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2013 Volume 29 Issue 8
2013, 29(8): 1563-1573
doi: 10.3969/j.issn.1001-4861.2013.00.304
Abstract:
A Li-air battery could provide much higher energy density than conventional lithium-ion battery, which is comparable to gasoline and, thus, many attentions have been paid to the Li-air battery in recent years. This paper summarizes the latest development of the cathode material and electrolyte in the non-aqueous Li-air battery. The cathode materials concern commercial carbon, artificial carbon with a defined morphology, catalyst and conducting polymer. Electrolytes concern widely used solvents including ester, ether, sulfone, amine and ionic liquid. Finally, the main problems in the non-aqueous Li-air battery have been pointed out and look forward to the future on non-aqueous Li-air battery.
A Li-air battery could provide much higher energy density than conventional lithium-ion battery, which is comparable to gasoline and, thus, many attentions have been paid to the Li-air battery in recent years. This paper summarizes the latest development of the cathode material and electrolyte in the non-aqueous Li-air battery. The cathode materials concern commercial carbon, artificial carbon with a defined morphology, catalyst and conducting polymer. Electrolytes concern widely used solvents including ester, ether, sulfone, amine and ionic liquid. Finally, the main problems in the non-aqueous Li-air battery have been pointed out and look forward to the future on non-aqueous Li-air battery.
2013, 29(8): 1574-1590
doi: 10.3969/j.issn.1001-4861.2013.00.305
Abstract:
Near-infrared (NIR) light has great potential in biomedical application due to its advantages such as deep penetration depth and low photodamage to biological tissues. If we want to use NIR light that has entered animal body, for in-vivo diagnosis and therapeutic intervention, a prerequisite is to obtain nanomaterials and/or nanodevices that can absorb or convert NIR light. This paper reviews the recent research progress in NIR-light-driven nanomaterials and/or nanodevices, including up-converting rare-earth nanophosphors, 980-nm laser-driven generator, and photothermal nanoagents. The main attention has been given to the biological application of these nanomaterials and/or nanodevices. At last, the present problems and the future development trends are pointed out.
Near-infrared (NIR) light has great potential in biomedical application due to its advantages such as deep penetration depth and low photodamage to biological tissues. If we want to use NIR light that has entered animal body, for in-vivo diagnosis and therapeutic intervention, a prerequisite is to obtain nanomaterials and/or nanodevices that can absorb or convert NIR light. This paper reviews the recent research progress in NIR-light-driven nanomaterials and/or nanodevices, including up-converting rare-earth nanophosphors, 980-nm laser-driven generator, and photothermal nanoagents. The main attention has been given to the biological application of these nanomaterials and/or nanodevices. At last, the present problems and the future development trends are pointed out.
2013, 29(8): 1591-1598
doi: 10.3969/j.issn.1001-4861.2013.00.311
Abstract:
Photodynamic therapy (PDT) is a clinically approved procedure. Due to its minimal normal tissue toxicity, negligible side effects and high selectivity, it has emerged as an efficient treatment method for many kinds of cancers. Recently, significant effort has been devoted to enhance its selectivity and phototoxicity toward malignant tissues. This review summarizes the recent research of photosensitizers, especially focuses on the progress of the third generation photosensitizers based on phthalocyanines.
Photodynamic therapy (PDT) is a clinically approved procedure. Due to its minimal normal tissue toxicity, negligible side effects and high selectivity, it has emerged as an efficient treatment method for many kinds of cancers. Recently, significant effort has been devoted to enhance its selectivity and phototoxicity toward malignant tissues. This review summarizes the recent research of photosensitizers, especially focuses on the progress of the third generation photosensitizers based on phthalocyanines.
2013, 29(8): 1599-1608
doi: 10.3969/j.issn.1001-4861.2013.00.306
Abstract:
In this review, the recent research progress of organic hybrid main group heterometallic chalcogenides based on antimony has been summarized. The structures and typical secondary building units of these compounds are described and classified. The roles of organic constituents as structure-directing agents or ligands are explored. The studies on their ion-exchange and photocatalytic properties are reviewed.
In this review, the recent research progress of organic hybrid main group heterometallic chalcogenides based on antimony has been summarized. The structures and typical secondary building units of these compounds are described and classified. The roles of organic constituents as structure-directing agents or ligands are explored. The studies on their ion-exchange and photocatalytic properties are reviewed.
2013, 29(8): 1609-1616
doi: 10.3969/j.issn.1001-4861.2013.00.315
Abstract:
Constructions and applications of nanostructured inorganic biointerface is one of the new emerging research fronts of inorganic chemistry. Nanostructured inorganic materials are showing their important roles in areas such as biomimetic interface, cell interface, and biological detection. Recently, inorganic nanostructures have been exploringly applied for the fundamental study of trace circulating tumor cells (CTCs) isolation. The isolation of trace CTCs is very important for the early diagnosis and prognosis monitor of cancer, and the study of cancer biology, etc. In this review, we mainly focus on the construction of nanostructured inorganic biointerface for trace CTCs isolation. The research progress is summarized and the future prospect is discussed.
Constructions and applications of nanostructured inorganic biointerface is one of the new emerging research fronts of inorganic chemistry. Nanostructured inorganic materials are showing their important roles in areas such as biomimetic interface, cell interface, and biological detection. Recently, inorganic nanostructures have been exploringly applied for the fundamental study of trace circulating tumor cells (CTCs) isolation. The isolation of trace CTCs is very important for the early diagnosis and prognosis monitor of cancer, and the study of cancer biology, etc. In this review, we mainly focus on the construction of nanostructured inorganic biointerface for trace CTCs isolation. The research progress is summarized and the future prospect is discussed.
