 eV. The as-prepared BIT photocatalysts exhibit higher photocatalytic activities in the degradation of methyl orange (MO) under visible light irradiation (λ>420 nm) compared with traditional N-doped TiO2 (N-TiO2). Layered BIT nanostructures show the highest photocatalytic activity. Up to 95.0% MO is decolorized after visible light irradiation for 360 min. In addition, the reason for the difference in the photocatalytic activities obtained at different conditions was studied based on the structures and morphologies.
2013, 29(11): 2422-2432
doi: 10.3969/j.issn.1001-4861.2013.00.379
Abstract:
Two lanthanide(Ⅲ) complexes, [Ln(atma)3(H2O)2]n have been synthesized (Ln=La (1) and Nd (2);Hatma=[5-amino-1,3,4-thiadiazol-2-yl]thioglycolic acid). The structure of Hatma ligand and complexes 1, 2 have been determined by X-ray structural analysis and the structure parameters were analyzed as follows: Hatma, monoclinic, C2/c, a=2.1419(9) nm, b=0.40076(17) nm, c=1.7500(8) nm, V=1.4950(11) nm3, Z=4;1, triclinic, P1, a=0.8820(3) nm, b=1.2306(4) nm, c=1.2586(4) nm, V=1.2913(7) nm3, Z=2;2, triclinic, P1, a=0.8834(4) nm, b=1.2283(5) nm, c=1.2510(5) nm, V=1.2821(9) nm3, Z=2. These two complexes are isomorphic and have one-dimensional chain and rich hydrogen bonds which result in three-dimensional supramolecular structures. The complexes were determined by IR, TGA, elemental analysis and single crystal X-ray diffraction. The antimicrobial assays indicate that the two complexes show better activities than free ligand Hatma. The promoting effects of the title complexes on rape and wheat growth were also tested preliminarily. CCDC: 902095, Hatma;830535, 1;830536, 2.
Two lanthanide(Ⅲ) complexes, [Ln(atma)3(H2O)2]n have been synthesized (Ln=La (1) and Nd (2);Hatma=[5-amino-1,3,4-thiadiazol-2-yl]thioglycolic acid). The structure of Hatma ligand and complexes 1, 2 have been determined by X-ray structural analysis and the structure parameters were analyzed as follows: Hatma, monoclinic, C2/c, a=2.1419(9) nm, b=0.40076(17) nm, c=1.7500(8) nm, V=1.4950(11) nm3, Z=4;1, triclinic, P1, a=0.8820(3) nm, b=1.2306(4) nm, c=1.2586(4) nm, V=1.2913(7) nm3, Z=2;2, triclinic, P1, a=0.8834(4) nm, b=1.2283(5) nm, c=1.2510(5) nm, V=1.2821(9) nm3, Z=2. These two complexes are isomorphic and have one-dimensional chain and rich hydrogen bonds which result in three-dimensional supramolecular structures. The complexes were determined by IR, TGA, elemental analysis and single crystal X-ray diffraction. The antimicrobial assays indicate that the two complexes show better activities than free ligand Hatma. The promoting effects of the title complexes on rape and wheat growth were also tested preliminarily. CCDC: 902095, Hatma;830535, 1;830536, 2.
2013, 29(11): 2433-2437
doi: 10.3969/j.issn.1001-4861.2013.00.339
Abstract:
The title complex, [Ni6(H2O)6(HTMT)6]·3(C2H5)3N·7H2O (1) (H3TMT=trithiocyanuric acid), was synthesized by slow evaperation, which was characterized by IR, elemental analysis, and single crystal X-ray diffraction. This complex crystallizes in trigonal, space group R3c, with a=b=1.8697(3) nm, c=3.9825(8) nm, γ=120°, V=12.057(4) nm3, C36H77N21Ni6O13S18, Mr=1941.36, Dc=1.596 gcm-3, Z=6, μ=1.91 mm-1, F(000)=6095, the final R=0.047, wR=0.151 for [Ni6(H2O)6(HTMT)6]·3(C2H5)3N·7H2O (1) observed reflections (I>2σ(I)). X-ray diffraction analysis reveals that the six nickel(Ⅱ) atoms are bridged by six HTMT2- and six water molecules into a hexanuclear building unit, the neutral hexanuclear building units are further connected into a three-dimensional framework through the O-H…O and O-H…N hydrogen bonding interactions. The photoluminescent property of complex (I) was also studied at room temperature.
