杂多化合物催化性能的研究—第四周期过渡金属取代的钼磷三元杂多化合物在环己烯氧化反应中的催化作用

The Catalytic Behaviour of Molybdophosphates Substituted by Transition Metal of Fourth Period in the Oxidation of Cyclohexene with H 2O 2

过渡金属单取代的杂多化合物［（ｎ－Ｃ４Ｈ９）４Ｎ］８－ｎ［ＰＺｎ＋ＢｒＭｏ１１Ｏ３９］（Ｚ＝Ｍ２＋ｎ、Ｆｅ３＋、Ｃｏ２＋、Ｎｉ２＋、Ｃｕ２＋）对以过氧化氢为氧化剂的环己烯氧化反应具有良好的催化性能．基于动力学、红外光谱及电化学方法的研究，对反应机理作了讨论．认为这类取代的杂多化合物与Ｈ２Ｏ２作用形成了活性中间体，活性中心为参与取代的过渡金属离子．

The heteropolyoxometalates mono substituted by transition metal, such as [( n C 4H 9) 4N] 8 n ·[PZ n+ BrMo 11 O 39 ] (Z=Mn 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ ), show good catalytic activity for the oxidation of cyclohexene using H 2O 2 as oxidant. On the basis of the results of kinetics, IR spectra and electrochemistry studies, the reaction mechanism was discussed. It is suggested that the substituted heteropolyoxometalate reacts with H 2O 2 to form an intermediate, and the substituted transition metal ion seems to be the center of activating H 2O 2.