两种新型Cu(Ⅱ)混配聚合物的合成和晶体结构

用水热法合成了2种新型的配位聚合物[Cu(4-Pya)(2,4-PydcH)]_n(1)和[Cu₂(2,6-Ndc)₂(Bpobp)]_n(2)(4-Hpya=4-吡啶羧酸,2,4-pydcH₂=吡啶-2,4-二羧酸,2,6-H₂ndc=2,6-萘二酸,Bpobp=4,4′-二(3-吡啶羟基)-联苯胺),并测定了其晶体结构。1属于正交晶系,Pna2₁空间群,晶胞参数a=2.138 20(2) nm,b=0.990 60(1) nm,c=0.608 40(1) nm,V=1.288 65(3) nm³,Z=4,R₁=0.023,wR₂=0.067。2属于三斜晶系,P1空间群,晶胞参数a=0.810 2(3) nm,b=0.997 9(4) nm,c=1.270 5(5) nm,α=86.282(6)°,β=73.517(5)°,γ=89.107(6)°,V=0.982 9(7) nm³,Z=2,R₁=0.082,wR₂=0.160 2。配合物1为三维结构,其中五配位的铜为扭曲的四方锥构型。配合物2展示了由车轮状二铜结构单元连接而成的非互穿的三维网络结构。     

Ce-MCM-48介孔分子筛的合成、表征和催化性能

尝试以混合模板剂pH调节水热合成掺入铈的介孔分子筛CeMCM48,并采用X射线衍射、高分辨透射电镜、紫外可见漫反射、X射线荧光光谱、氮气吸附脱附测试手段对样品进行表征.结果表明,新合成的掺铈介孔材料仍保持立方介孔的有序结构,有序性及吸附性能得到改善.所合成的掺铈的立方介孔分子筛对环己烷的液相氧化反应的催化活性和选择性较高.CeMCM48催化环己烷氧化反应的转化率较MCM48催化的转化率提高了8.3%～14.2%,对主要产物的选择性提高了63.4%～68.8%.     

吡嗪基联吡啶锌配位聚合物的结构及发光性质

以2,6-双(2-吡嗪基)-4,4'-联吡啶为配体,对苯二甲酸为辅助配体,水热条件下合成了锌配位聚合物[Zn(dpb)(p-bdc)]n·0.5n(dpb),并用元素分析、红外光谱、X射线单晶衍射对此配位聚合物进行了测试分析.单晶结构解析表明,它是通过对苯二甲酸桥连锌离子形成一维链结构的配位聚合物.此外,对配体及配位聚合物的荧光进行了研究.     

Research on the direct amination of benzene to aniline by NiAlPO4–5 catalyst

A series of NiAlPO₄–5 molecular sieves have been hydrothermally synthesized and shown high and stable activity in the direct amination of benzene to aniline with hydroxylamine hydrochloride as aminating agent. The as‐synthesized and calcined samples were investigated with XRD, SEM, TG, BET, NH₃‐TPD and FT‐IR to explore the crystalline, coordination and location of the incorporated transition metal ions. The results indicated that nickel ions were incorporated into the framework of AlPO₄–5 and the as‐synthesized catalysts were highly crystalline, and possessed good thermal stability. Among them, Ni(0.3)AlPO₄–5 showed the highest catalytic activity for the direct amination of benzene with the highest aniline yield of 73.2% and 100.0% selectivity to aniline. After the catalyst was reused for 5 times, the activity remained little change.     

RADIATION DEGRADATION OF CHITOSAN IN THE PRESENCE OF H2O2

INTRODUCTIONChitosan, poly-β-(1 -?4)-D-glucosamine, can be obtained from chitin by deacetylation with alkali. It is soluble indilute acidic medium due to the presence of amino groups. The use of chitosan in many areas, such as foodprocessing, biochemistry, Pharmaceuticals, medicine, and agriculture has been developed over the pastdecades[1,2].In recent years, it has been reported that many properties of chitosan depend on the molecular weight[3]. Thechitosan oligomers possess better fun…     

硝基苯异氰酸酯的制备及模拟计算

通过构型优化、热力学分析、电荷分布分析等计算,从理论上确定了硝基取代苯胺进行异氰化反应的容易程度为间硝基苯胺对硝基苯胺邻硝基苯胺.在此基础上对以固体光气与邻、间、对硝基苯胺为原料分别合成邻、间、对硝基苯基异氰酸酯的工艺进行了研究.结果表明,以乙酸乙酯作为反应溶剂,合成邻、间硝基苯基单异氰酸酯的最佳反应时间为6h,合成对硝基苯基单异氰酸酯的最佳反应时间5h,邻硝基苯胺、对硝基苯胺与固体光气的最佳物质的量比均为2∶1,间硝基苯胺与固体光气的最佳物质的量比为2.2∶1.在上述反应条件下,邻、间、对硝基苯基单异氰酸酯的收率分别达75.5%,76.9%和77.1%,纯度分别达99.6%,99.16%和85.7%,实验结果与理论推断基本相符.     