The title complex, [Ni6(H2O)6(HTMT)6]·3(C2H5)3N·7H2O (1) (H3TMT=trithiocyanuric acid), was synthesized by slow evaperation, which was characterized by IR, elemental analysis, and single crystal X-ray diffraction. This complex crystallizes in trigonal, space group R3c, with a=b=1.8697(3) nm, c=3.9825(8) nm, γ=120°, V=12.057(4) nm3, C36H77N21Ni6O13S18, Mr=1941.36, Dc=1.596 gcm-3, Z=6, μ=1.91 mm-1, F(000)=6095, the final R=0.047, wR=0.151 for [Ni6(H2O)6(HTMT)6]·3(C2H5)3N·7H2O (1) observed reflections (I>2σ(I)). X-ray diffraction analysis reveals that the six nickel(Ⅱ) atoms are bridged by six HTMT2- and six water molecules into a hexanuclear building unit, the neutral hexanuclear building units are further connected into a three-dimensional framework through the O-H…O and O-H…N hydrogen bonding interactions. The photoluminescent property of complex (I) was also studied at room temperature.
2013, 29(11): 2438-2444
doi: 10.3969/j.issn.1001-4861.2013.00.384
Abstract:
Two mononuclear copper(Ⅱ) complexes, [CuL(CH3CN)(ClO4)]ClO4(1) and cis-[CuL(NCS)2]·0.5C4H8O2(2) (L=2-[N,N-di(2-pyridylmethyl)aminomethyl]-6-aldehydo-4-methylphenol) have been synthesized and characterized by UV-Vis, FTIR, ESI-MS, elemental analysis and single crystal X-ray crystallography. Both 1 and 2 crystallize in a monoclinic system. Each copper(Ⅱ) ion locates in a distorted octahedron geometry. As a tetradentate chelating ligand, the Lcoordinates to copper(Ⅱ) ion via two pyridyl Natoms, one Natom of tertiary amine, and one phenol O atom. In 1, an acetonitrile molecule and a perchlorate anion also take part in coordination;while there are two cis-disposed NCS-ions in 2. CCDC: 938954, 1;938955, 2.
Two mononuclear copper(Ⅱ) complexes, [CuL(CH3CN)(ClO4)]ClO4(1) and cis-[CuL(NCS)2]·0.5C4H8O2(2) (L=2-[N,N-di(2-pyridylmethyl)aminomethyl]-6-aldehydo-4-methylphenol) have been synthesized and characterized by UV-Vis, FTIR, ESI-MS, elemental analysis and single crystal X-ray crystallography. Both 1 and 2 crystallize in a monoclinic system. Each copper(Ⅱ) ion locates in a distorted octahedron geometry. As a tetradentate chelating ligand, the Lcoordinates to copper(Ⅱ) ion via two pyridyl Natoms, one Natom of tertiary amine, and one phenol O atom. In 1, an acetonitrile molecule and a perchlorate anion also take part in coordination;while there are two cis-disposed NCS-ions in 2. CCDC: 938954, 1;938955, 2.
2013, 29(11): 2445-2449
doi: 10.3969/j.issn.1001-4861.2013.00.341
Abstract:
A coordination polymer {[Ni(H2BCPBA)2(H2O)4]}n (1, H3BCPBA=3,5-bi(4-carboxy-phenoxy)-benzoic acid) has been synthesized from H3BCPBA by using hydrothermal method and structurally characterized by elemental analysis, IR spectrum, UV spectroscopy, TG and single-crystal X-ray diffraction. Single-crystal X-ray analysis reveals that the coordination polymer 1 is crystallized in the triclinic system, space group P1. The Ni(Ⅱ) ion is six-coordinated by two oxygen atoms from H2BCPBA- ligand and four oxygen atoms from water molecules, generating a octahedral coordination geometry. UV spectroscopy study reveals that the coordination polymer exhibits strong ultraviolet absorption in the solid state at room temperature. CCDC: 837882.
