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本文系统研究了Keggin结构和Dawson结构两大系列几十个杂多酸(盐)及其钒和稀土衍生物LnHSiMo_(12),SiMo_(12-n)V_n,M_(1.5)PMo_(12),PMo(12-n)V_n,PW_(12-n)V_n,Ln(PMon_(11))_2,Sm(XMon_(11))_2和P_2Mo_(13-n)V_n等在溶液中的氧化还原性质,得到了它们的氧化序。发现Keggin结构杂多阴离子及其稀土衍生物还原电势与nq~2线性相关(n,q分别为中心离子的主量子数和电荷)。根据静电模型对两大系列杂多化合物的氧化还原规律性给予了合理说明。
In this paper, two series of dozens of heteropolyacids (salts) and their vanadium and rare earth derivatives, such as LnHSiMo_ (12), SiMo_ (12-n) V_n and M_ (1.5) PMo_ The redox properties of PMo (12-n) V_n, PW_ (12-n) V_n, Ln (PMon_ (11)) _2, Sm (XMon_ (11)) _2 and P_2Mo_ (13-n) Got their oxidation order. It is found that the reduction potential of heteropolyanions of Keggin structure and their rare earth derivatives is linearly related to nq ~ 2 (n and q are the principal quantum number and charge of central ion, respectively). According to the electrostatic model of the two series of heteropoly compounds redox regularity given a reasonable description.