Fe/SBA-15/carbon composites were synthesized by chemical vapor infiltration (CVI) method using ferrocene as concurrent iron and carbon precursor. Accordingly, Fe2O3 nanoparticles supported on mesoporous SBA-15 silica or metallic Fe homogeneously embedded in mesoporous carbon were selectively obtained either by oxidizing the carbon component in air or by removing the silica template using an aqueous NaOH solution. The Fe2O3/SBA-15 and Fe/carbon composites so obtained were thoroughly characterized by N2 adsorption/desorption isotherm measurements, powder X-ray diffraction (XRD), transmission electron microscopy and H2-temperature programmed reduction (H2-TPR). The effects of CVI duration time and temperature on their corresponding reduction states and particle dispersion, and consequently on their catalytic performances during benzylation reaction of benzene with benzyl chloride were examined and discussed.

A novel and effective method was described in this work to prepare two-dimensional hexagonally ordered mesoporous CMK-5 carbon materials. This method is based on the chemical vapor deposition (CVD) of ferrocene in the mesopores of SBA-15 at 500 degrees C, followed by graphitization at different temperatures. Both the silica/carbon composite and the resulting CMK-5 were characterized by N-2 adsorption, powder X-ray diffraction, Raman spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy (HRTEM), and thermogravimetric analysis. It was found that the ferrocene could be used as a new precursor to prepare CMK-5 nanopipes, with pipe thicknesses varying from 0.8 to 2.6 nm, by increasing the CVD time from 20 to 120 min. The resulting CMK-5 exhibits high Brunauer-Emmett-Teller (BET) surface area (1044-2449 m(2)/g) and large pore volume (1.13-2.20 cm(3)/g). The graphitization degree of the resulting CMK-5 was investigated by pyrolyzing the corresponding silica/carbon composite at different temperatures. Pyrolysis temperatures below 850 degrees C led to gradually improved graphitization degrees of CMK-5 nanopipes. Pyrolysis temperatures above 850 degrees C resulted in the partial collapse of ordered CMK-5 nanopipes accompanied by the appearance of a considerable amount of entangled graphitic ribbons. The structural evolution process of CMK-5 from ordered nanopipes to the final entangled graphitic ribbons was observed by HRTEM. The obtained CMK-5 was applied as a catalyst support of Pt for methanol oxidation. The electrochemical activities of Pt nanoparticles loaded on the CMK-5 carbon materials were investigated by cyclic voltammograms and compared with the commercial Pt/Vulcan XC-72 catalyst. It was found that the specific mass activity of Pt/CMK-5 was much higher than Pt/Vulcan XC-72.

Nitrogen-containing ordered mesoporous carbons (NOMCs) characteristic of CMK-3 were nanocasted from mesoporous silica SBA-15 using aniline as carbon precursor. The influence of synthesis condition on the structural parameters of NOMCs were systematically investigated using N2 adsorption, powder X-ray diffraction (XRD), transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), elemental analysis and thermogravimetric analysis (TGA). The 2D hexagonally ordered nitrogen-containing mesoporous carbon could be synthesized in a wide temperature range (600–950°C), with Brunauer–Emmett–Teller (BET) surface area varying from 988 to 1166m2/g and pore size tunable from 2.7 to 3.3nm. The N/C molar ratio in the framework of mesoporous carbon was found to be highly dependent on the synthesis condition and reduced from 9.5% to 4.8% as the synthesis temperature increased from 600 to 950°C. XPS showed that nitrogen atoms were incorporated in graphitic sheets as quaternary nitrogen and pyridine-like nitrogen. The ca. 0.6eV lower binding energy of Pt nanoparticles in contrast to that of bulk Pt indicated a strong interaction between nitrogen atoms and Pt nanoparticles, which was critical to the uniform dispersion of Pt nanoparticles on the nitrogen-containing mesoporous carbon. The CO stripping peak potentials depended on both the N/C ratio as well as Pt particles size. The activities of methanol oxidation on Pt/NOMCs were investigated by cyclic voltammograms and electrochemical impedance spectroscopy (EIS). The Pt/NOMCs showed generally high CO tolerance and comparable activity to Pt/XC-72 under the identical condition.