A coordination polymer {[Ni(H2BCPBA)2(H2O)4]}n (1, H3BCPBA=3,5-bi(4-carboxy-phenoxy)-benzoic acid) has been synthesized from H3BCPBA by using hydrothermal method and structurally characterized by elemental analysis, IR spectrum, UV spectroscopy, TG and single-crystal X-ray diffraction. Single-crystal X-ray analysis reveals that the coordination polymer 1 is crystallized in the triclinic system, space group P1. The Ni(Ⅱ) ion is six-coordinated by two oxygen atoms from H2BCPBA- ligand and four oxygen atoms from water molecules, generating a octahedral coordination geometry. UV spectroscopy study reveals that the coordination polymer exhibits strong ultraviolet absorption in the solid state at room temperature. CCDC: 837882.
2013, 29(11): 2450-2454
doi: 10.3969/j.issn.1001-4861.2013.00.361
Abstract:
The new coordination polymer named, {[Cd(L)(HBTC)(H2O)]·H2O}n (L=1,2-bis(1,2,4-triazol-1-ylmethyl)benzene, H3BTC=1,3,5-benzenetricarboxylic acid) has been synthesized hydrothermally and characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis and single-crystal X-ray diffraction analysis. The cadmium center is six coordinated with three OCOO-atoms from two different HBTC2- dianions and one water molecule locate in the equatorial positions, while apical sites are occupied by two Natoms from two distinct Lligands in a distorted octahedral geometry. The structural analysis shows that the complex possesses a two-dimensional 2D (4,4) layer structure, and displays a three-dimensional (3D) supramolecular structure via multiple intermolecular O-H…O hydrogen bonds. The fluorescence property of the complex also has been studied. CCDC: 917952.
The new coordination polymer named, {[Cd(L)(HBTC)(H2O)]·H2O}n (L=1,2-bis(1,2,4-triazol-1-ylmethyl)benzene, H3BTC=1,3,5-benzenetricarboxylic acid) has been synthesized hydrothermally and characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis and single-crystal X-ray diffraction analysis. The cadmium center is six coordinated with three OCOO-atoms from two different HBTC2- dianions and one water molecule locate in the equatorial positions, while apical sites are occupied by two Natoms from two distinct Lligands in a distorted octahedral geometry. The structural analysis shows that the complex possesses a two-dimensional 2D (4,4) layer structure, and displays a three-dimensional (3D) supramolecular structure via multiple intermolecular O-H…O hydrogen bonds. The fluorescence property of the complex also has been studied. CCDC: 917952.
2013, 29(11): 2455-2459
doi: 10.3969/j.issn.1001-4861.2013.00.364
Abstract:
Anovel cadmium-biimidazole compound [Cd(BIm)2](ClO4)(OH)·2H2O (1) (BIm=2,2'-biimidazole) has been synthesized via a hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Compound 1 features an isolated (0D) structure with the cadmium ions coordinating to four nitrogen atoms to give a distorted tetrahedron. Photoluminescent investigation shows that compound 1 exhibits an emission in the blue region. Theoretical study reveals that the emission is ascribed to ligand-to-metal charge transfer (LMCT). The spectral data of FT-IR are also reported. CCDC: 895386.
Anovel cadmium-biimidazole compound [Cd(BIm)2](ClO4)(OH)·2H2O (1) (BIm=2,2'-biimidazole) has been synthesized via a hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Compound 1 features an isolated (0D) structure with the cadmium ions coordinating to four nitrogen atoms to give a distorted tetrahedron. Photoluminescent investigation shows that compound 1 exhibits an emission in the blue region. Theoretical study reveals that the emission is ascribed to ligand-to-metal charge transfer (LMCT). The spectral data of FT-IR are also reported. CCDC: 895386.
2013, 29(11): 2460-2464
doi: 10.3969/j.issn.1001-4861.2013.00.343
Abstract:
Anovel 3d-4f heterometallic coordination polymer, namely, {[NdZn(H2pimda)3(Hpimda)(H2O)2]·H2O}n (1), (H3pimda=2-propyl-1H-imidazole-4,5-dicarboxylic acid) has been hydrothermally synthesized by using Nd2O3, Zn(NO3)2·6H2O and H3 pimda as raw materials, and characterized by elemental analysis, IR, TG analysis and single crystal X-ray diffraction. The complex 1 crystallizes in the monoclinic system, space group P21/c with a=1.19078(2) nm, b=1.30784(3) nm, c=2.74070(5) nm, β=97.9300(10)°, V=4.22741(14) nm3, Dc=1.652 g·cm-3, Z=4, R=0.0492 and wR=0.1115 (I>2σ(I)). Polymer 1 possesses two-dimensional (2D) network, which further build three-dimensional (3D) supramolecular architecture via N-H…O hydrogen-bonding interactions. Variable temperature magnetic susceptibility studies reveal that complex 1 displays weak antiferromagnetic coupling between the neighboring Nd(Ⅲ) ions. CCDC: 906826.