2013, 29(8): 1617-1625
doi: 10.3969/j.issn.1001-4861.2013.00.286
Abstract:
In this work, a series of La1-xCaxMnO3 perovskite nanoparticles were prepared through a sol-gel method and investigated as catalysts for the oxygen reduction reaction (ORR). The XRD, SEM and TEM characterization demonstrated high crystallinity of the synthesized particles having diameters of about 40 nm. The crystal structure was determined by Rietveld refinement, indicating variation of the lattice parameters with the amount of substituted Ca. The electrocatalytic properties of the samples were studied using rotating-disk and rotating ring-disk electrode techniques in KOH aqueous solution. Investigations on the composition-performance relationship of La1-xCaxMnO3 perovskites revealed that mixed Mn valence and medium Mn-O bond length favored the ORR electrocatalysis. Among the La1-xCaxMnO3 series, La0.7Ca0.3MnO3 exhibited outstanding ORR activity, enabled an apparent 4-electron pathway and showed superior durability compared to the benchmark carbon-supported Pt nanoparticles. Furthermore, metal-air cells assembled with La0.7Ca0.3MnO3 could deliver high charge and discharge capacity with flat plateaus. The considerable catalytic performances of La1-xCaxMnO3 nanoparticles indicate their promising application as low-cost and high-abundance catalysts in alkaline fuel cells and metal-air batteries.
In this work, a series of La1-xCaxMnO3 perovskite nanoparticles were prepared through a sol-gel method and investigated as catalysts for the oxygen reduction reaction (ORR). The XRD, SEM and TEM characterization demonstrated high crystallinity of the synthesized particles having diameters of about 40 nm. The crystal structure was determined by Rietveld refinement, indicating variation of the lattice parameters with the amount of substituted Ca. The electrocatalytic properties of the samples were studied using rotating-disk and rotating ring-disk electrode techniques in KOH aqueous solution. Investigations on the composition-performance relationship of La1-xCaxMnO3 perovskites revealed that mixed Mn valence and medium Mn-O bond length favored the ORR electrocatalysis. Among the La1-xCaxMnO3 series, La0.7Ca0.3MnO3 exhibited outstanding ORR activity, enabled an apparent 4-electron pathway and showed superior durability compared to the benchmark carbon-supported Pt nanoparticles. Furthermore, metal-air cells assembled with La0.7Ca0.3MnO3 could deliver high charge and discharge capacity with flat plateaus. The considerable catalytic performances of La1-xCaxMnO3 nanoparticles indicate their promising application as low-cost and high-abundance catalysts in alkaline fuel cells and metal-air batteries.
2013, 29(8): 1626-1632
doi: 10.3969/j.issn.1001-4861.2013.00.301
Abstract:
A hydrogen-deuterium exchange reaction model was constructed by combining the Sphere Particle Exchange Model (SPEM) and the Gas-Solid Surface Exchange Model, and programmed in terms of numerical algorithm using FORTRAN language to simulate the H-D exchange reaction in a column filled with palladium (Pd) particles. This model was then used to study the influence of the properties of Pd material, including its size and density in the column, the length of the column, the velocity of the gas flow and temperature, etc., on the exchange reaction. The calculation show that low flow velocity, high density and small size of Pd particles, longer column and higher temperature may accelerate the exchange reaction of D by H, while the diameter of column has no effect when the diffusion model used here holds.
A hydrogen-deuterium exchange reaction model was constructed by combining the Sphere Particle Exchange Model (SPEM) and the Gas-Solid Surface Exchange Model, and programmed in terms of numerical algorithm using FORTRAN language to simulate the H-D exchange reaction in a column filled with palladium (Pd) particles. This model was then used to study the influence of the properties of Pd material, including its size and density in the column, the length of the column, the velocity of the gas flow and temperature, etc., on the exchange reaction. The calculation show that low flow velocity, high density and small size of Pd particles, longer column and higher temperature may accelerate the exchange reaction of D by H, while the diameter of column has no effect when the diffusion model used here holds.
2013, 29(8): 1633-1638
doi: 10.3969/j.issn.1001-4861.2013.00.303
Abstract:
As newly emerging porous materials, metal-organic frameworks (MOFs) have been studied for applications in gas storage and separation. In this article, we introduce some computational tools for systematic characterization of the pore structure for MOFs and give some examples to discuss the usage of these tools.
As newly emerging porous materials, metal-organic frameworks (MOFs) have been studied for applications in gas storage and separation. In this article, we introduce some computational tools for systematic characterization of the pore structure for MOFs and give some examples to discuss the usage of these tools.
2013, 29(8): 1639-1644
doi: 10.3969/j.issn.1001-4861.2013.00.281
Abstract:
A new three-dimensional (3D) anionic open-framework aluminophosphate [C4H14N2][Al4P5O19OH] (AlPO-BDA) was hydrothermally synthesized by using 1,4-diaminobutane (BDA, C4H12N2) as a structure directing agent. The structure was determined by single-crystal X-ray diffraction structural analysis. AlPO-BDA was further characterized by powder X-ray diffraction (XRD), scanning electron microscope (SEM), elemental (CHN) and thermogravimetric (TG) analyses. The open-framework of AlPO-BDA contains 12-ring (12R) channels along [010] direction which are intersected with 8-ring (8R) channels running along [100] direction. In the presence of 1, 6-hexanediamine (HDA), 1, 5-pentanediamine (PDA), or 2-methylpentamethylenediamine (MPMD) and under hydrothermal condition, anionic open-frameworks with similar topology of AlPO-BDA can be obtained, which are denoted AlPO-HDA, AlPO-PDA, and AlPO-MPMD, respectively. However, their crystallographic symmetry and the shape of the channels are different. These results suggest that these amines have the same topological structure-directing effect but different structure-directing effect in the formation of these open-frameworks. The correlation between the calculated free volume and surface of the open-frameworks and the N-N distance of the diamines is observed. CCDC: 947284
A new three-dimensional (3D) anionic open-framework aluminophosphate [C4H14N2][Al4P5O19OH] (AlPO-BDA) was hydrothermally synthesized by using 1,4-diaminobutane (BDA, C4H12N2) as a structure directing agent. The structure was determined by single-crystal X-ray diffraction structural analysis. AlPO-BDA was further characterized by powder X-ray diffraction (XRD), scanning electron microscope (SEM), elemental (CHN) and thermogravimetric (TG) analyses. The open-framework of AlPO-BDA contains 12-ring (12R) channels along [010] direction which are intersected with 8-ring (8R) channels running along [100] direction. In the presence of 1, 6-hexanediamine (HDA), 1, 5-pentanediamine (PDA), or 2-methylpentamethylenediamine (MPMD) and under hydrothermal condition, anionic open-frameworks with similar topology of AlPO-BDA can be obtained, which are denoted AlPO-HDA, AlPO-PDA, and AlPO-MPMD, respectively. However, their crystallographic symmetry and the shape of the channels are different. These results suggest that these amines have the same topological structure-directing effect but different structure-directing effect in the formation of these open-frameworks. The correlation between the calculated free volume and surface of the open-frameworks and the N-N distance of the diamines is observed. CCDC: 947284
2013, 29(8): 1645-1648
doi: 10.3969/j.issn.1001-4861.2013.00.297
Abstract:
According to the famous chemist Yaghi's theory, hydroxyl group possesses the specific adsorption for CO2. In this paper, we report the synthesis of novel γ-cyclodextrin porous aromatic frameworks (CD-PAF-1) based on γ-cyclodextrin as building units with hydroxyl dehydration reaction. The material was characterized by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), CO2 and N2 gas sorption. A TG analysis showed that CD-PAF-1 is thermally stable up to 220 ℃ in air. CD-PAF-1 also has a high chemical stability and cannot be dissolved or decomposed in common solvents or concentrated hydrochloric acid. As we designed, hydroxyl groups in the skeletons adsorb a large amount of CO2. However, they do not adsorb N2 gas molecules. According to these features, CD-PAF-1 may be applied to capture and separate CO2 in industry.