Mesoporous graphitic carbon with high surface area (298.2 m2/g) was fabricated at 950°C using monodisperse colloid SiO2 with diameter of 26 nm as the template, styrene as the carbon precursor, and Ni as the catalyst. The obtained carbon material was characterized by powder X-ray diffraction, N2 adsorption, thermogravimetric analysis, and transmission electron microscopy. The presence of Ni was crucial to the formation of graphitized mesoporous carbon. The TiO2/graphitic carbon composite was prepared by loading TiO2 in the mesopores of the graphitic carbon via the sol-gel method. Both the surface area and pore volume of the composite were significantly reduced in contrast to the mesoporous graphitic carbon. The photoactivity of TiO2/graphitic carbon was investigated by photocatalytic degradation aqueous solutions of rhodamine B and phenol. The degradation of both rhodamine B and phenol followed first-order reaction kinetics, and the composite showed higher photoactivity than the pure anatase TiO2.

The mesoporous graphitized carbons were catalytically synthesized with the assistance of metal Ni by pyrolyzing polystyrene in the interstices of closed-packed silica spheres at 950°C. By using colloidal silica with 10nm, 36nm in diameter or the mixed colloidal silica as templates, mesoporous graphitized carbon with monomodal or bimodal pore size distribution were prepared. The obtained carbons were characterized by the powder X-ray diffraction, N2 adsorption, Raman spectrometry, high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray analysis and thermogravimetic analysis. It was found the presence of nanometer Ni in the silica template was crucial to the graphitization of the final mesoporous carbon. HRTEM revealed that the graphene layers were curved and seemed to be densely stacked parallel to the external surface of the silica spheres. The specific surface area and total pore volume of the resulting graphitized carbon were highly dependent on the proportion of two type of colloidal silica with different particle size (10 and 36nm, respectively). The experimental surface area and total pore volume were compared with theoretical value by supposing that the mesopores created by spherical silica could form cubic closed-packed structure. The difference between experimental and theoretical value was analyzed.

在乙腈中,以12-钼钨磷杂多酸和8-羟基喹啉为原料,合成了标题配合物[Mo(Ⅱ)(C9H6NO)2(H2O)2]淡黄色四方柱状晶体,并测定了其单晶结构.晶体属单斜C格子,空间群为Cc,每一晶胞中有4个配合单元,形成链状结构.晶胞参数为α=1.3358(3) nm, b=0.9412(2) nm, c=1.3550(3) nm, β=109.71(3)°, V=1.6038(6) nm3, Z=4, Dc=1.741 g/cm3, F(000)=848,结构的偏离因子R=0.0237, ωR=0.0648.KMnO4滴定法、ESR和磁化率测定表明,该配合物显顺磁性,μeff=4.81 B.M, n=4.钼(Ⅱ)离子周围有反式氧配位,O(1)-Mo-O(2)键角为150.89(12)°,其配位数是6,形成畸变八面体.

In this paper we describe the moleculare and crystal structures of the Na3[Hg(∥) (edta)Cl] · 6H2O (edta=ethylenediamine-N,N,N′,N′-tetraacetate). The crystal data are as follows: orthorhombic, a = 8.083(2) Å, b=13.870(3) Å, c=38.617(5) Å, V=4329.4(13) Å3, Z=8, Dc = 1.798 g · cm-3, μ=5.564 mm-1, F(000) = 2280, R=0.0317 and Rw = 0.0731 for 3883 unique reflections. In complex, the complex anion [Hg(∥) (edta)Cl]3- has a seven-coordination structure like a mono-capped trigonal-prism (C2v-MTP) in which the ecta4- acts as a hexadentate ligand with four O atoms and two N atoms and a Cl- caps a quadrilateral face as a seventh ligand. It can be known that the Hg2+ which-has a d10 electronic structure can form a high-coordinate compound with a hexadentate ligarid (edta) because it has a big ionic radius.