Anovel 3d-4f heterometallic coordination polymer, namely, {[NdZn(H2pimda)3(Hpimda)(H2O)2]·H2O}n (1), (H3pimda=2-propyl-1H-imidazole-4,5-dicarboxylic acid) has been hydrothermally synthesized by using Nd2O3, Zn(NO3)2·6H2O and H3 pimda as raw materials, and characterized by elemental analysis, IR, TG analysis and single crystal X-ray diffraction. The complex 1 crystallizes in the monoclinic system, space group P21/c with a=1.19078(2) nm, b=1.30784(3) nm, c=2.74070(5) nm, β=97.9300(10)°, V=4.22741(14) nm3, Dc=1.652 g·cm-3, Z=4, R=0.0492 and wR=0.1115 (I>2σ(I)). Polymer 1 possesses two-dimensional (2D) network, which further build three-dimensional (3D) supramolecular architecture via N-H…O hydrogen-bonding interactions. Variable temperature magnetic susceptibility studies reveal that complex 1 displays weak antiferromagnetic coupling between the neighboring Nd(Ⅲ) ions. CCDC: 906826.
2013, 29(11): 2465-2469
doi: 10.3969/j.issn.1001-4861.2013.00.356
Abstract:
Anew copper(Ⅱ) complex {[Cu2(Phen)4(NO3)][Cu(Phen)2(L)]2(L)2(NO3)3}·2H2O (1) with 2-benzoylbenzoic acid (HL) and 1,10-phenanthroline (Phen) as ligands has been synthesized. Crystal data for the complex are as follows: triclinic, space group P1, a=1.13857(5) nm, b=1.19349(7) nm, c=2.61531(13) nm, α=89.4280(10)°, β=82.753(2)°, γ=74.5370(10)°, V=3.3968(3) nm3, Dc=1.408 g·cm-3, Z=1, μ(Mo Kα)=0.700 mm-1, F(000)=1480, final discrepancy factors R10.0571, wR2=0.1334. In 1, there are two mononuclear cations [Cu(Phen)2(L)]+ and one dinuclear cation [Cu2(Phen)4(NO3)]3+, and the four central Cu(Ⅱ) ions are all penta-coordinated. The electrochemical, fluorescent and magnetic properties of 1 were investigated. The results show that the electron transfer in the electrode reaction of 1 is quasi reversible, and the electrode reaction corresponds to Cu(Ⅱ)/Cu(Ⅰ). When the exciting radiation set at 488 nm, 1 can give off strong fluorescence band at around 494 nm. In addition, 1 displays diamagnetic property in temperatures range of 300~52 K. CCDC: 929034.
Anew copper(Ⅱ) complex {[Cu2(Phen)4(NO3)][Cu(Phen)2(L)]2(L)2(NO3)3}·2H2O (1) with 2-benzoylbenzoic acid (HL) and 1,10-phenanthroline (Phen) as ligands has been synthesized. Crystal data for the complex are as follows: triclinic, space group P1, a=1.13857(5) nm, b=1.19349(7) nm, c=2.61531(13) nm, α=89.4280(10)°, β=82.753(2)°, γ=74.5370(10)°, V=3.3968(3) nm3, Dc=1.408 g·cm-3, Z=1, μ(Mo Kα)=0.700 mm-1, F(000)=1480, final discrepancy factors R10.0571, wR2=0.1334. In 1, there are two mononuclear cations [Cu(Phen)2(L)]+ and one dinuclear cation [Cu2(Phen)4(NO3)]3+, and the four central Cu(Ⅱ) ions are all penta-coordinated. The electrochemical, fluorescent and magnetic properties of 1 were investigated. The results show that the electron transfer in the electrode reaction of 1 is quasi reversible, and the electrode reaction corresponds to Cu(Ⅱ)/Cu(Ⅰ). When the exciting radiation set at 488 nm, 1 can give off strong fluorescence band at around 494 nm. In addition, 1 displays diamagnetic property in temperatures range of 300~52 K. CCDC: 929034.
