Highly effective and chemoselective hydrodeoxygenation of aromatic alcohols

Effective hydrodeoxygenation (HDO) of aromatic alcohols is very attractive in both conventional organic synthesis and upgrading of biomass-derived molecules, but the selectivity of this reaction is usually low because of the competitive hydrogenation of the unsaturated aromatic ring and the hydroxyl group. The high activity of noble metal-based catalysts often leads to undesired side reactions (e.g., saturation of the aromatic ring) and excessive hydrogen consumption. Non-noble metal-based catalysts suffer from unsatisfied activity and selectivity and often require harsh reaction conditions. Herein, for the first time, we report chemoselective HDO of various aromatic alcohols with excellent selectivity, using porous carbon–nitrogen hybrid material-supported Co catalysts. The C–OH bonds were selectively cleaved while leaving the aromatic moiety intact, and in most cases the yields of targeted compounds reached above 99% and the catalyst could be readily recycled. Nitrogen doping on the carbon skeleton of the catalyst support (C–N matrix) significantly improved the yield of the targeted product. The presence of large pores and a high surface area also improved the catalyst efficiency. This work opens the way for efficient and selective HDO reactions of aromatic alcohols using non-noble metal catalysts.

Porous carbon–nitrogen hybrid material-supported Co catalysts can effectively promote the chemoselective hydrodeoxygenation reaction of a various of aromatic alcohols in ethanol and hydrogen atmosphere, under relatively mild conditions.     

FCC硫转移剂MgAlCuFe复合氧化物的结构与性能:金属盐前体的影响

分别以硝酸盐、盐酸盐和硫酸盐为金属盐前体,采用共沉淀法合成了MgAlCuFe类水滑石前驱体,经过700℃焙烧6h后,制得三种新型FCC硫转移剂.运用X射线衍射、热重、氮气吸附和红外光谱对这三种硫转移剂的结构和性能进行了表征,并采用改装的WRP-3热重天平评价了其氧化吸硫和还原脱硫的性能.结果表明,三种金属盐均可得到结构规整的类水滑石前驱体,经过焙烧后得到复合氧化物MgAlCuFe.与采用盐酸盐和硫酸盐作前体相比,由硝酸盐制得的硫转移剂具有较大的比表面积,其饱和吸附硫容和氧化吸硫速率均较高,6min可达到1.54g/g的饱和吸附能力,同时具有较强的还原脱硫能力.     

氧化铝对Pt-SO4^2-／ZrO2-Al2O3固体酸催化剂结构与酸性的影响

通过混捏法制备了Pt-SO4^2-／ZrO2-Al2O3固体酸催化剂，考察了该催化剂在正构烷烃低温异构化反应中的催化稳定性．采用X射线衍射、差热分析、X射线光电子能谱、核磁共振、N2吸附-脱附和微量热等表征技术，对氧化铝的作用机理进行了研究．结果表明，氧化铝起到结构助催化剂作用，对四方相氧化锆具有稳定作用，并延迟了氧化锆的晶化，抑制了氧化锆的烧结，从而增大了催化剂的比表面积和孔容．XPS结果表明，Zr3d峰向低结合能方向移动，Al2p峰向高结合能方向移动，说明Al^3＋的电子向Zr^4＋偏移．微量热结果表明氧化铝的引入提高了催化剂的酸量和酸强度．^27Al固体核磁共振结果表明，Pt-SO4^2-／ZrO2-Al2O3中的六配位铝的结构发生了变化．氧化铝的引入还可能有助于氧化锆晶格缺陷的形成，焙烧过程中Al^3＋迁移进入氧化锆晶格并同晶取代Zr^4＋形成氧缺陷位，这些氧缺陷位在S=O键诱导下显示强酸性．     

Sm0.88Dy0.12Fe2合金的易磁化方向研究

运用穆斯堡尔效应，对Ｓｍ０．８８Ｄｙ０．１２Ｆｅ２合金的易磁化方向的变化进行了研究。结果表明；随着温度的升高，其易磁化方向从「１１０」渐变地转向「１１１」，在１５３至２１３Ｋ温度范围内，「１１０」和「１１１」两者共存，而并非由「１１０」其一温度突变至「１１１」。     

