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Table of Content

    10 March 2011, Volume 32 Issue 3
    Preface
    庆祝徐如人教授和庞文琴教授执教六十年暨八十华诞
    2011, 32(3):  1-8. 
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    Contents
    Cover and Content of Chemical Journal of Chinese Universities Vol.32 No.3(2011)
    2011, 32(3):  10. 
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    Reviews
    Bioinspired Hierarchical Micro/Nanostructure Materials
    WANG Nü, ZHAO Yong*, JIANG Lei*
    2011, 32(3):  421-428. 
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    This review gives a brief introduction to some living organisms with special structure and properties. The unique functions of organisms are usually related with their hierarchical structure. The development about synthesis and preparation of multilevel zero dimension and one dimension micro/nanostructured materials in recent years are presented. The zero dimension and one dimension micro/nanostructure materials are simply classified. Lastly, we give an outlook about the future development of micro/nanostructured materials.
    Articles
    Self-assembly of 3D Nanocrystal-superlattices
    MENG Ling-Rong, PENG Qing*, ZHOU He-Ping, LI Ya-Dong*
    2011, 32(3):  429-436. 
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    The assembly of nanocrystals into various ordered structures is key to their future applications. In this article, we describe the recent progresses in the assembly routes and mechanisms of the three-dimensional superlattices of nanocrystals. This review focuses on the techniques of nanocrystal assembly based on solvent evaporation of colloidal solutions, non-solvent diffusion, micelle-induced aggregation, hydrogen bonding linkage, electrostatic interactions, DNA base-pairing, external field-assistance, and oil-water interface templating. The existing challenges and future development of nanocrystals assembly are also discussed.
    Reviews
    Oxidative DNA Cleavage Mediated by Copper Complexes
    2011, 32(3):  437-450. 
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    In this review, the mechanism of the oxidative DNA cleavage promoted by copper complexes was discussed at first according to the DNA binding ability/mode, the reactive oxygen species (ROS) formation and the subsequent ROS-induced DNA damage. Combined with our works in this field, the complex nuclear number,metal centers,steric effect,charge,redox potential were investigated to clarify the the structral effects of copper complexes on their DNA cleaving behavior.In addition, the photo-induced DNA cleavage by copper complexes has also been surveied briefly. Finally, the different strategies for the specific DNA cleavage mediated by copper complexes were reviewed. All these should be helpful for the future design of copper-containing artificial nuclease of higher efficiency and specificity.
    Recent Advance of Hydrothermal Growth of ZnO and TiO2 Nano-tree Arrays
    ZHAO Feng-Hua YANG Xian-Feng GAO Qiong, WU Ming-Mei*
    2011, 32(3):  451-461. 
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    Branched tree-like nanoarrays are emerging as an exciting addition to the family of oriented semiconducting nanomaterials. Besides high temperature solid state and vapor-liquid-solid (VLS), a site-specific sequential nucleation and growth route to the systematic building of hierarchical, complex, and oriented ZnO micro/nanostructures in solution synthesis has been developed. Herein, we present a one-step, low cost, and environment-benign route to growing large-scale arrays of zinc oxide and titanium dioxide by solution chemistry. The growth mechanism and their possible applications have been suggested.
    Template Synthesis, Activation and Energy Storage Application of Porous Carbon Materials
    WANG Huan-Lei, GAO Qiu-Ming*
    2011, 32(3):  462-470. 
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    Template synthesis of porous carbon materials has attracted much attention because of its promising applications in energy-related fields. The recent development of template synthesis was reviewed in details. And traditional activation method was also applied to further tune pore structures of carbon materials prepared by using template method. Porous carbons used as hydrogen storage materials and electrode materials for supercapacitors were commented.
    Application of Two-dimensional Double Quantum Magic Angle Spinning NMR to Solid Functional Materials
    YU Zhi-Wu, ZHENG An-Min, WANG Qiang, DENG Feng*
    2011, 32(3):  471-484. 
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    In this paper, we briefly introduce the principle of two-dimensional double quantum magic angle spinning (DQ-MAS) NMR, and review the recent applications of DQ-MAS NMR technique (including 1H, 19F, 29Si, 31P and 27Al DQ-MAS NMR) to various solid functional materials. In addition, a perspective for the future of DQ-MAS NMR is also given.
    Review
    Applications and Related Mechanisms of Molecular Sieves in Medicine
    CHEN Bing-Peng, WANG Zhuo-Peng, LIU Jing-Jing, WANG Jin-Cheng*, YU Ji-Hong*
    2011, 32(3):  485-493. 
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    Molecular sieves have been considered for medical use due to their special structural features, excellent biological activity, biological stability and biocompatibility. Molecular sieves can be used as adjuvants in anticancer therapy, anti-microbial therapy, drug carriers, hemostatic, thrombolysis and so on. This paper will discuss the progress of molecular sieves in medical applications and related mechanisms.
    Letter
    Synthesis and Characterization of a Novel Framework Zinc-substituted MFI Zeolite
    Lü Xin-Chun*, ZHAO Rong, WU Tai-Liu, SUN Yao-Jun, TANG Yi
    2011, 32(3):  494-496. 
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    A suitable synthesis condition of MFI-like zincosilicalite was obtained and was first reported in this paper. The molar ratios is as follows: 0.3Na2O /0.08Zn(Ac)2 /SiO2 /0.15TPAOH /0.12 Citric acid/100H2O, the reaction was carried out at 200oC for 7~10 days. The synthesized samples were characterized with XRD, 29Si MAS NMR and EXAFS, etc. The results show that the obtained sample is MFI-like zeolite. 29Si MAS NMR and EXAFS indicate that Zn atoms have been incorporated into the framework.
    Articles
    Synthesis and Properties on Three Coordination Polymers of 4-(Pyridin-3-yl)benzoate with Zn(Ⅱ), Cd(Ⅱ) and Mn(Ⅱ)
    ZHANG Yue-Biao,ZHOU Hao-Long,HE Chun-Ting,XUE Wei,ZHANG Jie-Peng, CHEN Xiao-Ming*
    2011, 32(3):  497-502. 
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    Synthesis of Monodisperse Silica Microspheres with Solid Core and Mesopore Shell
    WEI Hao, HAN Lu, SHI Lin, TU Bo, ZHAO Dong-Yuan*
    2011, 32(3):  503-507. 
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    Well-dispersed silica microspheres(~500 nm) with solid core and ordered mesopore shell were synthesized by amphiphilic triblock copolymers(Pluronic P123) and quaternary ammonium surfactant(CTAB) as co-templates. The mesoporous silica shell with large surface area(188 m2/g) has mesochannels parallel to the spherical surface. Furthermore, the hydrothermal treatment(~130 ℃) was introduced to enlarge the pore size(~7.3 nm) and pore volume(0.23 cm3/g).
    AgLa(WO4)2 Dendritic Nanostructures: Template-free Hydrothermal Synthesis and Their Up-conversion Luminescence Property
    SONG Shu-Yan, HAN Wei-Qiang, ZHANG Hong-Jie*
    2011, 32(3):  508-514. 
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    AgLa(WO4)2 dendritic nanostructures with clean surfaces were synthesized through a low-cost hydrothermal method without introducing any template or surfactant. The formation mechanism was observed for the growth of dendritic nanostructures based on the experimental process. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, electron diffraction, and photoluminescence spectra were used to characterize these materials. The up-conversion luminescent properties of lanthanide ions doped AgLa(WO4)2 nanostructures are of particular interest for luminescent applications.
    Synthesis, Structure and Characterization of Novel 3D Metal-organic Coordination Polymers: [M6(TDC)6(hmt)2(DMF)6(H2O)3·(H2O)](M=Cd, Mn)
    XUE Ming, LI Yang-Xue, HUANG Lin, QIU Shi-Lun*
    2011, 32(3):  515-518. 