According to the famous chemist Yaghi's theory, hydroxyl group possesses the specific adsorption for CO2. In this paper, we report the synthesis of novel γ-cyclodextrin porous aromatic frameworks (CD-PAF-1) based on γ-cyclodextrin as building units with hydroxyl dehydration reaction. The material was characterized by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), CO2 and N2 gas sorption. A TG analysis showed that CD-PAF-1 is thermally stable up to 220 ℃ in air. CD-PAF-1 also has a high chemical stability and cannot be dissolved or decomposed in common solvents or concentrated hydrochloric acid. As we designed, hydroxyl groups in the skeletons adsorb a large amount of CO2. However, they do not adsorb N2 gas molecules. According to these features, CD-PAF-1 may be applied to capture and separate CO2 in industry.
2013, 29(8): 1649-1656
doi: 10.3969/j.issn.1001-4861.2013.00.261
Abstract:
The interactions between 2, 17-bis(sodiumsulphonato)-5, 10, 15-tris(pentafluorophenyl)-corrole (1) and its gallium complex (1-Ga) with calf thymus DNA (ct-DNA) had been studied by UV-Vis absorption spectroscopy, fluorescence spectroscopy, circular dichroism spectroscopy and viscosity experiments. Results revealed that 1 and 1-Ga bind to ct-DNA via an outside(groove) binding mode and the DNA binding ability follows an order of 1-Ga>1. Agarose gel electrophoresis experiments showed 1 and 1-Ga display good photonuclease activity with 1-Ga having a better DNA photocleavage performance and hydroxyl radical is the reactive species involved in the photocleavage process.
The interactions between 2, 17-bis(sodiumsulphonato)-5, 10, 15-tris(pentafluorophenyl)-corrole (1) and its gallium complex (1-Ga) with calf thymus DNA (ct-DNA) had been studied by UV-Vis absorption spectroscopy, fluorescence spectroscopy, circular dichroism spectroscopy and viscosity experiments. Results revealed that 1 and 1-Ga bind to ct-DNA via an outside(groove) binding mode and the DNA binding ability follows an order of 1-Ga>1. Agarose gel electrophoresis experiments showed 1 and 1-Ga display good photonuclease activity with 1-Ga having a better DNA photocleavage performance and hydroxyl radical is the reactive species involved in the photocleavage process.
2013, 29(8): 1657-1662
doi: 10.3969/j.issn.1001-4861.2013.00.284
Abstract:
N-doped TiO2 powers have been prepared using tetrabutyl titanate and urea. The properties of phase/size/absorbance were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-Vis absorption spectroscopy. The results indicate that particle size of N-doped TiO2 decreased and the absorption effect increased greatly. In order to prove the experimental results, we studied the doping mechanism using DFT. The band gap has been decreased effectively because of doping. Compared with substitutional N-doped TiO2, interstitial N-doped TiO2 is more beneficial to the light absorption.
N-doped TiO2 powers have been prepared using tetrabutyl titanate and urea. The properties of phase/size/absorbance were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-Vis absorption spectroscopy. The results indicate that particle size of N-doped TiO2 decreased and the absorption effect increased greatly. In order to prove the experimental results, we studied the doping mechanism using DFT. The band gap has been decreased effectively because of doping. Compared with substitutional N-doped TiO2, interstitial N-doped TiO2 is more beneficial to the light absorption.
2013, 29(8): 1663-1667
doi: 10.3969/j.issn.1001-4861.2013.00.293
Abstract:
Herein, the organic-inorganic hybrid phosphors has been designed and assembled by the intercalation of salicylic acid (HSA), as sensitizer, into the layered rare-earth hydroxides (LRHs) with the compositions of (Gd0.5Tb0.5-xEux)2(OH)5NO3·nH2O, through ion-exchange reaction under hydrothermal condition. More interestingly, the luminescence color of the SA--LRHs:xEu can be easily tuned from green to red due to the energy transfer from the Tb3+ to Eu3+ ions by changing the doping concentration of activator ions. In addition, the transparent and color-tunable luminescent film devices can be fabricated facilely with the use of SA--LRHs:xEu hybrids and polymethyl methacrylate (PMMA).
Herein, the organic-inorganic hybrid phosphors has been designed and assembled by the intercalation of salicylic acid (HSA), as sensitizer, into the layered rare-earth hydroxides (LRHs) with the compositions of (Gd0.5Tb0.5-xEux)2(OH)5NO3·nH2O, through ion-exchange reaction under hydrothermal condition. More interestingly, the luminescence color of the SA--LRHs:xEu can be easily tuned from green to red due to the energy transfer from the Tb3+ to Eu3+ ions by changing the doping concentration of activator ions. In addition, the transparent and color-tunable luminescent film devices can be fabricated facilely with the use of SA--LRHs:xEu hybrids and polymethyl methacrylate (PMMA).
