Classical Keggin intercalated into layered double hydroxides: facile preparation and catalytic efficiency in Knoevenagel condensation reaction

摘要

The family of polyoxometalate (POM) intercalated layered double hydroxides (LDHs) composite materials has shown great promise for the design of functional materials with numerous applications. It is known that intercalation of the classical Keggin polyoxometalate (POM) of [PW12O40]3- (PW12) into layered double hydroxides (LDHs) is very unlikely to take place by conventional ion exchange methods due to spatial and geometrical restrictions. In this paper, such intercalated compound of Mg0.73Al0.22(OH)2 [PW12O40]0.04•0.98H2O (Mg3Al-PW12) has been successfully obtained by adopting a spontaneous flocculation method. The Mg3Al-PW12 has been fully characterized using a wide range of methods (XRD, SEM, TEM, XPS, EDX, XPS, FT-IR, NMR, BET). XRD patterns of Mg3Al-PW12 exhibit no impurity phase usually observed next to the (003) diffraction peak. Subsequent application of the Mg3Al-PW12 as catalyst in Knoevenagel condensation reactions of various aldehydes and ketones with Z–CH2-Z‘ type substrates (ethyl-cyanoacetate and malononitrile) at 60 oC in mixed solvents (Vi-propanol:Vwater = 2 : 1) demonstrated highly efficient catalytic activity. The synergistic effect between the acidic and basic sites of the Mg3Al-PW12 composite proved to be crucial for the efficiency of the condensation reactions. Additionally, the Mg3Al-PW12 catalysed Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate demonstrated the highest turnover number (TON) of 47980 reported so far.