The complete catalytic cycle of CO oxidation with N2O is shown to occur on Ptn+ (see scheme); for Pt7+ it involves six different elementary reactions. Poisoning of the catalyst by sequential addition of CO is observed. The extent of poisoning can be adjusted with the ratio of N2O and CO partial pressures.

The gas-phase reactions of hydrated electrons with carbon dioxide and molecular oxygen were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Both CO2 and O2 react efficiently with (H2O)n- because they possess low-lying empty pi* orbitals. The molecular CO2- and O2- anions are concurrently solvated and stabilized by the water ligands to form CO2(-)(H2O)n and O2(-)(H2O)n. Core exchange reactions are also observed, in which CO2(-)(H2O)n is transformed into O2(-)(H2O)n upon collision with O2. This is in agreement with the prediction based on density functional theory calculations that O2(-)(H2O)n clusters are thermodynamically favored with respect to CO2(-)(H2O)n. Electron detachment from the product species is only observed for CO2(-)(H2O)2, in agreement with the calculated electron affinities and solvation energies.

Hydrated vanadium cations V + (H 2 O) n , n ¼ 5-30, are stored in the collision-free environment of an FT-ICR mass spectrometer and their reactions due to absorption of black body radiation are studied. Besides the loss of water ligands, the clusters show two different intracluster redox reactions, whose branching ratios are strongly size-dependent. Oxidation to the +II state results in V(OH) + (H 2 O) n ions, and a concurrent release of atomic hydrogen. Alternatively V(OH) 2 + (H 2 O) n clusters can form leaving vanadium in the +III state, common in aqueous solutions, and simultaneously molecular H 2 evaporates from the cluster. This behavior reflects the properties of transition metals, and the ability of vanadium to form stable compounds in a variety of oxidation states, and differs from the previously studied intracluster reactions involving the hydrated monovalent main group metals Mg + and Al + . These only react to their preferred oxidation states, MgOH + and Al(OH) 2 + , respectively.

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Nanodroplets that contain hydrated electrons provide information complementary to standard radiolysis techniques. Although the reaction of hydrated electrons with acetonitrile was observed in solution 25 years ago, its product has only now been identified in a gas‐phase experiment as the hydrogen adduct. The picture shows a solvent‐stabilized radical anion, which is suggested as a reactive intermediate.