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    Two metal-organic coordination polymers [M6(TDC)6(hmt)2(DMF)6(H2O)3 ? (H2O)] (JUC-85a and JUC-85b) (M = Cd or Mn, TDC = Thiophene-2,5-dicarboxylic, hmt = hexamethylenetetramine, DMF = N,N’-dimethylformamide and JUC = Jilin University China) have been synthesized by self-assembly of mixed ligands and corresponding transition metal salts under mild conditions, and characterized by single-crystal X-ray diffraction, elements analysis, TGA, topology analysis, PXRD and photoluminescent. X-ray crystallography reveals that JUC-85a and JUC-85b exhibit the same three-dimensional structure with a rare “loh1” type of (3,6)-connected networks. In addition, photoluminescent of JUC-85a has been characterized.
    Solvent Control over Structural Diversity of Two Manganese Complexes Based on Furan-2,5-dicaboxylate
    CHEN Wen-Xian, WU Geng-Huang, ZHUANG Gui-Lin, KONG Xiang-Jian*, LONG La-Sheng*, HUANG Rong-Bin, ZHENG Lan-Sun
    2011, 32(3):  519-526. 
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    Two complexes, namely, Mn(FDC)(H2O)3 (1) and [H2N(CH3)2]2?[Mn3(FDC)4]?2DMF?H2O (2) (H2FDC = Furan-2,5-dicarboxylate acid), have been synthesized through solvothermal reaction of manganese(II) chloride and furan-2,5-dicarboxylate acid at different solvent conditions. Single-crystal analysis reveals that an one-dimensional complex 1 was obtained when the reaction carried out in DMF/H2O, while a three-dimensional complex 2 was synthesized when the reaction carried out in DMF. Variable-temperature magnetic measurements and Quantum Monte Carlo (QMC) simulation indicate that both of complexes exhibit antiferromagnetic characteristic.
    Template-directed Synthesis of a Novel Oxalate Compound [Co(dien)2][NaCo2(C2O4)4] Using Co(Ⅲ) Complex as Template
    PAN Qin-He*, CHEN Qiang, HAN Yi-De, HU Tong-Liang*, BU Xian-He
    2011, 32(3):  527-531. 
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    By using Co(dien)2?Cl3 as the template, a novel oxalate compound [Co(dien)2][NaCo2(C2O4)4]?H2O has been synthesized under hydrothermal conditional. Its structure is determined by single-crystal X-ray diffraction analysis, elemental analyses, ICP, and X-ray powder diffraction. It crystallizes in monoclinic, space group C2/c with a = 1.3805(3) nm, b = 1.3017(3) nm, c = 1.5913(3) nm, β = 104.41(3)°, V = 2.7695(10) nm3, Z = 8. In this structure, the Co2+ cations are first linked to oxalate ligands to form a familiar chain-like building unit [Co(C2O4)2]n2n-, and then those chain-like building units are further connected by Na+ cations, which are dispersed between the chains, to construct a three dimensional oxalate open-framework of [NaCo2(C2O4)4]n3n-. The complex cations Co(dien)23+ are encapsulated inside the channels as template.
    Synthesis, Structures and Magnetism of Two New 3D Pillared-layer Cerium Mixed Carboxylate Porous Metal-organic Frameworks
    ZHU Wen-Hua, WANG Zhe-Ming*, GAO Song
    2011, 32(3):  532-537. 
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    Two new cerium mixed carboxylate porous metal-organic frameworks, [Ce2(fum)3(H2O)4?(bdc)?(H2O)2]n (1) and [Ce2(suc)2(ox)(H2O)4?(H2O)4]n (2) were synthe- sized by hydrothermal method with two kinds of carboxylic acid, respectively. They were characterized by elemental analysis, IR, TGA-DTA and single-crystal X-ray diffraction. Single-crystal X-ray diffraction indicates that complexes 1 and 2 are both 3D porous metal-organic frameworks with pillared layers. Complex 1 possesses a 3D framework structure consisting of Ce-fumarate layers pillared by fumarate ligands with intersected channels in two directions between the layers occupied by uncoordinated neutral p-benzenedicarboxylic acid and lattice water molecules. Similar to complex 1, complex 2 is a 3D structure with Ce-succinate layers pillared by oxalate ligands, which shows intersected channels in three directions between the layers filled with lattice water molecules.
    Synthesis,Structures and Catalytic Properties of Palladium(Ⅱ) Complexes Containing N-Heterocyclic Carbenes with Pyridinium Groups
    XU Wei-Feng, LI Yi-Zhi, CHEN Xue-Tai*, XUE Zi-Ling
    2011, 32(3):  538-544. 
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    Four air stable palladium(II) triiodine complexes containing N-heterocyclic carbenes with pyridinium groups [(NHC)PdI3] have been synthesized and characterized by NMR and elemental analyses. The molecular structures of two compounds have been confirmed by single-crystal X-ray diffraction. These NHC-Pd(II) complexes are active catalysts in the Suzuki-Miyaura cross-coupling reactions under atmosphere conditions with moderate conversion
    Contents
    Syntheses, Structures and Electrochemical Properties of Dinuclear Au(Ⅰ) Complexes Including Crown Ether Annelated Dithiolate Ligands
    JI Yong, HU Liang, ZHANG Rui, LI Yi-Zhi, ZUO Jing-Lin*, YOU Xiao-Zeng
    2011, 32(3):  545-551. 
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    A series of new gold(I) complexes containing crown ether annelated dithiolate ligands, [(3O-C2S4)Au2(PPh3)2] (1, 3O-C2S42?=1,4,7-trioxa-10,13-dithiacyclopentadec-11-ene-11,12-dithiolate), [(4O-C2S4)Au2(PPh3)2] (2, 4O-C2S42?=1,4,7,10-tetraoxa-13,16-dithiacyclooctadec-14-ene-14,15- dithiolate),[(3O-C6S8)Au2(PPh3)2] (3, 3O-C6S82?=2-{4,5-dithia-(3',6',9'-trioxaundecyl)-1,3-dithiol-2- ylidene}- 1,3-dithiol-4,5-dithiolate)), and [(4O-C6S8)Au2(PPh3)2] (4, 4O-C6S82?=2-{4,5-dithia-(3',6',9', 12'-tetr- aoxatetradecyl)-1,3-dithiol-2-ylidene}-1,3-dithiol-4,5-dithiolate); and the sulphur-rich dithiolate gold(I) complex [(btdt)Au2(PPh3)2] (5, btdt=benzotetrathiafulvalenedithiolate), have been prepared and characterized. The crystal structures of complexes 1-3 and 5 have been determined. Redox properties of these compounds have been investigated by cyclic voltammetry and complex 4 shows significant response for Na+ ions with a large positive shift of ca. 55 mV.
    Articles
    Solvothermal Synthesis of the Magnetite Micro-nano Particles(Fe3O4) with Different Morphologies
    GAO Qian, ZHANG Ji-Lin, HONG Guang-Yan*, NI Jia-Zuan
    2011, 32(3):  552-559. 
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    Abstract: The micro-nano magnetite particles (Fe3O4) with hydrophilic, good distribution, superparamagnetic and different shape were synthesized using a solvothermal method, where FeCl3 ? 6H2O as iron source, ethylene glycol or 1,2-propylene glycol as solvent, PEG as surfactant, and NaOH or KOH as the alkali source. Their morphologies, structures, and magnetism were characterized. The results showed that the products all were cubic phase of Fe3O4, with an adjustable particle size from 20nm to 600nm. We observed that the influences on the morphology of the alkali type and amount, reaction time, solvent and other conditions and found that the amount of alkali was the greatest impact. In this paper, the processes of formation of different morphologies Fe3O4 were discussed, and a reasonable mechanism is also briefly suggested. The resulting Fe3O4 particles with superparamagnetic property at room temperature can basically to meet the biomedical requirements.
