REACTION OF NITRIDES OF MOLYBDENUM AND TUNGSTEN WITH HYDROGEN-PEROXIDE TO FORM INORGANIC PROTON CONDUCTORS

Reactions of nitrides of Mo, W, V, and Ti with hydrogen peroxide, espe cially Mo and W, were investigated. The reactions were characterized b y elemental analysis, NMR, IR, Raman, XPS, TOF mass, and TG/DTA spectr oscopy and titration of ammonia and peroxo group. The major oxometalat e species in reaction solution for Mo and W were [MoO(O-2)(2)(OOH)](2) (2-) and [W2O3(O-2)(4)(H2O)(2)](2-), respectively. As for the nitrogen -containing species, ammonium ions were initially formed, followed by the nitrate ions. Protons formed by the reaction take part in the form ation of ammonia. The removal of unreacted hydrogen peroxide and the e vaporation to dryness resulted in the formation of isopolymetalates. T he peroxooctamolybdate, peroxododecatungstate, and decavanadate were s uggested to be formed. Among them, the peroxopolytungstate was the mos t thermally stable and provided homogeneous thin films. The films show ed protonic conductivity and the logarithm of conductivity changed lin early with the relative humidity or the inverse of the temperature.