H4AsW18O62]7-, A novel Dawson heteropolyanion and two of its sandwich-type derivatives [Zn4(H2O)2(H4AsW15O56)2]18-, [Cu4(H2O)2(H4AsW15O56)2]1: cyclic voltammetry and electrocatalytic properties towards nitrite and nitrate

Magnesium can be reversibly deposited electrochemically from solutions of ethereal solvents, with Grignard reagents (RMgX) or complexes of Mg(AX3-nRn+1)2 stoichiometry as the electrolytes (A=Al, B; X=Cl, Br; R=alkyl or aryl groups). These processes are far from being simple reactions of the Mg/Mg++ couple, since the above electrolytes in solutions have complicated structures in which the ether molecules play an important stabilization role. In addition, Mg deposition processes in all of the above solutions are accompanied by adsorption phenomena. The surface chemistry of magnesium electrodes was studied in situ by FTIR spectroscopy, using an internal reflectance mode. The electrolyte solutions studied included tetrahydrofuran (THF) solutions of the RMgX electrolytes (R=butyl, ethyl, methyl benzyl, and X=Cl, Br); Mg(AlCl2BuEt)2; Mg(AlCl3Bu)2 and Mg(BPh2Bu2); Bu, Et, Ph=butyl, ethyl and phenyl groups, respectively. It was clear from these studies that Mg electrodes do not develop stable passivation in these solutions (i.e. formation of surface films). The nature of the adsorbed species in the above systems is discussed, based on the spectral results.