2013, 29(11): 2470-2474
doi: 10.3969/j.issn.1001-4861.2013.00.322
Abstract:
Anew one-dimensional cyanide-bridged FeⅢ-CuⅡ complex {[Fe(1-CH3im)(CN)4(μ-CN)Cu(cyclam)]·H2O}n (1-CH3im=1-methylimidazole, cyclam=1,4,8,11-tetraazacyclotetradecane) (1) has been synthesized by the reaction of [Cu(cyclam)](ClO4)2 and a pentacyanideferrite building blocks K2[Fe(1-CH3im)(CN)5]. Single crystal X-ray diffraction analysis reveals the structure of complex 1 is polymer type with two different metal centers which is alternated linked by cyanide group from the [Fe(1-CH3im)(CN)5]2- building blocks. Complex 1 (C19H32CuFeN11O, Mr=549.95) crystallizes in triclinic space group P1 with a=0.83256(17) nm, b=0.89938(18) nm, c=0.9983(2) nm, α=111.94(3)°, β=95.06(3)°, γ=116.90(3)°, V=0.5877(2) nm3, Z=1, Dc=1.554 g·cm-3, μ=1.558 mm-1, F(000)=286, the final R10.0519 and wR2=0.1353. Magnetic investigations show that complex 1 exhibits a weak ferromagnetic coupling between CuⅡ and low-spin FeⅢ through the cyanide bridge. CCDC: 908099.
Anew one-dimensional cyanide-bridged FeⅢ-CuⅡ complex {[Fe(1-CH3im)(CN)4(μ-CN)Cu(cyclam)]·H2O}n (1-CH3im=1-methylimidazole, cyclam=1,4,8,11-tetraazacyclotetradecane) (1) has been synthesized by the reaction of [Cu(cyclam)](ClO4)2 and a pentacyanideferrite building blocks K2[Fe(1-CH3im)(CN)5]. Single crystal X-ray diffraction analysis reveals the structure of complex 1 is polymer type with two different metal centers which is alternated linked by cyanide group from the [Fe(1-CH3im)(CN)5]2- building blocks. Complex 1 (C19H32CuFeN11O, Mr=549.95) crystallizes in triclinic space group P1 with a=0.83256(17) nm, b=0.89938(18) nm, c=0.9983(2) nm, α=111.94(3)°, β=95.06(3)°, γ=116.90(3)°, V=0.5877(2) nm3, Z=1, Dc=1.554 g·cm-3, μ=1.558 mm-1, F(000)=286, the final R10.0519 and wR2=0.1353. Magnetic investigations show that complex 1 exhibits a weak ferromagnetic coupling between CuⅡ and low-spin FeⅢ through the cyanide bridge. CCDC: 908099.
2013, 29(11): 2475-2479
doi: 10.3969/j.issn.1001-4861.2013.00.355
Abstract:
Anovel zinc coordination polymer {[Zn(cpds)(dpa)]·H2O}n (1) (H2cpds=6,6'-dithiodinicotinic acid, dpa=dipyridin-2-ylamine) has been hydrothermally synthesized and structurally characterized by single-crystal. Complex 1 crystallizes in the triclinic system, space group P1 with a=0.8467(2), b=1.1674(3), c=1.2265(3) nm, α=73.605(3)°, β=78.656(3)°, γ=81.484(3)°, V=1.1347(5) nm3, Dc=1.850 g·cm-3, Z=2. Single-crystal X-ray analysis reveal that compound 1 contains an infinite 1D chain structure, and the 1D chain was stacked together to form a 3D supramolecular network. Additionally, the fluorescent property and TG analysis for compound 1 were also measured and discussed. CCDC: 931127.
Anovel zinc coordination polymer {[Zn(cpds)(dpa)]·H2O}n (1) (H2cpds=6,6'-dithiodinicotinic acid, dpa=dipyridin-2-ylamine) has been hydrothermally synthesized and structurally characterized by single-crystal. Complex 1 crystallizes in the triclinic system, space group P1 with a=0.8467(2), b=1.1674(3), c=1.2265(3) nm, α=73.605(3)°, β=78.656(3)°, γ=81.484(3)°, V=1.1347(5) nm3, Dc=1.850 g·cm-3, Z=2. Single-crystal X-ray analysis reveal that compound 1 contains an infinite 1D chain structure, and the 1D chain was stacked together to form a 3D supramolecular network. Additionally, the fluorescent property and TG analysis for compound 1 were also measured and discussed. CCDC: 931127.