2013, 29(8): 1668-1674
doi: 10.3969/j.issn.1001-4861.2013.00.256
Abstract:
A new 3D coordination polymer [Ni2(bte)5(γ-Mo8O26)]·5H2O(1) (bte=1, 2-bis(1, 2, 4-triazol-1-y1)ethane), has been synthesized under hydrothermal conditions and characterized by elemental analyses, thermogravimetric analysis (TGA) and single crystal X-ray diffraction. The crystal structure analysis indicates that in compound 1, the bte ligands link the Ni(Ⅱ) ions and construct a unique 2D metal-organic layer. The γ-[Mo8O26]4- anions show two different functions: (i) it acts as a structural directing agent embeding in the 2D metal-organic layer; (ii) it is functionalized by the bte ligands through Mo-N bonds for bridging this 2D metal-organic layer and finally inducing a 3D framework of 1 with the Schläfli symbol of {32·44·54·62·73}{32·46·56·6}2. In addition, the electrochemical and fluorescence properties of the title compound have been studied. CCDC: 881771.
A new 3D coordination polymer [Ni2(bte)5(γ-Mo8O26)]·5H2O(1) (bte=1, 2-bis(1, 2, 4-triazol-1-y1)ethane), has been synthesized under hydrothermal conditions and characterized by elemental analyses, thermogravimetric analysis (TGA) and single crystal X-ray diffraction. The crystal structure analysis indicates that in compound 1, the bte ligands link the Ni(Ⅱ) ions and construct a unique 2D metal-organic layer. The γ-[Mo8O26]4- anions show two different functions: (i) it acts as a structural directing agent embeding in the 2D metal-organic layer; (ii) it is functionalized by the bte ligands through Mo-N bonds for bridging this 2D metal-organic layer and finally inducing a 3D framework of 1 with the Schläfli symbol of {32·44·54·62·73}{32·46·56·6}2. In addition, the electrochemical and fluorescence properties of the title compound have been studied. CCDC: 881771.
2013, 29(8): 1675-1679
doi: 10.3969/j.issn.1001-4861.2013.00.312
Abstract:
Graphene-CdS nanocomposite is a very promising optoelectronic material, and its optoelectronic properties are critically dependent on the distribution of CdS nanoparticles (NPs) on single sheets of graphene. Herein, we developed a facile one-step one-pot microwaving method to produce graphene-CdS nanocomposite, only involving of a few minutes' microwaving of the mixture of graphene oxide (GO), dihydrate acid cadmium and thioacetamide in 90% ethylene glycol solvent. The whole process is simple, efficient and environmental friendly. This method is an improvement of our previous dimethyl sulfoxide method (Adv. Mater., 2010,22:103-106). Using stoichiometric thioacetamide as the sulfur source, the current method avoided the byproduct of hazard hydrogen sulfide gas of the previous method. While using GO as the initial material, which was simultaneously reduced during the microwaving process as CdS NPs grew on graphene sheet, guaranteed that graphene was mainly single-layer sheets in the final nanocomposite. TEM and XRD results show that well-crystallized CdS NPs of a blende structure with an average diameter of about 5.7 nm nicely distributed on single graphene sheets with almost no aggregation.
Graphene-CdS nanocomposite is a very promising optoelectronic material, and its optoelectronic properties are critically dependent on the distribution of CdS nanoparticles (NPs) on single sheets of graphene. Herein, we developed a facile one-step one-pot microwaving method to produce graphene-CdS nanocomposite, only involving of a few minutes' microwaving of the mixture of graphene oxide (GO), dihydrate acid cadmium and thioacetamide in 90% ethylene glycol solvent. The whole process is simple, efficient and environmental friendly. This method is an improvement of our previous dimethyl sulfoxide method (Adv. Mater., 2010,22:103-106). Using stoichiometric thioacetamide as the sulfur source, the current method avoided the byproduct of hazard hydrogen sulfide gas of the previous method. While using GO as the initial material, which was simultaneously reduced during the microwaving process as CdS NPs grew on graphene sheet, guaranteed that graphene was mainly single-layer sheets in the final nanocomposite. TEM and XRD results show that well-crystallized CdS NPs of a blende structure with an average diameter of about 5.7 nm nicely distributed on single graphene sheets with almost no aggregation.
2013, 29(8): 1680-1686
doi: 10.3969/j.issn.1001-4861.2013.00.314
Abstract:
Complex [La2(NO3)6(H2L)2]·CH2Cl2 (1) has been synthesized by reactions of N,N'-bis(2-hydroxy-3-meth-oxybenzylidene)-1,3-propanediamine (H2L) with La(NO3)3·6H2O. X-ray diffraction analysis reveals that complex 1 exhibits a dinuclear structure bridged by two H2L ligands. Complex [La2(NO3)2(H2L)4](PF6)4·4H2O·2CH2Cl2 (2) can be transformed from 1 with the introduction of (NH4)(PF6), which exhibits a dinuclear structure linked by two NO3- anions. The PF6- counterion plays an essential role on steering the structural transformation. CCDC: 937367, 1; 937368, 2.
Complex [La2(NO3)6(H2L)2]·CH2Cl2 (1) has been synthesized by reactions of N,N'-bis(2-hydroxy-3-meth-oxybenzylidene)-1,3-propanediamine (H2L) with La(NO3)3·6H2O. X-ray diffraction analysis reveals that complex 1 exhibits a dinuclear structure bridged by two H2L ligands. Complex [La2(NO3)2(H2L)4](PF6)4·4H2O·2CH2Cl2 (2) can be transformed from 1 with the introduction of (NH4)(PF6), which exhibits a dinuclear structure linked by two NO3- anions. The PF6- counterion plays an essential role on steering the structural transformation. CCDC: 937367, 1; 937368, 2.