    Amino Acid Bifunctionalized Mesoporous Silica Nanoparticles with Controllable Particle Size and Dispersibility
    WANG Yu, HAN Lu, CHE Shun-Ai*
    2011, 32(3):  560-570. 
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    Amino acid bifunctionalized mesoporous silica nanoparticles with controllable particle size and dispersibility were synthesized via the cooperative self-assembly of surfactants, co-structure-directing agents (CSDAs), and a silica source. Uniform distributions of acid and base organic groups on the mesopore surfaces were formed by interactions between the counter charged surfactant head groups and ionic parts of CSDAs. The particle size has been well tuned with different amount of co-solvent or dispersant, while the dispersibility of the bifunctionalized mesoporous nanoparticles have been achieved through changing the pH of the solution to convert the chargement between cationic ammonio-anionic carboxylate and to shift the electrostatic force between the nanoparticles.
    Hydrothermal Synthesis and Crystal Structure of a Novel Sandwich Germanotungstate: [Ni(dien)(H2O)3]2[Ni(Hdien)2]{[Ni(dien)]2·Ni4(H2O)2(GeW9O34)2}·10H2O
    LI Xin-Xiong, FANG Wei-Hui, YANG Guo-Yu*
    2011, 32(3):  571-576. 
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    A novel organic-inorganic hybrid germanotungstate [Ni(dien)(H2O)3]2[Ni(Hdien)2] -{[Ni(dien)]2Ni4(H2O)2(GeW9O34)2}?10H2O (1) (dien = diethylenetrimine) has been synthesized under hydrothermal conditions and characterized by IR spectroscopy, TGA, elemental analysis, Energy-Dispersive X-ray Spectroscopy (EDS) and single-crystal X-ray structural analysis. Crystal data for 1: Triclinic, P-1, a = 11.937(3) ?, b = 14.323(3) ?, c = 16.394(4) ?, α = 93.424(2)o, β = 96.058(3)o, γ = 109.758(4)o, V = 2609.4(10) ?3, Z = 1. X-ray crystallographic study reveals that 1 was built from [Ni(dien)]2+ decorated Weakley- type sandwich polyoxoanion linked by [Ni(Hdien)2]4+ cations to form a 1-D linear structure, which further stack 3-D network.
    Enantiomer Separation in the Hydrothermal Synthesis of Open-framework [Al4P5O19(OH)][C6H18N2] and [Ga8P8O32F5.5][C6H18N2]2[H3O+]1.5
    2011, 32(3):  577-583. 
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    A new three-dimensional open-framework aluminophosphate [Al4P5O19(OH)]?[C6H18N2](AlPO-MPMD) and a new three-dimensional open-framework gallophosphate [Ga8P8O32F5.5]?[C6H18N2]2?[H3O+]1.5 (GaPO-MPMD) were hydrothermally synthesized with 2-methyl-1,5- pentamethylene diamine (MPMD) as structure directing agent. The compounds were characterized by single crystal and powder X-ray diffraction (XRD) analyses, TGA-DTA, solid MAS NMR analysis, optical rotation analysis, experimental and simulated vibrational circular dichroism (VCD) analysis. The results confirmed that S type of enantiomer of MPMD is preferredly included in the resulting open-framework of AlPO-MPMD and GaPO-MPMD. The in situ enantiomer (chiral) separation of organic structure directing agent under hydrothermal synthesis is achieved.
    Synthesis of Urchin-like Nickel Sulfide Hollow Spheres and Their Electrochemical Performance
    LANG Lei-Ming, XU Zheng*
    2011, 32(3):  584-589. 
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    Urchin-like nickel sulfide hollow spheres composed of nanorods were synthesized via a solvthermal method using thioacetamide as sulfur source and ethylene glycol as solvent. The result of XRD indicated that there were two kinds of phase structure including α and β in the NiS products and the major product was β-NiS. The formation process of urchin-like nickel sulfide hollow spheres was investigated by monitoring the morphology variation of the product with reaction time. The results showed that urchin-like solid microspheres were formed firstly, then hollow structure were obtained via further “Ostwald ripening” process. Charge-Discharge and cyclic performance of the products were determined as an cathode of lithium-ion batteries. The first discharge-charge capacity was 900 mAhg-1, and 200mAhg-1 was still remained after 50 cycles.
    Solvent Effect for the Synthesis of Metal\|organic Framework
    ZHAO Huan-Yu, JIN Zhao, SUN Fu-Xing, ZHU Guang-Shan*
    2011, 32(3):  590-594. 
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    Two novel compounds Cd(OBA)(bipy)?DMF (1) and Cd(OBA)(bipy) (2) (OBA = 4,4’-Oxybis(benzoic acid), bipy = 4,4'-bipyridine) were synthesized under hydrothermal (solvothermal) by using DMF and water as solvent respectively. X-ray diffraction analyses reveal that both the compounds are in the monoclinic and C2/c space group Compound 1 exhibits a two-dimension framework and compound 2 is a three-dimension framework.
    Room-temperature Synthesis and Oxygen-reduction Catalytic Performance of Hollow ZnMn2O4 Nanospheres and Nanocubes
    WANG Hong-Bo, CHENG Fang-Yi, TAO Zhan-Liang, LIANG Jing*, CHEN Jun
    2011, 32(3):  595-600. 
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    This paper reports on the room-temperature synthesis of ZnMn2O4 spinels. The formation of hollow ZnMn2O4 with nanospheres and nanocubes structures is accomplished by reduction of amorphous MnO2 precursors using NaBH4 in aqueous solution containing Zn2+. The structure, morphology, composition and surface properties of the as-prepared products are characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) measurements. It is found that the size of as-prepared hollow ZnMn2O4 nanospheres and nanocubes is about 400?600 nm with wall thickness of 40nm, and that the walls of the hollow ZnMn2O4 nanostructures are densely aggregated by tiny particles with diameter of 5?6 nm. Furthermore, the activities of for oxygen reduction reaction (ORR) in alkaline media of the as-prepared hollow ZnMn2O4 nanospheres and nanocubes are also investigated. The experimental results show that the hollow ZnMn2O4 nanospheres exhibits better electrocatalysis performance with a high current density and an electron transferred number of 3.5, indicating their promising application as low-cost catalysts for ORR.
    Fabrication and Characterization of Flexible Nanostructured α-Al2O3 Fibers
    JIA Yu-Na, CHEN Dai-Rong, JIAO Xiu-Ling*
    2011, 32(3):  601-604. 
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    This paper reported the dense flexible α-Al2O3 fibers with nanostructures fabricated by sol-gel-electrospinning process. The microstructure of fibers and mechanical properties such as fracture strength and elongation were characterized. Moreover, the factors affecting the fiber properties were discussied. The α-Al2O3 fibers were composed with 30~50nm nanoflakes, and no small holes or cracks were observed in those, which exhibted superior good thermal shock resistance and higher fracture strength and elongation compared with the commercial α-Al2O3 fibers.
    Flux Synthesis of a New Uranyl Silicate K6(UO2)3Si8O22
    LEE Cheng-Shiuan, WANG Sue-Lein, LII Kwang-Hwa
    2011, 32(3):  605-608. 
