Reaction of O2 with hydroxylamine or its salts over a number of supported gold catalysts containing Au nanoparticles (at 10–70 � C) has been studied at atmospheric pressure for the in situ generation of H2O2 (required for organic oxidation reactions in the synthesis of fine/specialty chemicals) in aqueous (water) or non-aqueous medium. Hydrogen peroxide in high yields with harmless by-products (viz. water and nitrogen) can be generated in situ by the reduction of O2 by hydroxylammonium sulfate (or chloride) or hydroxylamine using the supported gold catalysts particularly Au/Gd2O3, Au/La2O3 and Au/MgO, in aqueous (water) or non-aqueous (viz. methanol) medium at close to ambient conditions. The reduction of O2 by hydroxylammonium salt to H2O2, however, requires preneutralization of the salt by alkali; in the absence of the neutralization, only water is formed in the reaction. � 2006 Elsevier B.V. All rights reserved.