2013, 29(8): 1687-1695
doi: 10.3969/j.issn.1001-4861.2013.00.294
Abstract:
Three mononuclear cadmium(Ⅱ), manganese(Ⅱ) and nickel(Ⅱ) complexes having 2-thiophenimidazo[4,5-f][1,10]phenanthroline (TIP) and 2-(5-bromothiophen)imidazo[4,5-f][1,10]phenanthroline (5-Br-TIP) ligands formulated as [cis-Cd(NO3)(TIP)2] (1), [cis-MnCl2(5-Br-TIP)2] (2) and [cis-NiCl2(TIP)2] (3), have been synthesized and structurally compared. They are characterized by elemental analysis, FT-IR, UV-Vis spectra, luminescence spectra and X-ray single-crystal structural analysis. All of them are 1:2 mononuclear complexes with the same cis configuration, among which complex 1 is eight-coordinated and the others are six-coordinated. Ligands TIP and 5-Br-TIP in complex 1~3 are essentially planar with the dihedral angles between imidazole and thiophene rings in the range of 3.9(1)°~9.2(1)°. CCDC: 922633, 1; 922634, 2; 922635, 3.
Three mononuclear cadmium(Ⅱ), manganese(Ⅱ) and nickel(Ⅱ) complexes having 2-thiophenimidazo[4,5-f][1,10]phenanthroline (TIP) and 2-(5-bromothiophen)imidazo[4,5-f][1,10]phenanthroline (5-Br-TIP) ligands formulated as [cis-Cd(NO3)(TIP)2] (1), [cis-MnCl2(5-Br-TIP)2] (2) and [cis-NiCl2(TIP)2] (3), have been synthesized and structurally compared. They are characterized by elemental analysis, FT-IR, UV-Vis spectra, luminescence spectra and X-ray single-crystal structural analysis. All of them are 1:2 mononuclear complexes with the same cis configuration, among which complex 1 is eight-coordinated and the others are six-coordinated. Ligands TIP and 5-Br-TIP in complex 1~3 are essentially planar with the dihedral angles between imidazole and thiophene rings in the range of 3.9(1)°~9.2(1)°. CCDC: 922633, 1; 922634, 2; 922635, 3.
2013, 29(8): 1696-1702
doi: 10.3969/j.issn.1001-4861.2013.00.299
Abstract:
One novel organic-inorganic hybrid supramolecular compound, ([(4-IA-NH3)·(18-crown-6)]2·(Cu2Cl6) (1), has been synthesized and characterized by IR spectroscopy, XRPD, thermogravimetric analysis and single crystal X-ray diffraction (where 4-IA-NH3+=4-iodobenzenaminium; 18-crown-6=1,4,7,10,13,16-hexaoxacyclooctadecane). The organic [(4-IA-NH3)·(18-crown-6)]+ cation assemblies and inorganic Cu2Cl62- anions arrange alternately to build the macrocycle-based rotator-stator supramolecular inclusion. Temperature-dependent dielectric constants of compound 1 show no distinct dielectric anomalies, suggesting no phase transition within the measured temperature range (130~450 K). A high dielectric constant above 350 K at a low frequency of 500 Hz suggests that the increase in the disorder molecular thermal motion and/or H-bonding dipole interactions. CCDC: 919514.
One novel organic-inorganic hybrid supramolecular compound, ([(4-IA-NH3)·(18-crown-6)]2·(Cu2Cl6) (1), has been synthesized and characterized by IR spectroscopy, XRPD, thermogravimetric analysis and single crystal X-ray diffraction (where 4-IA-NH3+=4-iodobenzenaminium; 18-crown-6=1,4,7,10,13,16-hexaoxacyclooctadecane). The organic [(4-IA-NH3)·(18-crown-6)]+ cation assemblies and inorganic Cu2Cl62- anions arrange alternately to build the macrocycle-based rotator-stator supramolecular inclusion. Temperature-dependent dielectric constants of compound 1 show no distinct dielectric anomalies, suggesting no phase transition within the measured temperature range (130~450 K). A high dielectric constant above 350 K at a low frequency of 500 Hz suggests that the increase in the disorder molecular thermal motion and/or H-bonding dipole interactions. CCDC: 919514.
2013, 29(8): 1703-1709
doi: 10.3969/j.issn.1001-4861.2013.00.309
Abstract:
A platinum sensitizer-cobalt dinuclear complex, [Pt(tBu3tpy)([C≡C-C6H4N])-Co(dmgH)2PyCl, 5] (tBu3tpy=4,4',4"-tri(tert-butyl)-2,2':6',2"-terpyridine, C6H4N=4-pyridyl, dmgH=dimethylglyoxime, Py=pyridine), has been synthesized and characterized. The complex 5 shows absorption spectra in the visible region, which are assigned to mainly metal-to-ligand charge transfer (MLCT) character from the platinum sensitizer part. The cobalt moiety in complex 5 could quench the luminescence of the platinum part, indicating a possible process of intramolecular electron transfer. This dinuclear complex has been used for light-driven catalytic hydrogen production from water in the presence of triethanolamine (TEOA). The hydrogen production is affected by many factors, such as pH value and solvent. And the results show that this molecular catalyst could be decomposed to release the platinum based photosensitizer, as confirmed by absorption spectra and mass spectrometry.
A platinum sensitizer-cobalt dinuclear complex, [Pt(tBu3tpy)([C≡C-C6H4N])-Co(dmgH)2PyCl, 5] (tBu3tpy=4,4',4"-tri(tert-butyl)-2,2':6',2"-terpyridine, C6H4N=4-pyridyl, dmgH=dimethylglyoxime, Py=pyridine), has been synthesized and characterized. The complex 5 shows absorption spectra in the visible region, which are assigned to mainly metal-to-ligand charge transfer (MLCT) character from the platinum sensitizer part. The cobalt moiety in complex 5 could quench the luminescence of the platinum part, indicating a possible process of intramolecular electron transfer. This dinuclear complex has been used for light-driven catalytic hydrogen production from water in the presence of triethanolamine (TEOA). The hydrogen production is affected by many factors, such as pH value and solvent. And the results show that this molecular catalyst could be decomposed to release the platinum based photosensitizer, as confirmed by absorption spectra and mass spectrometry.