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    A new uranyl silicate, K6(UO2)3Si8O22, has been synthesized by a flux method and characterized by single-crystal X-ray diffraction, solid-state NMR, and photoluminescence spectroscopy. The 3D framework structure contains UO6 tetragonal bipyramids and a new type of (Si8O22)12- unit. Crystal data: K6(UO2)3Si8O22, C2/m (No. 12), a = 1.24092(9) nm, b = 1.45678(8) nm, c = 0.81199(5) nm, β = 103.992(4)o, V = 1.4240(1) nm3, Z = 2,R1 = 0.0329 and wR2 = 0.0796.

    Articles
    Luminescence and Near-infrared Emission of Rare Earth Core-shell Nanomaterials Synthesized via Mesoporous Silica Nanoparticles as Template
    ZHANG Dao-Jun, FAN Zhi-Qiang, ZHANG Wen, WANG Xue-Min, LIU Yun-Ling, HUO Qi-Sheng*
    2011, 32(3):  609-612. 
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    We have utilized a homogeneous precipitation method to fabricate core-shell Y2O3∶Er, Eu nanomaterials with colloidal mesoporous silica nanoparticles as templates followed by heat treatment at 800 ℃, and the luminescence properties of the as-synthesized nanomaterials have been investigated in detail. The core-shell nanoparticles exhibit properties of photoluminescence and near-infrared(NIR) luminescence. And Y2O3 is a promising host matrix for downconversion and NIR luminescence due to its good chemical, thermal stability and low phonon energy. The core-shell nanoparticles may have some advantages for potential applications in drug delivery or optical imaging.
    High Temperature Synthesis of Hydrothermally Stable Micro-mesoporous Silica and Al-Doped Mesoporous Silica via Rigid Template
    NAN Hai-Ming, QI Juan-Juan, CAI Qiang*, SUN Qian-Yao*, XU Chun-Ming, LI Heng-De
    2011, 32(3):  613-617. 
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    Abstract: High temperature condition is helpful to obtain hydrothermally stable mesoporous silica. In this paper, we synthesized micro-mesoporous silica (designated as TCM-1) and Al-doped mesoporous silica (Al-TCM-1) under high temperature. The self-assembly of α-linolenic acid, which transformed to a rigid mesophase template via inter-micelle polymerization, were successfully leveraged to fabricate hydrothermally stable mesoporous silicas that retained a BET surface area of 678 m2g-1 after hydrothermal treatment in boiling water for 5 days. The 29 Si MAS NMR spectras of as calcined TCM-1 indicates Q4 silicons (Qn= Si(OSi)n(OH)4-n) are dominating, which can explain the high hydrothermal stability of the material.
    Hydrothermal Synthesis and Electrochemical Lithium Storage Performance of Flower-like NH4V4O10 Micro/Nano Structures
    REN Xiao-Ning, LIANG Jing, TAO Zhan-Liang, CHEN Jun*
    2011, 32(3):  618-623. 
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    Flower-like NH4V4O10 micro/nano structures have been prepared via a template-free hydrothermal route. The structure, morphology and composition of the as-synthesized products are characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements. The diameter and length of the “petal” of the as-synthesized flower-like NH4V4O10 are about 100 nm and several microns, respectively. Effects of hydrothermal reaction parameters are also investigated,such as the reaction temperature and dwell time on the structure and morphology of the products. The electrochemical lithium storage of the as-synthesized products is also investigated. The experimental results show that the flower-like NH4V4O10 micro/nano structures exhibit high discharge specific capacity of 307 mAh?g-1, indicating their promising application as cathode materials for lithium-ion batteries.
    Bubble Template Synthesis of MFe2O4(M=Co,Zn) Hollow Microspheres and Their Application in Li-ion Batteries
    CHEN Xiao-Mei, GUAN Xiang-Feng, LI Li-Ping, LI Guang-She*, ZHENG Jing
    2011, 32(3):  624-629. 
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    In this work, we designed and developed a bubble template-assisted method to prepare self-assembled ferrite hollow microspheres, by which homogeneously distributed CoFe2O4 (M=Co, Zn) hollow microspheres with the particle sizes of around 350 nm were obtained. The obtained hollow microspheres were assembled into cells and evaluated as negative electrodes of Li-ion battery by galvanostatic charge-discharge technique at a current density of 2 Ag-1. It was found that the first discharge and charge capacities were 1339 mAhg?1 and 936 mAhg?1 for CoFe2O4, and 1402 mAhg?1 and 992 mAhg?1 for ZnFe2O4. After 20 cycles, the charge capacities of CoFe2O4 and ZnFe2O4 remained 446 mAhg?1 and 634 mAhg?1, respectively, which are better than those previously reported. It indicates that self-assembled hollow structures are promising in improving the electrochemical performance for lithium ion battery applications.
    Synthesis and Lithium Storage Properties of Hollow Fe2O3/Graphene Nanocomposites
    ZOU Qiong, ZAI Jian-Tao, LIU Ping*, QIAN Xue-Feng*
    2011, 32(3):  630-634. 
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    Hollow Fe2O3/Graphene nanocomposites were synthesized by a hydrothermal method, and they were characterized by XRD and SEM. A plausible formation mechanism of the composite could be based on the catalytic oxidation of carboxyl et. al. groups of GO in the presence of Fe3+ ions to form GNS, and the released CO2 provided templates for the formation of hollow Fe2O3, and then hollow Fe2O3/Graphene nanocomposites were formed in-situ. The obtained nanocomposites show excellent Li storage performances. After 50 cycles, a capacity of 520 mAh g-1 (437 mAh g-1) was kept at a high current density of 200 mA g-1 (400 mA g-1).
    Luminescence Resonance Energy Transfer in Au@SiO2/LaF3∶Ce, Tb Nanostructures
    FENG Wei, ZHAO Guang-Yao, SUN Ling-Dong, YAN Chun-Hua*
    2011, 32(3):  635-640. 
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    Au@SiO2/LaF3:Ce,Tb nanostructures were synthesized simply by the coprecipitation of LaF3:Ce,Tb in the presence of Au@SiO2 nanoparticles. The as-obtained nanostructures were used as a model system to investigate the luminescence resonance energy transfer (LRET) process, where LaF3:Ce,Tb, Au, and SiO2 served as long-lifetime donor, quenching acceptor, and distance spacer, respectively. The LRET efficiency decreased with the increase of thickness of silica shell. The LRET process could still be observed even when the thickness of silica shell increased up to 42 nm. This long-distance LRET phenomenon can be attributed to the long lifetime of Tb3+ and the “point-to-surface” transfer model modified for Au nanoparticle acceptor. This result indicates that the analogous systems could be employed to study the LRET processes that take place over larger distances (> 10 nm).
    Contents
    Synthesis and Electrochemical Performance of a New Spherical LiFePO4
    ZHANG Hao-Jie, WANG Kai-Xue, CHEN Jie-Sheng*
    2011, 32(3):  641-643. 
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    Using glucose as a carbon source, we successfully obtained carbon-coated LiFePO4 spheres with controlled size and morphology. Fe5(PO4)4(OH)3?2H2O spheres with a diameter of about 5μm were first formed through hydrothermal reaction, and the surface of the Fe5(PO4)4(OH)3?2H2O spheres was uniformly coated with glucose. After carbonization at 500 oC, the Fe3(PO4)2(OH)2 spheres coated with carbon were obtained. Upon sintering with Li2CO3, the sphere morphology remains intact whereas the composition of the spheres converts to LiFePO4. The as-prepared LiFePO4 particles exhibit superior electrochemical performance.
    Articles
    Synthesis, Characterization and Fluorescent Properties of Two 3D Open-framework Rare-earth Sulfates [Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4(Ln=Gd, Eu)
    GE Gen-Wu LIU Mei-Pin NI Zhi-Gang Hong-Bin DU
    2011, 32(3):  644-649. 
