新型层柱微孔材料ZnAl-XW_9Cu_3(X=Si^(4+),Ga^(3+))的合成、表征及其酯化活性研究

Synthesis, Characterization and Catalytic Activity of New Layered Microporous Materials ZnAl-XW 9Cu 3(X=Si 4+ ,Ga 3+ )

采用水热合成与离子交换法，合成了过渡金属铜三取代的Ｋｅｇｇｉｎ结构杂多阴离子ＸＷ９Ｃｕ３（Ｘ＝Ｓｉ４＋，Ｇａ３＋）柱撑ＺｎＡｌ型硝酸根阴离子粘土．元素分析、ＸＲＤ和ＩＲ对产物的组成和结构测试结果表明，被嵌入到阴离子粘土层间的杂多阴离子仍保持其原有的Ｋｅｇｇｉｎ结构，而阴离子粘土的层间距却从０８９ｎｍ增大到１４６ｎｍ．ＥＳＲ结果表明，ＧａＷ９Ｃｕ３进入粘土层间后，由于层板的影响，ＣｕＯ６八面体中Ｃｕ—Ｏ键的离子性有所增强．催化实验结果表明，柱撑产物对乙酸与正丁醇的酯化反应具有较高的催化活性和极高的选择性．

The tungstosilic and tungstogallic heteropolyanions trisubstitufed with transition metal coppor XW 9Cu 3(X=Si 4+ ,Ga 3+ ) have been incorporated into the interlayer of ZnAl-NO 3 type anion clay by means of hydrothermal ion-exchange. The measurement results of elamentary analysis, XRD and IR showed that the Keggin structure of the gallery heteropolyanions was maintained and the new pillared anion clay with basal spacing of 1 46±0 01 nm was obtainted. ESR indicated that because of influence of layered region polar of Cu—O bond in CuO 6 Octahedron was heightened in a degree after GaW 9Cu 3 were intercalated into the interlayer. Catalytical tests exhibit that the intercalated derivetives have higher catalytic activity and very high selectivity for esterification reaction of acetic acid with n-butanol.