2013, 29(11): 2480-2484
doi: 10.3969/j.issn.1001-4861.2013.00.370
Abstract:
Two sandwich-like coordination polymers based on Ag(Ⅰ) and mixed flexible ligands, {[Ag2(bpa)2(bpp)2]·2H2O}n (1) and {[Ag(bpa)(bpp)]·2H2O}n (2) (bpa-=4-biphenylacetate, bpp=1,3-bis(4-pyridyl)propane), have been synthesized by solution reactions of Hbpa, bpp and [Ag(NH3)](OH) with the same ratio under different experimental conditions. They were characterized by single-crystal X-ray diffraction, EA, IRand XRD. Complex 1 is a two-dimensional network based on T-shaped coordination Ag(Ⅰ) ions and Ag…Ag interactions. In 2, the distorted tetrahedral coordination Ag(Ⅰ) ions are further organized by π…π stacking interactions into another two-dimensional network. 1 and 2 exhibit different and intense emissions in the visible region. CCDC: 922168,1;922167, 2.
Two sandwich-like coordination polymers based on Ag(Ⅰ) and mixed flexible ligands, {[Ag2(bpa)2(bpp)2]·2H2O}n (1) and {[Ag(bpa)(bpp)]·2H2O}n (2) (bpa-=4-biphenylacetate, bpp=1,3-bis(4-pyridyl)propane), have been synthesized by solution reactions of Hbpa, bpp and [Ag(NH3)](OH) with the same ratio under different experimental conditions. They were characterized by single-crystal X-ray diffraction, EA, IRand XRD. Complex 1 is a two-dimensional network based on T-shaped coordination Ag(Ⅰ) ions and Ag…Ag interactions. In 2, the distorted tetrahedral coordination Ag(Ⅰ) ions are further organized by π…π stacking interactions into another two-dimensional network. 1 and 2 exhibit different and intense emissions in the visible region. CCDC: 922168,1;922167, 2.
2013, 29(11): 2485-2490
doi: 10.3969/j.issn.1001-4861.2013.00.350
Abstract:
Anew coordination polymer, namely [Cd(NH2bdc)(e-urea)]n (1) (H2NH2bdc=2-amino-1,4-benzenedicar-boxylic acid, e-urea=2-imidazolidinone) has been urothermally synthesized by using urea derivative 2-imidazoli-dinone as solvent and its structure and fluorescence property have also been investigated. The crystallography analysis reveals that the centric Cd(Ⅱ) ion is seven coordinated by carboxylate oxygen atoms from NH2bdc ligands and oxygen atoms of e-urea molecules forming a distorted pentagonal-bipyramidal coordination geometry. The adjacent Cd(Ⅱ) centers are bridged by oxygen atoms of e-urea molecules and carboxylate groups of NH2bdc ligands forming an infinite 1Dchain. Thus 1Dchains are further connected together by NH2bdc ligands into a 3D coordination framework with 1D tunnels. Luminescent study shows that complex 1 displays a strong blue emission at room temperature. CCDC: 902023.
Anew coordination polymer, namely [Cd(NH2bdc)(e-urea)]n (1) (H2NH2bdc=2-amino-1,4-benzenedicar-boxylic acid, e-urea=2-imidazolidinone) has been urothermally synthesized by using urea derivative 2-imidazoli-dinone as solvent and its structure and fluorescence property have also been investigated. The crystallography analysis reveals that the centric Cd(Ⅱ) ion is seven coordinated by carboxylate oxygen atoms from NH2bdc ligands and oxygen atoms of e-urea molecules forming a distorted pentagonal-bipyramidal coordination geometry. The adjacent Cd(Ⅱ) centers are bridged by oxygen atoms of e-urea molecules and carboxylate groups of NH2bdc ligands forming an infinite 1Dchain. Thus 1Dchains are further connected together by NH2bdc ligands into a 3D coordination framework with 1D tunnels. Luminescent study shows that complex 1 displays a strong blue emission at room temperature. CCDC: 902023.