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    Two novel 3-D open framework rare-earth sulfates, [Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4 (Ln = Gd, 1; Eu, 2) were solvothermally synthesized in a water-ethanol mixed solvent system by using piperazine as a template and characterized by single-crystal X-ray diffraction. The two compounds are isostructural and crystallize in the monoclinic system, space group P21/c with unit cell parameters of a = 19.691(3) ?,b = 19.249(3) ?,c = 13.186(2) ?, β = 92.33(0)o,V = 4993.5(1) ?3, Z =4 for 1, and a = 19.7233(8) ?,b = 19.2791(8) ?,c = 13.2095(5) ?,β = 92.329(1)o,V = 5018.7(3) ?3, Z = 4 for 2, Both compounds consist of 2D sheets of 8-membered rings and 16-membered rings constructed from edge- or corner-sharing SO4, GdO8 and GdO9 polyhedra. The 2D sheets stack parallel with each other and are pillared by SO4 tetrahedra to form a 3-D open framework, in which the protonated piperazine molecules are located to balance the negative charges of the framework. The solid-state fluorescence spectra of compound 2 show the characteristic luminescent behavior of Eu3+ ions.
    Based on Solvents Effect Building Novelty Polyoxometalates Supermolecule Compounds
    FU Hai, WANG Xiao-Lan, CHEN Wei-Lin, MENG Jing-Xin, LI Yang-Guang*, WANG En-Bo*
    2011, 32(3):  650-654. 
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    Abstract Two classic polyoxometalate-based compounds, (H2BBI)3[P2W18O62]?H2O (1), H2(H2BBI)2[P2W18O62]?2H2O (2), BBI=1, 1-(1, 4-butanediyl)-bis(imidazole), have been synthesized under different solvents. And the structure was characterized by elemental analysis, single crystal X-ray diffraction. Compound 1 was constructed into a novel 3D supermolecule though bridge oxygen atoms of Dawson type anions, N atoms of BBI organic ligands and free water molecules. Compound 2 was resulted in chiral space group P1 though changing the spatial framework of the organic ligands BBI with changing the solvent. We studied photocatalysis of the two compounds.
    Self-aggregation Inducing High-ratio cBN Microcrystals Growth in Hydrothermal Solution
    ZHANG Xiao1,2, LIAN Gang1*, TAN Miao1, ZHANG Shun-Jie1,2, CUI De-Liang1*, WANG Qi-Long2
    2011, 32(3):  655-661. 
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    Hydrothermal method has been used to synthesize of cBN. However, it is found that BN samples prepared by this method are usually mixtures of cBN, hBN and other phases, which severely limits the applications of cBN. So, it is expected to exploit new methods by which cBN can be quickly separated from other impurity phases. In this paper, we report a method, developed by using the self-aggregation phenomenon of cBN crystallites, to prepare large cBN crystallites agglomerates under some specific hydrothermal conditions, and then to separate them from the other phases. The particle size and its uniformity of the agglomerates can be improved by increasing the reaction temperature and the concentration of reactants, and improving the uniformity of reaction solution has similar effect. In contrast, increasing the pressure of reaction solution leads to opposite trend. The possibilities of using this phenomenon to purify the cBN samples in practice and control the growth process of cBN crystallites have also been discussed. Besides, a simple model has been proposed to explain the mechanism of the self-aggregation phenomenon.
    Fast Crystallization of ECR-1 Zeolite for Organotemplate-free
    REN Li-Min1, ZHU Long-Feng1, DING Hong1, YANG Cheng-Guang1, MENG Xiang-Ju2, XIAO Feng-Shou2*
    2011, 32(3):  662-666. 
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    Aluminosilicate ECR-1 zeolite with 12-membered channels was successfully synthesized at 120 ?C for 4 days in the absence of organic templates. Compared with ECR-1 synthesized at 100 ?C for 15 days, the crystallization of ECR-1 at 120 ?C is very fast (4 days), which are reasonably related to their difference in synthesis mechanism. Furthermore, a series of techniques such as IR spectroscopy, N2 isotherm, SEM micrograph, ICP analysis, 29Si NMR spectroscopy, and catalytic cracking of cymene were used to characterize ECR-1 zeolite, confirming the successful synthesis.
    Synthesis and Characterization of m-BiVO4 via Ionic Liquid-assisted Hydrothermal Synthesis
    CHEN Qing SUN Yan DUAN Xiao-Chuan ZHENG Wen-Jun*
    2011, 32(3):  667-672. 
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    Ionic liquid-assisted hydrothermal technique was used for the synthesis of Clinobisvanite (m-BiVO4) micron-sheet crystal and the crystal structure was refined by Rietveld method. m-BiVO4 has a monoclinic symmetry with space group I2/b. Synthesized products were characterized by XRD, IR and SEM methods. The primary results indicated that the amount of ionic liquid and pH value played crucial roles in controlling the morphology of as-prepared m-BiVO4. Particularly, the amount of ionic liquid [BMIM]Br can effectively control the shape of m-BiVO4 by the adsorption on the (001) plane of m-BiVO4.
    Hydrothermal Synthesis and Characterization of POM-based Supramolecular Complexes with Mixed Ligands
    DU Cheng-Bo, WANG Chun-Ling, FENG Su-Jiao, REN Yuan-Hang, KONG Zu-Ping, YUE Bin*, HE He-Yong*
    2011, 32(3):  673-677. 
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    Four POM-based coordination polymers with mixed 4,4’-bipy and 2,2’-bipy/phen, [Cu(4,4’-bipy)(2,2’-bipy)2]2[SiW12O40]?4H2O (1), [Ag4(4,4’-bipy)3(2,2’- bipy)2][SiW12O40]?2H2O (2), [Cu(4,4’-bipy)(phen)]2[H3O]2[SiW12O40]?8H2O (3) and [Cu(4,4’-bipy-Cl)(phen)]2[H3O][PW12O40]?H2O (4) (bipy = bipyridine, phen = phenanthroline), were synthesized under hydrothermal condition and characterized by IR, TG, elemental analysis, and single-crystal X-ray diffraction. Compound 1 is crystallized in the monoclinic system, space group P21/n, with a = 1.2858(4) nm, b = 2.0890(7) nm, c = 1.5580(5) nm, β = 102.306(4)o, V = 4.089(2) nm3, Z = 2, R1 = 0.0451, wR2 = 0.0934. Compound 2 is crystallized in the monoclinic system, space group P21/n, with a = 1.2766(4) nm, b = 2.1258(6) nm, c = 1.4491(4) nm, β = 104.774(4)o, V = 3.803(2) nm3, Z = 2, R1 = 0.0429, wR2 = 0.0730. Compound 3 is crystallized in the monoclinic system, space group C2/m, with a = 1.9850(8) nm, b = 1.4072(6) nm, c = 1.2108(5) nm, β = 110.629(6)o, V = 3.165(2) nm3, Z = 2, R1 = 0.0885, wR2 = 0.1647. Compound 4 is crystallized in the monoclinic system, space group C2/m, with a = 2.0376(7) nm,b = 1.4031(5) nm, c = 1.3784(5) nm, β = 93.502(6)o, V = 3.933(2) nm3, Z = 2, R1 = 0.0561, wR2 = 0.1491. The catalytic activity of these compounds was tested in the epoxidation of styrene and compound 3 and 4 exhibited high conversion of styrene and selectivity to epoxide.
    Microwave-assisted Solvothermal Synthesis of Bis(nicotinate)zinc
    GAO Fei, WANG Ying, LIU Xiao-Yang*
    2011, 32(3):  678-682. 