Through the reaction of Co2(CO)8 with four thiuram [R2NC(S)S]2*,four new sulfur-capped trinuclear cobalt carbonyl clusters Co3(CO)7(μ3-S) (μ, η2-S*C*NR2) ( I : R= Me; II : R=Et; III : R=i-Pr; IV : NR= -N Hexagon sign], were prepared and characterized by elementary analysis, IR, 1H NMR and MS spectroscopy. The crystal structure of the cluster Co3(CO)7(μ3-S)[μ, η2-S*C*'N(i-Pr)2](III) was determined by X-ray single crystal diffraction method. The crystal of III is monoclinic, belonging to space group P21/n, and the cell parameters are as follows: a=1. 145 2(2) nm, b=1. 502 8(3) nm, c=1. 214 4(2) nm; α= 90°, β=92. 15(3)°, γ=90°; V=2. 088 5(7) nm3, Z=4, F(000)=1 096, Dc=1. 747 mg · m-3, μ=2. 588 mm-1, R=0.040 7, Rw=0. 062 4. The structural analysis shows that cluster III has a pyrimidal Co3S framework and contains a heterocylic bridging bidentate ligand[μ, η2-S*C*N(i-Pr)2] linked to the Co2 and Co3 atoms of the cluster by a cobalt-carbon and a cobalt-sulfur bond respectively.

Co2 (CO) 8 与 4个二硫代双 (烷基硫代甲酰胺 )类前配体 [R2 NC(S) S]2 反应 ,得 4个含烷基硫代甲酰胺基的三核钴羰基硫簇合物 .通过元素分析、IR、 1H NMR和 MS等方法表征了它们的结构 ,用 X射线衍射法测定了其中一个簇合物 Co3 (CO) 7(μ3 - S) [μ,η2 - SCN(i- Pr) 2 ]( )的晶体结构 .晶体属单斜晶系 ,P2 1/n空间群 ,晶胞参数 a=1.1452 (2 ) nm,b=1.50 2 8(3) nm,c=1.2 144 (2 ) nm,α=90°,β =92 .15(3)°,γ =90°,V =2 .0 885(7) nm3 ,Z=4 ,F (0 0 0 ) =10 96 ,Dc=1.74 7mg· m-3 ,GOF(F2 ) =0 .835,μ=2 .588nm-1.最终因子 R[I>2 σ(I) ]=0 . 0 4 0 7,Rw=0 .0 6 2 4

各种各样的氨基多羧酸类配合物多年来一直是化学家们较为感兴趣的研究课题之一[1～4].特别是近年来,氨基多羧酸类配体作为一些有毒重金属的排泄剂[5]和与一些放射性金属离子形成配合物后作为核医学的显影剂[6]等方面得到了广泛的应用.金属Hg是有毒的,一般情况下,人们不希望它留在体内,但有时人们又不得不接触和使用它.因此,研究金属离子Hg2+与氨基多羧酸类配体形成配合物的性质及结构对于更好地了解Hg的生物活性会有一定的帮助.过去人们曾普遍认为金属离子Hg2+配合物的配位数是比较低而且比较单一的.最近的实验结果表明,如果配体合适,金属离子Hg2+也能形成相当高配位数的配合物.继八配位的[Hg(Ⅱ)(nta)2]4-配合物[7]之后,本文又报道了金属离子Hg2+与edta(乙二胺-N,N,N′,N′-四乙酸)形成的配合物,通过X-射线衍射仪的测定,得到了它不太常见的配位结构.

The title complex was synthesised and its molecular and crystal structures were determined by single-crystal X-ray reflection structure analysis. The crystal data are as follows: K [ InIII (EDTA)(H2O)] · 2H2O (EDTA = ethylene-diamine-N, N, N′ , N′-tetraacetate) , Monoclinic, Cc space group, a = 0.9096(2) nm, b = 1. 1996(2) nm, c = 1. 5144(3) nm, β= 99. 40(3)°, V= 1.6302 . (6)3, Z = 3, Dc= 1.498 g·cm-3, μ = 1.325 mm-1, F(000) = 726, R = 0.0320 and RW = 0.0903 for 2315 observed independent reflections. The complex anion [ InIII (EDTA) ( H2O) ]- has a seven-coordinate pseudo-pentagonal bipyramidal (PB-D5h) structure, in which the EDTA serves as a hexadentate ligand with two N atoms and four O atoms and one water molecule (H2 O) directly coordinated to the central metal ion In as a seventh ligand.

K4H2CoW12O40·2TiO2·9H2O crystallizes from an aqueous solution of Na2WO4, Co(OAc)2 and Ti(SO4)2. The compound has very similar i.r. and u.v. spectra to those of [CoW12O40]6− and [CoW11TiO40]8− but its polarographic behaviour is different from that of [CoW11TiO40]8− and exhibits only reduction of tungsten(VI). A single crystal structural analysis indicates that this compound consists of the heteropolyanion [CoW12O40]6−, titanium–oxygen chain, potassium ions and water molecules.