Molecular Design and Catalysis of Layred Zirconium Phosphonate

有机膦酸锆化合物的通式为Zr（O_3PR）_2，可以得到具有多种层状结构的晶体。本文研究了二维膦酸锆衍生物的制备和表征。本文还研究了两种复合膦酸锆（侧链和柱撑）的单晶结构，并用X射线衍射（XRD）、<13>C-、<31>P-MASNMR等方法进行了表征，它们是由磷酸锆或有机膦酸锆组成的层状结构。每个layr由平面的锆桥接通过膦酸酯基团交替以上和以下的Zr原子平面，在夹层区域中的双层的方式远离基底表面取向。以乙酸的酯化反应为反应体系，考察了膦酸锆的催化性能。当复合膦酸锆在单晶相中同时具有酸性和疏水性时，催化剂在反应介质中不溶胀，催化活性较高。复合材料变得可接近任何反应物分子并改善疏水性。

Zirconium organophosphonates, whose compounds have the general formula Zr(O_3PR)_2 can be obtained in crystalline forms with various layred structures. The preparation and characterization of two-dimensional zirconium phosphonate derivatives have been investigated. Two composite zirconium phosphonates (pendant and pillared) in single crystal phase have also been invesigated and characterized by XRD,_<13>C-, and _<31>P-MASNMR.These compounds are lamellar structures comprising zirconium phosphated or organophosphonates. Each layr consists of planes of zirconium bridged through phosphonate groups that alternate above and below the Zr atom planes, oriented away from the basal surfaces in a bilayred fashion in the interlayr region. The catalytic performance over zirconium phosphonate is evaluated by esterification of acetic acid. When the composite zirconium phosphonate is composed with an acidic function and with a hydrophobic function in single crystal phase, the catalytic activity showed a higher activity without swelling of the catalyst in the reaction media. The composite materials become accessible to any reactant molecule and improve hydrophobicity.