A novel template-free sol–gel synthesis of silica materials with mesoporous structures and zeolitic walls

Hierarchical porous materials with zeolite structures show great promise in catalysis due to combining the advantages of zeolites and mesoporous materials. Here a novel template-free sol–gel method is developed to synthesize hierarchical porous silica materials. This method involves solvothermal recrystallization of the xerogel converted from uniform silicalite-1 precursor sol via vacuum drying process. The zeolite sol and the solid samples were characterized by laser light scattering, XRD, N₂ adsorption/desorption isotherm, FTIR, SEM, TEM and thermal analysis technologies. The results show that we obtain two novel materials with different mesoporous structures and silicalite-1 walls by using different recrystallization media, one of which has irregular arrays of mesopores, the other possesses 3D wormhole mesoporous structure. We speculate that formation of different mesoporous structures results from different nucleation and growth process of materials     

Impetus for solvothermal synthesis technique: synthesis and structure of a novel 1-D borophosphate using ionic liquid as medium

A novel borophosphate compound has been synthesized under solvothermal conditions using ionic liquid as a medium and structurally characterized by single-crystal X-ray diffractions. The compound crystallizes in the monoclinic, space group P2(1)/n, a=8.089(8) Å, b=13.977(12) Å, c=8.441(8) Å, β=112.517(11)°, Z=2, V=881.7(14) Å³, R₁=0.03, wR₂=0.079 and S=1.01. Its structure consists of a 1-D straight chain that is built of the alternative linkage of mutually perpendicular four-member rings. Other characterizations by IR and thermal and elemental analyses are also described.     

环己烯水合制备环己醇的研究Ⅰ. 分子筛结构及晶粒大小的影响

考察了三种不同结构的分子筛(ZSM-5,MCM-22及β)以及不同晶粒大小的ZSM-5分子筛对环己烯水合反应的催化活性. 结果表明,具有12元环孔道体系的β分子筛对环己烯的转化率(9.6%)最高,但对环己醇的选择性(35.4%)最差. MCM-22分子筛的活性很低,其环己烯转化率只有0.8%. 而孔口为10元环结构的ZSM-5分子筛则具有较高的活性(环己烯转化率7.5%)和产物选择性(99.2%),因此是较好的水合催化剂. ZSM-5分子筛的晶粒大小对其环己烯水合反应活性有明显的影响,分子筛晶粒越细,则水合反应活性越高,其原因在于晶粒变细增大了分子筛的外比表面积,从而增加了接近孔口处的活性中心的数量.     

新型免疫电极法测定乙型肝炎表面抗原

本文报道一种新型的乙型肝炎抗体膜片。测试时,仅需将25μl被检血清滴注于该膜上,经孵育与洗涤即可制得抗原与抗体复合物膜。用复合物膜组装成免疫电极,测定血清样品中乙型肝炎表面抗原含量。电极的线性范围是20～320ng/ml,方法的日间相对标准偏差为10.78％(n=4,m=5),对血清中可能存在的一些其它抗原具有较好的选择性。105例临床血清样本,本法与酶联免疫吸附分析法测定结果符合率为86％。乙肝抗体膜片系一次性使用,4℃可保存半年以上。     

THE INFLUENCE OF LIPIDS ON THE FLOW BEHAVIOUR OF SOME CHINESE AND NORWEGIAN CRUDE OILS

The influence of lipids on the flow behaviour of some Chinese, Norwegian crudes and synthetic oil (N-octane) was investigated by viscosity determination and by optical microscopy- The flow behaviour of these waxy crudes was improved when paraffins were separated from the oil and formed small independent particles instead of dissolved in the oil at temperature below the appearance point of the paraffins.     

A novel and effective Zn/PEI-MCM catalyst for the acetylene hydration to acetaldehyde

The introduction of PEI can enhance the metal-support interaction to make the better metal dispersion and more active sites, and the charge transfer from N atom to Zn species, especially for the Zn/P-MCM-12 catalyst with about 88% C₂H₂ conversion and 85% selectivity.