We have systematically studied redox properties of two series of several dozen heteropoly acids （salts） and their derivatives with vanadium and rare-earth elements with Keggin and Dawson structures, e. g. LnHSiMo<...We have systematically studied redox properties of two series of several dozen heteropoly acids （salts） and their derivatives with vanadium and rare-earth elements with Keggin and Dawson structures, e. g. LnHSiMo<sub>12</sub>, SiMo<sub>12-n</sub>V<sub>n</sub>, M<sub>1.5</sub>PMo<sub>12</sub>, PMo<sub>12-n</sub>V<sub>n</sub>, PW<sub>(</sub>12-n<sub>V</sub><sub>n</sub>, Ln(PMo<sub>11</sub>)<sub>2</sub>, Sm(XMo<sub>11</sub>)<sub>2</sub> and P<sub>2</sub>Mo<sub>18-n</sub>V<sub>n</sub>, etc., and obtained their sequence of oxidation. It was found that there is a linear relationship between the reduction potentials of heteropoly anions and the derivatives of heteropoly anions with rare-earth elements with Keggin structure and nq<sup>2</sup> （n and q are the principal quantum number and charge of the central ion respectively）. On the basis of the electrostatic model the regularity of oxidation and reduction was rationalized.展开更多
基金Project supported by the National Natural Science Foundation of China.
文摘We have systematically studied redox properties of two series of several dozen heteropoly acids （salts） and their derivatives with vanadium and rare-earth elements with Keggin and Dawson structures, e. g. LnHSiMo<sub>12</sub>, SiMo<sub>12-n</sub>V<sub>n</sub>, M<sub>1.5</sub>PMo<sub>12</sub>, PMo<sub>12-n</sub>V<sub>n</sub>, PW<sub>(</sub>12-n<sub>V</sub><sub>n</sub>, Ln(PMo<sub>11</sub>)<sub>2</sub>, Sm(XMo<sub>11</sub>)<sub>2</sub> and P<sub>2</sub>Mo<sub>18-n</sub>V<sub>n</sub>, etc., and obtained their sequence of oxidation. It was found that there is a linear relationship between the reduction potentials of heteropoly anions and the derivatives of heteropoly anions with rare-earth elements with Keggin structure and nq<sup>2</sup> （n and q are the principal quantum number and charge of the central ion respectively）. On the basis of the electrostatic model the regularity of oxidation and reduction was rationalized.