2013, 29(11): 2491-2496
doi: 10.3969/j.issn.1001-4861.2013.00.348
Abstract:
The title complex [Ni(DTPB)H2Cl]Cl(BF4)2·4H2O (DTPB＝1, 1, 4, 7, 7-pentakis(1H-benzimidazol-2-ylmethyl)-1, 4, 7-triazaheptane) has been synthesized and structurally characterized, and its superoxide dismutase (SOD) catalytic activity was investigated by UVspectra. The results showed that the title complex exhibited distorted octahedron geometry, it can inhibit pyrogallol oxidation, IC50 of the complex was 29.8 mg·L-1, and its SOD activity was affected by reaction temperatures and pH values. CCDC: 606551.
The title complex [Ni(DTPB)H2Cl]Cl(BF4)2·4H2O (DTPB＝1, 1, 4, 7, 7-pentakis(1H-benzimidazol-2-ylmethyl)-1, 4, 7-triazaheptane) has been synthesized and structurally characterized, and its superoxide dismutase (SOD) catalytic activity was investigated by UVspectra. The results showed that the title complex exhibited distorted octahedron geometry, it can inhibit pyrogallol oxidation, IC50 of the complex was 29.8 mg·L-1, and its SOD activity was affected by reaction temperatures and pH values. CCDC: 606551.
2013, 29(11): 2497-2502
doi: 10.3969/j.issn.1001-4861.2013.00.283
Abstract:
Aneodymium(Ⅲ) coordination polymer, namely, {[Nd2(ox)(cb)2(H2O)2]·3H2O}n (1) (ox=oxalate, cb=carbonate) (1), has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, powder X-ray diffraction, and single-crystal X-ray diffraction. Structural determination reveals that the neodymium ions are bridged by μ2-ox and μ4-cb ligands to give a 3D framework including 2D channels of 0.53 nm×0.41 nm along the b axis and 0.59 nm×0.84 nm along the c axis, respectively. It can also be described as a (4,5)-connected {44.62}{44.66} topological 3D framework. Solid-state 1 emits the intensely NIR characteristic luminescence of Nd3+ ion at room temperature. CCDC: 917863.
Aneodymium(Ⅲ) coordination polymer, namely, {[Nd2(ox)(cb)2(H2O)2]·3H2O}n (1) (ox=oxalate, cb=carbonate) (1), has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, powder X-ray diffraction, and single-crystal X-ray diffraction. Structural determination reveals that the neodymium ions are bridged by μ2-ox and μ4-cb ligands to give a 3D framework including 2D channels of 0.53 nm×0.41 nm along the b axis and 0.59 nm×0.84 nm along the c axis, respectively. It can also be described as a (4,5)-connected {44.62}{44.66} topological 3D framework. Solid-state 1 emits the intensely NIR characteristic luminescence of Nd3+ ion at room temperature. CCDC: 917863.
2013, 29(11): 2503-2508
doi: 10.3969/j.issn.1001-4861.2013.00.354
Abstract:
A new 1Dcadmium(Ⅱ) coordination polymer, {[Cd(4',4-Hhbc)2(bpp)2]}n (1, 4',4-Hhbc=4'-Hydroxyl-biphenyl-4-carboxylate, bpp=1,3-bis(4-pyridyl)propane), has been hydrothermally synthesized and structurally characterized by elemental analysis, IRspectroscopy, TGA, powder X-ray diffraction, UV-Vis and single crystal X-ray diffraction. Structural determination reveals that 1 exhibits an interesting 1D chain structure. Solid-state 1 emits the intensely indigotin photoluminescence with fluorescence lifetime of 3.2 ns (440 nm) at room temperature. CCDC: 854723.
A new 1Dcadmium(Ⅱ) coordination polymer, {[Cd(4',4-Hhbc)2(bpp)2]}n (1, 4',4-Hhbc=4'-Hydroxyl-biphenyl-4-carboxylate, bpp=1,3-bis(4-pyridyl)propane), has been hydrothermally synthesized and structurally characterized by elemental analysis, IRspectroscopy, TGA, powder X-ray diffraction, UV-Vis and single crystal X-ray diffraction. Structural determination reveals that 1 exhibits an interesting 1D chain structure. Solid-state 1 emits the intensely indigotin photoluminescence with fluorescence lifetime of 3.2 ns (440 nm) at room temperature. CCDC: 854723.
