具有16元环超大孔道磷酸钒化合物的水热合成及表征  

Hydrothermal Syntheses and Characterizations of Vanadium Phosphates with Extra-large 16-Ring Channels

作　　者：李莉[1] 颜岩[1] 王大明[2] 郑大方[1] 李激扬[1] 

机构地区：[1]吉林大学无机合成与制备化学国家重点实验室,长春130012 [2]吉林大学麦克德尔米德实验室,长春130012

出　　处：《高等学校化学学报》2014年第11期2285-2290,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21271081);新世纪优秀人才支持计划(批准号:NCET-11-0197)资助~~

摘　　要：分别以正丁胺、正丙胺和哌啶为模板剂,在水热条件下合成了具有超大孔穴的开放骨架磷酸钒化合物VPO-n(n=1,2,3),并对其进行了X射线衍射(XRD)、电感耦合等离子体光谱(ICP)、元素分析、热重分析(TG)、扫描电子显微镜(SEM)、X射线光电子能谱分析(XPS)及单晶结构解析等表征.XRD结果表明,VPO-n(n=1,2,3)与报道的超大孔磷酸钒化合物[HN(CH2CH2)3NH]K1.35[V5O9(PO4)2]·xH2O(简称VPO-DABCO)具有相同结构.对VPO-1的单晶结构解析表明,其结晶属于立方晶系,Im3m空间群,晶胞参数a=b=c=2.6586(3)nm,α=β=γ=90°,V=18.791(4)nm3.VPO-1的无机骨架具有三维交叉的8元环和16元环孔道,以及最大窗口为32元环的超大空穴.详细考察了不同模板剂对合成产物的影响,结果表明,不同的有机胺模板剂可以影响产物的形貌、结构对称性和晶胞参数,并对骨架中孔道的尺寸具有一定的调控作用.Using n-butylamine,n-propylamine and piperidine as templates or structure directing agents（ SDAs）,three new open-framework vanadium phosphates VPO-n（ n =1,2,3） were hydrothermally synthesized. These compounds were characterized by single-crystal and powder X-ray diffractions,ICP,elementary analysis,TGA,SEM and XPS analyses. VPO-1 crystallizes in the cubic system,space group Im3 m,with a =b = c = 2. 6586（ 3） nm,α = β = γ = 90°,V = 18. 791（ 4） nm^3. The structure of VPO-1 has 3D intersecting8-ring and extra-large 16-ring channels,as well as large cavities with 32-ring windows. VPO-n（ n = 1,2,3）are iso-structures,which are analogous to [HN（ CH2CH2）3NH]K1. 35[V5O9（ PO4）2]·H2O synthesized by triethylenediamine（ DABCO） as template. Structure comparison of these compounds indicates that the organic templates not only influence the symmetry and cell parameters of the crystal structure,but also can control the opening sizes and shapes of the channels and the cages in the resulting structures.

关 键 词：水热合成 磷酸钒 超大孔 有机模板剂 

分 类 号：O611.4[理学—无机化学]