(NiV_(13)O_(38))^(7-)的电子结构和催化性质的探讨

Studies on the Electronic Structure and Catalytic Properties of Heteropoly Anion（NiV_(13)O_(38)）^(7-)

使用SCC－DV－Xα方法研究了高钒杂多化合物（NiV13O38）7-的电子结构，并探讨了它的催化性质·结果表明，（NiV13O38）7-是一种比Keggin结构更强的催化剂。分析了该阴离子中的键的强弱关系，认为配位数越少的氧与V形成的键越强．并分析了前线轨道HOMO，LUMO的组成，从而得出它的催化活性中心是Ni，V、一配位端氧，二、三配位桥氧，五配位中心氧的结论。

The electronic structure and catalytic properties of heteropoly anion with high content of vanadium （NiV_(13)O_(38)）^(7-) have been calculated for the first time by SCCDV-Xα method. The results show that （NiV_(13)O_(38)）7- is a better catalyst than anion of Keggin structure scuh as （PMo_(12)O_(40)）^(3-). The strength of bonds in （NiV_(13)O_(38)）^(x-) has been discussed, and a conclusion has obtained that the bonds which are formed by oxygen with vanadium are stronger if the number of coordination of oxygen is smaller. In addition, the distributions of frontier orbitals, the HOMO and the LUMO have been analysed and concluded that Ni, V, Ot (which coordination number is one), Ob (which coordination number is two or three), central oxygen (which coordination number is five) are all of the activity centres catalysis.