Ce-MCM-48介孔分子筛的合成、表征和催化性能

Cerium incorporated MCM-48 molecular sieves have been hydrothermally synthesized by both a mixed template and a variable pH approach. The samples were characterized by various physicochemical methods, including X-ray diffraction, transmission electron microscopy, diffuse reflectance UV-vis spectroscopy, XRF spectroscopy, nitrogen adsorption. These results reveal that cerium is incorporated in MCM-48 in the form of well-dispersed tetra-coodinated cerium ion. Maintaining the proper concentration of cerium and adjusting the pH allows for a more ordered structure with a much higher specific surface area than that of MCM-48. Ce-MCM-48 was employed in the liquid phase oxidation of cyclohexane with aqueous H2O2. The results showed that Ce-MCM-48 is more active as a catalyst for the liquid phase oxidation of cyclohexane. The oxidation conversion catalyzed by Ce-MCM-48 is 8.3 %-14.2% higher than that catalyzed by MCM-48 and the selectivity for the main products increase by 63.4%-68.8%. Accordingly, Ce-MCM-48 has been shown to have important potential applications.     

基于2,2＇,6,6＇-联苯四酸的两个新配位聚合物的水热合成与晶体结构

通过2,2＇,6,6’-联苯四酸与相应金属硝酸盐和第二配体的水热反应合成了2个具有不同结构的配位聚合物[Co(bta)0.5(2,2’-bipy)(H2O)]n(1)和{[Cd2,(bta)(H2biim)2(H2O)]·H2O}n(2)(H4bta=2,2’,6,6’-联苯四酸,2,2'-bipy=2,2’-联吡啶,H2biim=1H,1’H-2,2’-联咪唑),并测定了其晶体结构.1和2都是一维链结构,并且1和2都属于单斜晶系,P21/c空间群.bta配体在1和2中分别采取η6,μ4六齿和η5,μ4-五齿配位模式,同时bta配体中2个苯环的夹角在化合物1和2中分别是64.80°和64.86°.1与2分别在170℃和120℃以下保持热稳定性.     

Theoretical Study on the Catalytic Activity and Sulfur Resistibility of Amorphous Alloy Ni-B-P

In the present paper,one hundred cluster models NinBP (n=1～6) have been designed and studied by density functional theory (DFT) to get an insight into the local structure,catalytic properties and sulfur resistibility of amorphous alloy Ni-B-P. The configurations in triplet state are found more stable than those in the singlet state. It is found that as the content of Ni in the clusters increases,the value of Fermi level in clusters fluctuated,which shows that the content of Ni can influence the Fermi level to a certain extent. Based on the Fermi level and DOS,we consider the activity of catalyst in hydrogenation reaction is the best in cluster Ni3BP. On the basis of the charge of clusters NinBP (n=1～6),we conclude the amorphous alloy Ni-B-P with high Ni content has better sulfur resistibility and the best hydrogenation activity,strong sulfur resistibility appears in clusters Ni3BP,and the amorphous alloy Ni60B20P20 with similar proportion is expected to prepare in the future.     

二维钡配位聚合物[Ba( μ5-1，8-nap)]n的水热合成、晶体结构和荧光性质

通过水热法合成得到1个以1,8-萘二酸(1,8-nap)为配体的Ba(Ⅱ)配合物 [Ba(μ₅-1,8-nap)]_n(1)。X射线单晶衍射测定结果表明：配合物属于单斜晶系,空间群P2₁/c。配合物最小不对称单元由1个九配位的钡原子和1个1,8-萘二酸配体构成。每个1,8-萘二酸配体连接五个钡原子,每个钡原子连接五个1,8-萘二酸配体,在(100)平面上形成二维双层结构。此外,对配合物的固态荧光性质做了测定,结果显示其在紫光区有荧光发射。