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    Bis(nicotinate)zinc was successfully synthesized under microwave-assisted solvothermal condition and the influences of reaction time, temperature, solvent, substrate concentration and heating method on the crystallization of the complexes were disscussed. With combination of the microwave-assisted solvothermal method and the conventional solvothermal method, the product so obtained not only has the advantages of microwave heating, but also has a large particle size that suitable for structural analysis.
    Contents
    Synthesis, Characterization and Luminescence of a New Diamondoid MOF Based on Tetrazole Derivative
    QIN Jun-Sheng, LAN Ya-Qian, WANG Hai-Ning, LI Lian-Jie, WANG Xin-Long, SUN Xiu-Yun*, SHAO Kui-Zhan, SU Zhong-Min*
    2011, 32(3):  683-687. 
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    A self-assembly reaction between the ligand 5-Amino-tetrazole (HATZ) and zinc(II) nitrate enables the formation of Zn(ATZ)2?DMA (1), which is characterized by X-ray powder diffraction (XRPD), IR spectrum and elemental analysis. Single-crystal X-ray analysis indicates that 1 exhibits a 3D microporous four-connected diamondoid (dia) topology with the channel dimensions of about 12.7 ? × 8.9 ? along the [100] direction. PLATON calculations show void space of ca. 53.5% per unit cell. The luminescent spectrum of 1 shows a strong blue fluorescence at room temperature.
    Articles
    Detection of Ascorbic Acid by Quantum Fluorescence Probe
    ZHANG Li-Pei, HU Bo, WANG Jian-Hua*
    2011, 32(3):  688-693. 
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    CdTe quantum dots of highly fluorescent is prepared in aqueous solution with mercaptopropanoic acid (MPA) as stabilizer. The fluorescence of the CdTe QDs is significantly quenched with blue shift on the addition of Mn2+ due to the change of the surface structure and chemical properties of the QDs. The fluorescence recovery is afterwards achieved in the presence of a small amount of ascorbic acid. This provides a novel QD-based turn-on fluorescent probe for the detection of ascorbic acid. When using QDs of 1.91 nm in size and a concentration of 1.67 uM in the presence of 0.25 mM Mn2+, the recovered fluorescence is linearly related with the ascorbic acid concentration within 0.25-16 uM, with a correlation coefficient of 0.9980 and a detection limit of 36 nM. The probe has been applied for the detection of ascorbic acid in Vc tablets and human whole blood samples.
    Ring-opening Reaction of Aziridines with α-Carbanion of Oximes
    CHEN Dong-Dong, DING Chang-Hua, HOU Xue-Long*, DAI Li-Xin
    2011, 32(3):  694-699. 
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    Aziridine is a very useful synthetic intermediate in organic synthesis. The ring-opening reaction of aziridine with various heteroatom nucleophiles has received intensive attention by organic chemists. However, the development of using carbon nucleophiles, especially unstabilized carbon nucleophiles, falls far behind. In this regard, we reported ring-opening reaction of α-carbanion of acetophenone oxime with aziridines in the presence of HMPA, affording corresponding products in moderate to good yields. Tetralone oxime is also a suitable substrate for some monosubstituted aziridines. This method offers a new example of the ring-opening reaction of carbanion with aziridines.
    Different Assemblies of Monotonous Maleonitriledithiolate\|modified β-Cyclodextrins in Solution
    WANG Qi, CHENG Xian, HE Rui, WANG Dong-Ni, LU Chang-Sheng*, MENG Qing-Jin
    2011, 32(3):  700-711. 
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    Mono[2-deoxy-2-(O-p-toluensulfonyl)]-β-cyclodextrin (2-Ots-β-cyclodextrin, compound 1) was substituted with 2-butenedinitrile-2,3-dimercapto sodium salt to give the product mono[2-deoxy-2-(2-butenedinitrile-2,3-dimercapto sodium salt)]-β-cyclodextrin (2-Mnt-β-cyclodextrin, compound 2). Compound 2 was characterized by IR spectroscopy, UV spectroscopy, thermogravimetry, 1H- and 13C-NMR spectroscopy. Different from its isomer mono[6-deoxy-6-(2-butenedinitrile-2,3-dimercapto sodium salt)]-β-cyclodextrin (6-Mnt-β-cyclodextrin) showing splitting Cotton effects via mutual inclusion complexation, 2-Mnt-β-cyclodextrin exhibited the absence of any circular dichroism (CD) signal in solution. In the meantime, quantum chemistry methods (time dependent-density functional theory, TD-DFT) were recruited in assisting assignment and prediction of the CD signals in spectra. Based on both the theoretical approach and experimental data, the different conformations of the two ionized isomers were revealed.
    Highly Diastereroselective Synthesis of Dihydrofurans Catalyzed by PE-supported Pyridinium
    CHEN Shuai-Shuai, LUO Shi-Zhong, LI Jun-Fang, LIU Chun-Rong, SUN Xiu-Li, TANG Yong*
    2011, 32(3):  712-716. 
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    The ylide reaction is one of the most useful approaches in forming ring compounds, and highly efficient catalysis of ylide reaction becomes one of the important frontiers in organic synthetic research. Polymer supported catalysis with tunable loading may increase the efficiency of the catalysis and avoid the volatilization of the ylide catalysis which might be savory and poisonous. In the presence of catalytic (O-NX) TiCl3 and MMAO, 4-(undec-10-enyl)pyridine was triumphantly inserted into the polyethylene chains. This PE supported pyridine proved to be an excellent recoverable and reusable organocatalyst. In the presence of catalytic amount of PE-supported pyridine and Fe(Tcpp)Cl, α-ylidene-β-diketones reacted with diazoacetate affording dihydrofurans respectively in up to 96% yield with high diastereoselectivities. The catalyst could be easily recovered after the reaction by cooling the reaction mixture to room temperature because the solubility of the PE-supported catalyst is dependent on the temperature and comonomer content. The yield of the reaction was almost maintained with excellent selectivity which was higher than 90% in 3 runs. This application allowed PE to be used as a cheap, readily prepared, easy separation, no-volatility, low noxious and recoverable catalyst support.
    Specific Conversion of Diester-diterpenoid Aconitum Alkaloids Components into Hydrolysis Monoester-diterpenoid Alkaloids Components and Lipo-alkaloids Components
    LIU Wen-Long, LIU Zhi-Qiang, SONG Feng-Rui, LIU Shu-Ying*
    2011, 32(3):  717-720. 
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    Methods of specific conversion of diester-diterpenoid aconitum alkaloids components into hydrolysis monoester-diterpenoid alkaloids components and lipo-alkaloids components have been established, conversion percentages were over 90%. Electrospray ionization tandem mass spectrometry was used to monitor conversion degree and identify conversion products, also to detect by-products.
    UV Raman Spectroscopic Studies on Rapid Synthesis of AM-6 Zeolite and Formation Mechanism of —V—O—V— Atomic Wires
    GUO Mei-Ling, FAN Feng-Tao, GUO Qiang, FENG Zhao-Chi*, LI Can*
    2011, 32(3):  721-725. 
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    The synthesis of AM-6 zeolite with remarkable short time, 4 hours, has been reported in this work. The effects of the K+/V4+ ratio and the pH value of the initial gel on the purity and crystallinity of AM-6 zeolite have been investigated. The synthesis condition optimized at K+/V4+=3 and pH=12.5. The formation mechanism of the –V-O-V- atomic wires in AM-6 is monitored by UV Raman spectroscopy in combination with UV-Vis spectroscopy and X-ray diffraction patterns. It turns out that the formation of the VO3- chains composed of corner-sharing VO4 in the silicate gel plays an important role in the formation of -V-O-V- atomic wires in AM-6 crystals.