2013, 29(8): 1710-1716
doi: 10.3969/j.issn.1001-4861.2013.00.307
Abstract:
A new Co(Ⅱ) coordination polymer {[Co(dpa)(H2O)4]·(dpdo)·(H2O)}n (1) (H2dpa=2,2'-biphenyldicarboxy-late, dpdo=4,4'-bipyridine-N,N'-dioxide) has been synthesized and characterized by IR spectroscopy, UV-Vis spectroscopy, elemental analysis, XRPD, TGA and X-ray single-crystal structure analysis. The Co(Ⅱ) atom has a distorted octahedral coordination environment with a set of oxygen donors from two dpa2- ligands and four coordinated water molecules. Each dpa2- ligand is bounded to two cobalt centers and each cobalt atom is coordinated by two dpa2- ligands thereby generating a 21 helical chain. The helical chains further interact with each other and form a 2D network through multiform O-H…O hydrogen bonds with the help of the solvent water. In the solid state the adjacent layers are separated by dpdo units to form a 3D framework. Upon the excitation at 275 nm, the polymer 1 shows one emission peak at 430 nm in the solid state. CCDC: 922034.
A new Co(Ⅱ) coordination polymer {[Co(dpa)(H2O)4]·(dpdo)·(H2O)}n (1) (H2dpa=2,2'-biphenyldicarboxy-late, dpdo=4,4'-bipyridine-N,N'-dioxide) has been synthesized and characterized by IR spectroscopy, UV-Vis spectroscopy, elemental analysis, XRPD, TGA and X-ray single-crystal structure analysis. The Co(Ⅱ) atom has a distorted octahedral coordination environment with a set of oxygen donors from two dpa2- ligands and four coordinated water molecules. Each dpa2- ligand is bounded to two cobalt centers and each cobalt atom is coordinated by two dpa2- ligands thereby generating a 21 helical chain. The helical chains further interact with each other and form a 2D network through multiform O-H…O hydrogen bonds with the help of the solvent water. In the solid state the adjacent layers are separated by dpdo units to form a 3D framework. Upon the excitation at 275 nm, the polymer 1 shows one emission peak at 430 nm in the solid state. CCDC: 922034.
2013, 29(8): 1717-1723
doi: 10.3969/j.issn.1001-4861.2013.00.317
Abstract:
New adsorption gel (OW-NH2) was prepared by chemically immobilizing functional group of amine orange waste. For the system of Mo(Ⅵ) coexisted with Re(Ⅶ), Pb(Ⅱ), Fe(Ⅲ), Zn(Ⅱ), Mn(Ⅶ) Ca(Ⅱ) and Cu(Ⅱ), the gel exhibits selectivity only for Mo(Ⅵ). The maximum adsorption capacity for Mo(Ⅵ) is 1.71 mmol·g-1, and the adsorption behavior obeys the Langmuir model. The adsorption mechanism of molybdenum anion could be explained as the anion exchange reactions. In addition, the excellent adsorption characteristics for Mo(Ⅵ) are confirmed by separation of Mo(Ⅵ) from Mo-Re containing industrial effluent.
New adsorption gel (OW-NH2) was prepared by chemically immobilizing functional group of amine orange waste. For the system of Mo(Ⅵ) coexisted with Re(Ⅶ), Pb(Ⅱ), Fe(Ⅲ), Zn(Ⅱ), Mn(Ⅶ) Ca(Ⅱ) and Cu(Ⅱ), the gel exhibits selectivity only for Mo(Ⅵ). The maximum adsorption capacity for Mo(Ⅵ) is 1.71 mmol·g-1, and the adsorption behavior obeys the Langmuir model. The adsorption mechanism of molybdenum anion could be explained as the anion exchange reactions. In addition, the excellent adsorption characteristics for Mo(Ⅵ) are confirmed by separation of Mo(Ⅵ) from Mo-Re containing industrial effluent.
2013, 29(8): 1724-1732
doi: 10.3969/j.issn.1001-4861.2013.00.289
Abstract:
A new dinuclear cobalt complex with mixed ligands, (C4H9)4N2(Co(mnt)2)2(bpy) (1) (C56H78Co2N14S8)((C4H9)4N=tetrabutylammonium, mnt=maleonitriledithiolate and bpy=2,2'-bipyrimidyl) has been synthesized and characterized by single-crystal X-ray structure determination. Complex 1 is of monoclinic system, space group P21/c, with a=2.368 2(2) nm, b=1.582 11(13) nm, c=1.873 85(16) nm, β=105.834(2)°. Each cobalt center was coordinated with two mnt groups and bridged by 2,2'-bipyrimidyl ligand in complex 1. It was then investigated by thermogravimetric analysis (TGA), UV, IR, X-ray photoelectron spectroscopy (XPS), and cyclic voltammograms (CVs). Magnetic susceptibilities measurements of complex 1 revealed weak antiferromagnetic exchange interactions between the adjacent Co(Ⅱ) ions. CCDC: 919857.
A new dinuclear cobalt complex with mixed ligands, (C4H9)4N2(Co(mnt)2)2(bpy) (1) (C56H78Co2N14S8)((C4H9)4N=tetrabutylammonium, mnt=maleonitriledithiolate and bpy=2,2'-bipyrimidyl) has been synthesized and characterized by single-crystal X-ray structure determination. Complex 1 is of monoclinic system, space group P21/c, with a=2.368 2(2) nm, b=1.582 11(13) nm, c=1.873 85(16) nm, β=105.834(2)°. Each cobalt center was coordinated with two mnt groups and bridged by 2,2'-bipyrimidyl ligand in complex 1. It was then investigated by thermogravimetric analysis (TGA), UV, IR, X-ray photoelectron spectroscopy (XPS), and cyclic voltammograms (CVs). Magnetic susceptibilities measurements of complex 1 revealed weak antiferromagnetic exchange interactions between the adjacent Co(Ⅱ) ions. CCDC: 919857.
