Experimental and Computation Studies of the Reaction of Hydrogen Peroxide and Methyl Hydroperoxide on Molybdenum Hydrogen Bronze Surfaces

Molybdenum hydrogen bronze is a unique material that can react with both hydrogen and organic peroxides and render them harmless. During the course of the reaction, the color and electrical conductivity of this material changed dramatically. Using the color change, the reaction rate of molybdenum hydrogen bronze with hydrogen peroxide has been measured colorimetrically. The reaction rate was found to be first order with respect to both the color change and concentration of hydrogen peroxide. The adsorption and dissociation mechanisms were also studied on molybdenum oxide and hydrogen bronze surfaces by means of density–functional computations. On molybdenum oxide clusters, both hydrogen peroxide and methyl hydroperoxides adsorb molecularly and do not dissociate. However, on the hydrogen bronze surfaces, both compounds can dissociate through a pathway involving either H–O or O–O bond cleavage. The O–O dissociation pathway is only energetically favorable for the methyl hydroperoxide. The chemical reaction on the molybdenum hydrogen bronze surface is made possible by the increased electron density at the surface with respect to the oxide due to the contribution from the HOMO orbital.