    Influence of CuInSe2 Nanocrystals Concentration on the Performance of CuInSe2/P3HT Hybrid Photodetectors
    WANG Jian-Jun, GUO Yu-Guo, WAN Li-Jun*
    2011, 32(3):  726-730. 
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    CulnSe2 is a promising light-absorbing material suitable for high-efficiency solar cells. It possesses many advantageous properties for solar applications: its band gap energy is at the red edge of the solar spectrum; it is direct band-gap semiconductor with correspondingly high absorption coefficients. The hybrid CulnSe2-P3HT material combining the advantages of the two materials will be widely applied in the photoelectric field. In this paper,the high performance hybrid photodetectors were fabricated and the influence of CulnSe2 nanocrystals concentration on the performance of the CulnSe2-P3HT hybrid photodetectors was investigated. As the CulnSe2 nanocrystals concentration was increased, the switching ratio reached a maximum value at a moderate CulnSe2 nanocrystals concentration,while the temporal response was faster.
    Phenylsulfonic Acid Functionalized Porous Phosphate Heterostructure Materials as Strong Solid Acids
    LI Ying, LIU Ke, HUA Wei-Ming, YUE Ying-Hong*, GAO Zi
    2011, 32(3):  731-737. 
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    A series of phenylsulfonic acid functionalized porous phosphate heterostructure (PPH) materials were prepared by co-condensation method and characterized by SEM, FT-IR, 29Si MAS NMR, TG and N2 adsorption. Their catalytic behavior for alkylation of hydroquinone with tert-butanol was compared. ZrP-0.4-2-10%-PhSO3H is a more active catalyst for the reaction in comparison to others. The conversion of hydroquinone and yield of 2-tert-butylhydroquinone on the catalyst reach 85.4% and 58.5% at 150 oC. The activity correlates well with the amount of the accessible acid sites on its surface. The catalyst is stable and reusable, and the product yield is only reduced by 10% after four runs. The reduction in activity is probably caused by leaching of phenylsulfonic group or deposition of coke on the active sites.
    Synthesis and Characterization of Aluminum-pillared Saponite and Its Catalytic Properties in Hydroisomerization of n-Decane
    ZHAO Xiao-Hong, WANG Yong-Rui, MU Xu-Hong*, MIN En-Ze
    2011, 32(3):  738-742. 
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    Well-ordered trioctahedral saponites were successfully synthesized in strong basic system under high temperature, and were intercalated with Keggion ions. XRD, 27Al MAS-NMR, N2 adsorption and desorption , FTIR spectra of pyridine adsorption, TGA-DTA and TEM were used for the characterization of the synthetic aluminum-pillared saponites. The results illustrated that pillared saponites were highly-ordered and thermal stable above 800℃.Besides,after being pillared by aluminium oligmer,the Al-pillared synthetic saponite showed high conversion and hydroisomerization yield in the catalytic reaction of n-decane.
    Preparation, Characterization and Basic Catalytic Properties of Nitrogen-incorporated FAU Zeolites
    WANG Tao, WU Guang-Jun, LI Lan-Dong*, GUAN Nai-Jia
    2011, 32(3):  743-747. 
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    Dehydration-nitridation method is employed to prepare nitrogen-incorporated HY zeolites. High crystallinity and specific surface area of parent HY are well preserved in nitrogen-incorporated HY zeolites. The base strength of HY framework is enhanced due to the replacement of oxygen by nitrogen with lower electronegativity. The acidity and basicity of nitrogen-incorporated HY zeolite are characterized by IR spectra using NH3 and CO2 as probe molecules and temperature-programmed desorption of CO2. The amounts of L-acid sites decrease, while the amount of L-acid sites and base sites increase after nitridation. Moreover, new base sites with moderate strength are created after nitridation. Compared to parent HY zeolite, the nitridized sample exhibits improved basic catalytic performance in Knoevenagel condensation reaction.
    Methanol-tolerant Carbon Supported Phthalocyanine-platinum Nanocomposite Catalytic Cathode
    ZHENG Ning, LIU Yan*, WANG Yuan*
    2011, 32(3):  748-752. 
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    A H2Pc-Pt/C nanocomposite catalyst was prepared and characterized by TEM, XRD and ICP. In an O2-saturated H2SO4 solution containing methanol (0.5 M), the onset potential over the H2Pc-Pt/C-Nafion? electrode shifted by more than 200 mV toward positive relative to that over an electrode prepared with a commercial Pt/C-JM catalyst and Nafion? (Pt/C-JM-Nafion?), and the specific current density at 0.85V of the H2Pc-Pt/C-Nafion? electrode for oxygen reduction reaction (ORR) is about 7 times larger than that of the Pt/C-JM-Nafion? electrode. Different from FePc, H2Pc does not form ethanol soluble complex with Nafion?. The excellent methanol tolerance of H2Pc-Pt/C-Nafion? is mainly derived from the presence of high active and selective catalytic sites for ORR in the catalytic electrode.
    Kinetics Study of Hydrolysis Catalyzed by Immobilized Enzyme in Nanozeolite Modified Microchannel Reactors
    WANG Zhou-Jun, LI Xiang, WANG Chen-Chen, TANG Yi, ZHANG Ya-Hong*
    2011, 32(3):  753-757. 
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    In this paper, nanozeolite modified microchannel reactors are constructed by assembling zeolite nanocrystals into capillary using layer-by-layer method. And then lipase is immobilized on the nanozeolites which are assembled in the microreactors. The nanozeolite modified microreactors could incorporate excellent biocaptibility and large external area of nanozeolites and high efficiency and fast mass diffusion of microreactors together. Hydrolysis of 4-nitrophenyl palmitate (4-NPP) is carried out as a probe reaction to study the hydrolysis kinetics catalyzed by immobilized lipase in the microreactors. By comparing the characteristic parameters (Km and Vmax) from Michaelis-Menten equation, it is found that efficiency of enzymatic hydrolysis in such nanozeolite modified microchannel reactors could be 3 or more times higher than that of the same reaction in conventional reactors. In addition affinity between enzyme and substrates is also enhanced in the nanozeolite modified microchannel reactors.
    Predicting Hydrogen Adsorption Uptake in Metal-Organic Framework(MOF) Containing Unsaturated Coordinate Coppers Using Molecular Simulation
    WANG Lin, SUN Ying-Xin, MIAO Yan-Lin, SUN Huai*
    2011, 32(3):  758-764. 
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    In this paper, we report force field predictions of hydrogen uptakes for MOFs materials that contain unsaturated coordinate copper metal complexes. The ab initio calculations were performed using RI-UMP2 method with the TZVPP basis set and BSSE correction on square-coordinated copper-acidic complex and hydrogen molecules. A force field was developed based on the ab initio energetic data. The resulting force field was applied to predict hydrogen adsorption isotherms at different temperatures and pressures using GCMC method. The ab initio results indicate that the square-coordinated copper has stronger interaction with hydrogen than tetrahedral-coordinated zinc. However, existing experimental data has not realized the potential yet. In order to predict hydrogen uptakes for similar materials, we adjusted the force field parameters using known experimental isotherm of CuBTC and predicted hydrogen uptakes for other three similar MOFs relative to CuBTC.
    Synthesis and MTO Catalytic Performance of SAPO-34
    LI Jun-Fen, FAN Wei-Bin*, DONG Mei, HE Yue, QIN Zhang-Feng, WANG Jian-Guo
    2011, 32(3):  765-771. 