2013, 29(8): 1733-1737
doi: 10.3969/j.issn.1001-4861.2013.00.313
Abstract:
The synthesis, crystal structure and magnetic properties of a new six-coordinated high-spin (HS) Mn(Ⅲ) Schiff base complex, [MnⅢ(3-MeO-sal-N(1,5,9,13))]ClO4H2O (1) are described. The ligand 3-MeO-sal-N(1,5,9,13) is a hexadentate Schiff base obtained from N,N'-bis(3-aminopropyl)-1,3-propanediamine and 2-hydroxy-3-methoxy benzaldehyde. Compound 1 crystallizes in monoclinic space group P21/c, with a=0.806 43(2) nm, b=2.049 31(4) nm, c=1.709 74(3) nm, β=101.302 0(10)°, V=2.770 77(10) nm3, Z=4, R=0.055 4 and wR=0.136 0 (I >2σ(I)). Single crystal X-ray diffraction analysis reveals that the Mn site has a tetragonally compressed octahedral geometry. The magnetic susceptibilities measurements indicate the HS ground state in the temperature range 1.8~300 K. The magnetic data are well fitted by Zero-Field-Splitting (ZFS) Hamiltonian, showing a D >0 parameter, in line with the compressed octahedron pattern. CCDC: 926103.
The synthesis, crystal structure and magnetic properties of a new six-coordinated high-spin (HS) Mn(Ⅲ) Schiff base complex, [MnⅢ(3-MeO-sal-N(1,5,9,13))]ClO4H2O (1) are described. The ligand 3-MeO-sal-N(1,5,9,13) is a hexadentate Schiff base obtained from N,N'-bis(3-aminopropyl)-1,3-propanediamine and 2-hydroxy-3-methoxy benzaldehyde. Compound 1 crystallizes in monoclinic space group P21/c, with a=0.806 43(2) nm, b=2.049 31(4) nm, c=1.709 74(3) nm, β=101.302 0(10)°, V=2.770 77(10) nm3, Z=4, R=0.055 4 and wR=0.136 0 (I >2σ(I)). Single crystal X-ray diffraction analysis reveals that the Mn site has a tetragonally compressed octahedral geometry. The magnetic susceptibilities measurements indicate the HS ground state in the temperature range 1.8~300 K. The magnetic data are well fitted by Zero-Field-Splitting (ZFS) Hamiltonian, showing a D >0 parameter, in line with the compressed octahedron pattern. CCDC: 926103.
2013, 29(8): 1738-1744
doi: 10.3969/j.issn.1001-4861.2013.00.273
Abstract:
This work aims to develop a jet co-precipitation process in a tee mixer reactor to synthesize copper pyrithione (CPT). The morphology and size of CPT in dispersion were investigated by using SEM and small angle light scattering (SALS). The rod-like primary particles were obtained via the jet co-precipitation process. These primary particles tend to form aggregates with a fractal dimension of 2.1 in aqueous solutions. The effect of the reaction temperature and stoichiometry ratio of sodium pyrithione (SPT)/CuSO4 on the size of particles aggregates was studied. Decreasing the reaction temperature can reduce the size of the aggregates in terms of average radius of gyration, <Rg>. The excess of SPT is also beneficial to reducing <Rg>. When SPT excess reaches a certain value, e.g. ~25%, <Rg> decreases slightly with a further SPT excess.
This work aims to develop a jet co-precipitation process in a tee mixer reactor to synthesize copper pyrithione (CPT). The morphology and size of CPT in dispersion were investigated by using SEM and small angle light scattering (SALS). The rod-like primary particles were obtained via the jet co-precipitation process. These primary particles tend to form aggregates with a fractal dimension of 2.1 in aqueous solutions. The effect of the reaction temperature and stoichiometry ratio of sodium pyrithione (SPT)/CuSO4 on the size of particles aggregates was studied. Decreasing the reaction temperature can reduce the size of the aggregates in terms of average radius of gyration, <Rg>. The excess of SPT is also beneficial to reducing <Rg>. When SPT excess reaches a certain value, e.g. ~25%, <Rg> decreases slightly with a further SPT excess.
2013, 29(8): 1745-1752
doi: 10.3969/j.issn.1001-4861.2013.00.295
Abstract:
The chiral ligand 2,5-bis(4,5-pinene-2-pyridyl) pyrazine (L) and its rhenium(Ⅰ) complex [Re(CO)3Cl(L)]·DMF were synthesized. X-ray crystallographic analysis show that L crystallizes in monoclinic P21 space group while [Re(CO)3Cl(L)]·DMF crystallizes in orthorhombic P212121 space group. The Re(Ⅰ) atom is six-coordinated by two nitrogen atoms (N1, N2) from the chiral ligand, three carbon atoms (C1, C2 and C3) from CO, and one chlorine atom (Cl1). Both ligand and [Re(CO)3Cl(L)]·DMF show optical activity as manifested by the CD and VCD spectra. Upon excitation, the ligand and Re(Ⅰ) complex emit at 420 and 650 nm, respectively. Both the ligand and Re(Ⅰ) complex show second-order non-linear optic (NLO) properties, and the second harmonic generation (SHG) responses are ~0.4 and ~0.3 times that of urea, respectively. CCDC: 921976, complex; 921977, ligand.
The chiral ligand 2,5-bis(4,5-pinene-2-pyridyl) pyrazine (L) and its rhenium(Ⅰ) complex [Re(CO)3Cl(L)]·DMF were synthesized. X-ray crystallographic analysis show that L crystallizes in monoclinic P21 space group while [Re(CO)3Cl(L)]·DMF crystallizes in orthorhombic P212121 space group. The Re(Ⅰ) atom is six-coordinated by two nitrogen atoms (N1, N2) from the chiral ligand, three carbon atoms (C1, C2 and C3) from CO, and one chlorine atom (Cl1). Both ligand and [Re(CO)3Cl(L)]·DMF show optical activity as manifested by the CD and VCD spectra. Upon excitation, the ligand and Re(Ⅰ) complex emit at 420 and 650 nm, respectively. Both the ligand and Re(Ⅰ) complex show second-order non-linear optic (NLO) properties, and the second harmonic generation (SHG) responses are ~0.4 and ~0.3 times that of urea, respectively. CCDC: 921976, complex; 921977, ligand.
