Study of the Reaction of Hydroxylamine with Iridium Atomic and Cluster Anions (n = 1-5).

Elucidating the multifaceted processes of molecular activation and subsequent reactions gives a fundamental view into the development of iridium catalysts as they apply to fuels and propellants, for example, for spacecraft thrusters. Hydroxylamine, a component of the well-known hydroxylammonium nitrate (HAN) ionic liquid, is a safer alternative and mimics the chemistry and performance standards of hydrazine. The activation of hydroxylamine by anionic iridium clusters, Irn- (n = 1-5), depicts a part of the mechanism, where two hydrogen atoms are removed, likely as H2, and Irn(NOH)- clusters remain. The significant photoelectron spectral differences between these products and the bare clusters illustrate the substantial electronic changes imposed by the hydroxylamine fragment on the iridium clusters. In combination with DFT calculations, a preliminary reaction mechanism is proposed, identifying the possible intermediate steps leading to the formation of Ir(NOH)-.