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    Effects of SiO2/Al2O3, P2O5/Al2O3 and H2O/Al2O3 ratios in the synthesis gel on the crystallization of SAPO-34 were systematically studied with triethylamine as a templating molecule for the purpose of improving its catalytic performance in MTO reaction. Pure SAPO-34 phase can only be synthesized with the synthesis gel having a SiO2/Al2O3 ratio larger than 0.25, demonstrating the structure-directing role of Si. Nevertheless, a further increase in the Si content in the synthesis gel led to not only the formation of Al2O3 but also the decrease in the crystallinity, surface area and catalytic stability of SAPO-34. The P2O5/Al2O3 and H2O/Al2O3 ratios in the synthesis gel also significantly influenced the crystallization and catalytic performance of SAPO-34. When P2O5/Al2O3 and H2O/Al2O3 were 1.1 and 36 respectively, the synthesized sample with a (P+Si)/Al ratio close to 1 showed high surface area and appropriate acidity, resulting in a catalytic lifetime of 520 min without lowering olefin selectivity. The catalytic performance of SAPO-34 is also highly dependent on its calcination conditions. The sample calcined at 550 oC for 8 h in flowing air showed a much higher catalytic stability (its catalytic lifetime reached 580 min) than the sample calcined for 10 h under the same conditions as a result of different hydrocarbon residuals kept in SAPO-34 after calcination.
    Synthesis of Amine/methyl Bifunctionalized SBA-15 with Hexagonal Platelet Morphology and Its Application in Bilirubin Adsorption
    TANG Tao, LI Xiao-An, ZHAO Yan-Ling, XU Yao, WU Dong*, SUN Yu-Han
    2011, 32(3):  772-777. 
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    To effectively remove bilirubin, amine/methyl bifunctionalized SBA-15 materials (AMS) were directly synthesized by co-condensation of 3-aminopropylmethyldiethoxysilane and tetraethoxysilane using an amphiphilic block copolymer as template under acidic-catalyzed and inorganic-salt-assisted conditions. XRD, N2 sorption analysis, TEM, FTIR and 29Si MAS NMR were used to identify the well-ordered mesostructure and the grafting of amine and methyl groups on the surface of the synthesized materials. The addition of inorganic salt KCl was proven to play an important role in the formation of the highly ordered mesostructure. Increasing KCl concentration from 1.0 to 2.0 M, the morphologies of AMS samples shift from hexagonal platelet to fiberlike morphology. The AMS sample with platelet morphology exhibited faster bilirubin adsorption rate and higher bilirubin adsorption capacity than AMS and pure SBA-15 samples with fiberlike morphology. This could be attributed to the fast molecular transport based on the short mesopore channels and the strong interaction between organic groups (amine and methyl) of AMS and bilirubin molecule.
    Contents
    Catalytic Oxidative Desulfurization of Model Oil by MoO3/Mesoporous Al2O3
    LI Yu-Hui, FENG Li-Juan*, WANG Jing-Gang, ZHOU Xuan, CHENG Bin-Bin, WANG Xiao-Yan, LI Chun-Hu
    2011, 32(3):  778-782. 
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    In the MoO3/mesoporous Al2O3-H2O2 system,a simulated oil consisting of model sulfur compounds, such as benzothiophene (BT) , dibenzothiophene (DBT) ,4 ,6-dimethyldibenzothiophene (4 ,6-DMDBT) and thiophene (Th) , and cyclohexane as solvent was employed in the oxidative desulfurization study .The effects of catalyst, dosage of oxidation agent and reaction condition on desulfurization activity were investigated .It was showed that the removal efficiency of DBT at 60℃ was as high as 99.4% when the content of MoO3, dosage of catalyst and the molar ratio of H2O2 to sulfur were 20% ,1.5% and 4, respectively. Under the optimum conditions, the oxidative activity of the model sulfur compounds follows the order of DBT > 4,6-DMDBT >BT>Th.
    Articles
    Highly Selective Oxidation of Cyclohexene via Trivacant Keggin-type Phosphotungstate as Catalysts
    AN Wen-Jia, XU Lin*
    2011, 32(3):  783-786. 
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    The oxidation of cyclohexene with 30% hydrogen peroxide was catalyzed by trivacant Keggin-type polyoxometalates tetra-butylammonium salts [A-α-PW9O34]9- and [(FeШ(OH2)2)3(A-α-PW9O34)2]9-. The effects of reaction conditions such as molar ratio of cyclohexene to H2O2 , reaction time and catalyst amount on the catalyst activity were investigated. The catalyst [(C4H9)4N]9[A-α-PW9O34] showed a high selectivity (≥ 99 % ) for cyclohexene oxide with the cyclohexene conversion of 55 %. The catalyst [(C4H9)4N]9[(FeШ(OH2)2)3(A-α-PW9O34)2] showed a cyclohexene conversion of 17 % and a 2-cyclohexene-1-one selectivity of 99 % .
    Selective Adsorption Desulfurization Performance and Adsorptive Mechanisms of NiY Zeolites
    SONG Li-Juan*, PAN Ming-Xue, QIN Yu-Cai, JU Xiu-Fang, DUAN Lin-Hai, CHEN Xiao-Lu
    2011, 32(3):  787-792. 
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    NiY zeolites were prepared by liquid phase ion exchange method and the adsorbents were characterized by XRD, TEM, ICP, Nitrogen adsorption and Py-IR. The adsorptive behavior of thiophene (T), 2-methylthiophene(2-MT), 3-methylthiophene(3-MT), tetrahydrothiophene(THT), benzothiophene(BT), dibenzothiophene(DBT), 4-methyldibenzothiophene(4-MDBT) and 4,6-dimethyldiben-zothiophene (4,6-D MDBT) on NiY zeolites were investigated by fixed bed, the latest generation of SCD detectors(GC-SCD) and Fourier Transform Infrared (FT-IR). The results show the breakthrough adsorption capacity of different sulfur compounds, and the order is: THT > BT ≈ DBT ≈ 4,6-DMDBT > 4-MDBT > 3-MT ≈ 2-MT > T,which indicates that the steric hindrance of sulfur compounds is not the crucial factor for their adsorptive properties on NiY zeolites. The mechanisms of thiophene and thiophene derivatives interacting with NiY zeolites were different, but the direct S-M interaction is the domain process. Thiophene and thiophene alkyl complex adsorbed on the surface acidity can subsequently undergo the opening of the heterocyclic rings, and the polymer molecules will plug the pore of zeolite, resulting in decreasing of the desulfurization capacity of NiY. Adsorption mechanisms and surface acidity of NiY zeolites are the key factors for the selective adsorption desulfurization.
    Novel Fluorescent Vesicular Sensor for Saccharides Based on Boronic Acid\|diol Interaction
    LI Guang-Quan, YU Jing-Sheng, LI Guo-Wen*
    2011, 32(3):  793-796. 
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    Abstract A novel amphiphile containing two functional groups of both quinolinium and boronic acid, N-(boronobenzyl)-8-hexadecyloxyquinolinium bromide (BHQB), has been synthesized. Scanning electron microscopy (SEM) indicated the formation of bilayer vesicles in the ethanol/water solution (?=0.6). Differential scanning calorimrtry (DSC) established the presence of crystal-to-liquid crystal transition at 52.4 oC. The vesicular fluorescence properties upon binding with carbohydrates have been studied in ethanol/water buffer at pH 7.4. Addition of saccharides to the vesicular solution, the fluorescent intensities of quinoliniun in BHQB vesicles centered at 425 nm increased gradually and 508 nm decreased dramatically with increasing concentration of saccharides. The change tendency of fluorescent intensities of the BHQB vesicles with concentration of saccharides followed in the order of glucose > fructose. The pH profiles of the fluorescence intensity were studied in the absence and in the presence of sugars. These results suggest that the BHQB vesicles may be developed as a continuous monitoring and implantable fluorescence vesicular sensor, which might be applied in the practical field.