电化学及现场光谱电化学方法研究在质子介质中混合价H_nAs_2Mo_(18)O_(62)^(6-)(n=2,4,6,8)多阴离子簇的电还原行为

Electroreduction Behavior Studies of Mixed-Valence Heteropolyanion H_nAs_2Mo_(18)O_(62)^(6-)(n=2,4,6,8) in Proton Media by in-situ Electrochemical Spectroelectrochemical Method

以电化学及现场紫外可见近红外及现场红外光谱电化学方法对Dawson结构多阴离子簇As2 Mo18O6 -6 2在高氯酸酸化的乙腈溶液中的电还原过程进行了研究 ,结果表明 ,该多阴离子在质子介质中经历四步可逆的两电子还原反应 ,多阴离子簇的还原伴随着产物的质子化 ,质子化的位置在Mo—O—Mo桥键的桥氧上 ,由于质子化诱导极化作用使Mo

Electroreduction behavior of mixed-valence heteropolyanion H nAs 2Mo 18O 6- 62 with Dawson structure in acetonitrile solution containing perchloric acid was investigated by electrochemical and in-situ UV-visible-near-IR and in-sitr IR spectroelectrochemical method.The results indicate that the heteropolyanion undergoes four step reversible two electron reductions,the reduction is followed by the protonation of the products and the position of protonation is on the bridged oxygen of Mo-O-Mo bridge bond.Because of induced effect of protonation,the IR absorption of Mo=O moves to shorter wavelength(blue shift) and the intensity is increased.