2013, 29(8): 1753-1758
doi: 10.3969/j.issn.1001-4861.2013.00.187
Abstract:
A plasmonic AgCl:Ag nanoparticles supported on SiO2 has been prepared using polyol precipitation method followed by photoreduction. On the basis of characterization, it was found that SiO2@AgCl:Ag nanoparticles exhibit shaped cube-tetrapods. The as-prepared catalysts show strong absorption in visible region due to surface plasmon resonance of Ag nanograins, which are beneficial for photocatalytic degradation of toxic persistent organic pollutants, e.g., rhodamine B, under visible light irradiation. For example, only two minutes was taken to decompose rhodamine B molecules with the assistance of SiO2@AgCl:Ag. Furthermore, radical scavenger effects demonstrate that O2·- and ·OH radicals are main active oxidation species in photocatalytic reaction. These features mean SiO2@AgCl:Ag can find applications in the fields of water disinfection and environmental remediation.
A plasmonic AgCl:Ag nanoparticles supported on SiO2 has been prepared using polyol precipitation method followed by photoreduction. On the basis of characterization, it was found that SiO2@AgCl:Ag nanoparticles exhibit shaped cube-tetrapods. The as-prepared catalysts show strong absorption in visible region due to surface plasmon resonance of Ag nanograins, which are beneficial for photocatalytic degradation of toxic persistent organic pollutants, e.g., rhodamine B, under visible light irradiation. For example, only two minutes was taken to decompose rhodamine B molecules with the assistance of SiO2@AgCl:Ag. Furthermore, radical scavenger effects demonstrate that O2·- and ·OH radicals are main active oxidation species in photocatalytic reaction. These features mean SiO2@AgCl:Ag can find applications in the fields of water disinfection and environmental remediation.
2013, 29(8): 1759-1768
doi: 10.3969/j.issn.1001-4861.2013.00.308
Abstract:
Lithium storage performances of TiO2 nanotube arrays on copper substrate as electrodes in lithium-ion batteries were investigated. Amorphous TiO2 nanotube arrays were prepared via a sacrificial template method from outward coating of TiO2 and inward etching of Cu(OH)2 nanorod array templates on copper substrate. Anatase TiO2 nanotube arrays were obtained by post-heating the sample at 500 ℃ for 4 h. The samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The electrochemical performances of amorphous and anatase TiO2 nanotube arrays were investigated by galvanostatic charge-discharge measurements, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The results indicate that compared with amorphous TiO2 nanotube arrays, anatase TiO2 nanotube arrays exhibit a superior rate capability and cycling performance due to their lower amounts of adsorbed water, higher crystallization, lower charge-transfer resistance, higher lithium-ion diffusion coefficient, and more stable one-dimensional tubular structure. They show an initial specific discharge capacity of 353 mAh·g-1 and 243 mAh·g-1 even after 40 cycles at 0.2C. At a high rate of 8C, their discharge capacity can reach 90 mAh·g-1.
Lithium storage performances of TiO2 nanotube arrays on copper substrate as electrodes in lithium-ion batteries were investigated. Amorphous TiO2 nanotube arrays were prepared via a sacrificial template method from outward coating of TiO2 and inward etching of Cu(OH)2 nanorod array templates on copper substrate. Anatase TiO2 nanotube arrays were obtained by post-heating the sample at 500 ℃ for 4 h. The samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The electrochemical performances of amorphous and anatase TiO2 nanotube arrays were investigated by galvanostatic charge-discharge measurements, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The results indicate that compared with amorphous TiO2 nanotube arrays, anatase TiO2 nanotube arrays exhibit a superior rate capability and cycling performance due to their lower amounts of adsorbed water, higher crystallization, lower charge-transfer resistance, higher lithium-ion diffusion coefficient, and more stable one-dimensional tubular structure. They show an initial specific discharge capacity of 353 mAh·g-1 and 243 mAh·g-1 even after 40 cycles at 0.2C. At a high rate of 8C, their discharge capacity can reach 90 mAh·g-1.
2013, 29(8): 1769-1776
doi: 10.3969/j.issn.1001-4861.2013.00.310
Abstract:
A 2-substituted-8-hydroxyquinoline ligand (E)-2-[2-(4-Methoxyphenyl)ethenyl]-8-hydroxyquinoline (HL) was synthesized in two steps from the readily available and cheap 8-hydroxyquinaldine and characterized by LC-MS, NMR spectroscopy, elemental analysis and X-ray crystallography. Using solvothermal method, a crystalline complex Zn2L4(1) was obtained by reacting Zn(Ⅱ) ions with ligand HL. X-ray structural analysis shows that 1 exhibits a binuclear core, which is bridged by two 8-hydroxyquinoline rings. The supramolecular structure of 1 features a 3D supramolecular structure constructed by π…π aromatic stacking interactions, nonclassical C-H…O hydrogen bonds and C-H…π interactions. The aggregation behavior of zinc salts and HL in solutions was investigated with UV-vis and PL spectra. Additionally, we also studied the photophysical properties of compound 1 by PL. The results showed that complex 1 exhibits a red shift compared with free ligand HL and emits yellow luminescence. CCDC:923979,HL;923980,1.
A 2-substituted-8-hydroxyquinoline ligand (E)-2-[2-(4-Methoxyphenyl)ethenyl]-8-hydroxyquinoline (HL) was synthesized in two steps from the readily available and cheap 8-hydroxyquinaldine and characterized by LC-MS, NMR spectroscopy, elemental analysis and X-ray crystallography. Using solvothermal method, a crystalline complex Zn2L4(1) was obtained by reacting Zn(Ⅱ) ions with ligand HL. X-ray structural analysis shows that 1 exhibits a binuclear core, which is bridged by two 8-hydroxyquinoline rings. The supramolecular structure of 1 features a 3D supramolecular structure constructed by π…π aromatic stacking interactions, nonclassical C-H…O hydrogen bonds and C-H…π interactions. The aggregation behavior of zinc salts and HL in solutions was investigated with UV-vis and PL spectra. Additionally, we also studied the photophysical properties of compound 1 by PL. The results showed that complex 1 exhibits a red shift compared with free ligand HL and emits yellow luminescence. CCDC:923979,HL;923980,1.
