铈杂多配离子-水滑石超分子层柱材料ZnAl-Ce(PMoV)_2的插层组装、表征及催化性能  

Synthesis,Characterization and Catalytic Properties of Layered Double Hydroxide Pillared with Cerium Heteropoly Complex Ion

作　　者：蒋维[1] 莫桂娣[1] 金烈[1] 曾和平[2] 

机构地区：[1]茂名学院应用化学系,广东茂名525000 [2]华南师范大学化学系,广东广州510637

出　　处：《中国稀土学报》2007年第1期32-38,共7页Journal of the Chinese Society of Rare Earths

摘　　要：以十四酸根阴离子柱撑Zn-Al水滑石Zn0.77Al0.22(OH)2.0.22C13H27COO.0.81 H2O(记为ZnAl-14A)为预撑前体,在水溶液中用离子交换法将以2∶17缺位杂多酸根离子(P2Mo16VO61)11-记为(P Mo V)为配体的稀土杂多配阴离子Ce(P2Mo16VO61)219-(记为Ce(PMoV)2)插层组装到水滑石层板间,合成了一种具有大的层间距(3.37 nm)的超分子插层材料Zn0.77Al0.23(OH)2.0.0105[Ce(P1.9Mo15.7V1.1O61)2].0.011C13H27COO.0.83H2O(记为ZnAl-Ce(PMoV)2)。用ICP,IR,XRD和DTA对产物的组成和结构进行了表征。结果表明,该产物中Ce(PMoV)2配阴离子沿其长轴垂直于层板的方向分布于水滑石层间;产物具有规整的层状结构和热稳定性;产物对乙酸与正丁醇的酯化反应,二甘醇的脱水-环化反应和H2O2氧化环己烷的反应有良好的催化性能,且易于回收重复使用。Heteropoly complex anion, Ce （P2Mo16 VO61 ） 2^19- （abbreviated as Ce （PMoV）2） was intercalated into the interlayer space of ZnAl type layered double hydroxide through Zn0.77Al0.22 （ OH ）2· 0.22C13 H27 COO· 0.81H2O （abbreviated as ZnAl-14A） precursor in an aqueous solution by ion exchange and the pillared layered compound, Zn0.77Al0.23 （ OH）2· 0. 0105 [ Ce（P1.9Mo15.7V1.1O61 ）2]· 0.011 C13 H27COO· 0.83H20 （abbreviated as ZnAl-Ce（PMoV2）） with higher interlayer space （3.37 nm） was obtained. The composition, structure and properties of the pillared material were characterized by ICP, XDR, IR and DTA. The results show that myristic radical anion of ZnAl-14A precursor can be replaced by complex anion Ce（PMoV）2 under special controlled reaction conditions. The pillared hydrotalcite was in regular layered structure with good crystallinity and thermally stability （the temperature of the loss of the hydroxyl groups from the layer sheets was about 450 ℃ and the temperature of the decomposition of Ce （PMoV） 2 of ZnAl- Ce（PMoV）2 was about 350℃ ）. The orientation of the intercalated anion Ce （PMoV）2 was deduced. It was also found that the new material had good catalytic activity and selectivity for esterification of acetic acid with n-butyl alcohol （the conversion of acetic acid was 96%, and the selectivity of butylester acetate was 89%）, dehydration-cyclization of diethylene glycol （the conversion of dietylene glycol was 94%, and selectivity of 1, 4-Dioxane was 84% ） and oxidation of cyclohexane （the total yield of hexalin and anone was 39%, and the selectivity of hexalin was 71%）. ZnAlCe（PMoV）2 could be easily recovered and repeatedly used.

关 键 词：铈的杂多配离子 插层水滑石 合成 催化性能 稀土 

分 类 号：O611.4[理学—无机化学]