Gas-Phase Reactions of Nickel and Nickel Oxide Clusters with Nitrogen Oxides. 3. Reactions of Cations with Nitric Oxide

Abstract

A fast flow reactor−quadrupole mass spectrometer system coupled with a laser vaporization source is used to study the gas-phase reactions of nickel and nickel oxide cluster cations with nitric oxide. Pseudo-first-order bimolecular rate constants are reported for the reactions of NO with nickel and nickel oxide cluster cations and O2 reactions with nickel cluster cations. The product distributions indicate that several different reaction mechanisms occur between NO and Ni x + and Ni x O y +. Competing processes such as oxidation, NO addition, and replacement of oxygen with nitric oxide are observed to occur. Also, the presence of magic peaks in the distributions indicates unusually stable product cluster species.

Thermal Desorption and Reaction of NO Adsorbed on Rhodium Cluster Ions Studied by Thermal Desorption Spectroscopy

“…Moreover, the pseudo-first-order rate constant, k n , m , for the formation of Rh n + (NO) m from Rh n + (NO) m−1 and NO was obtained by the least-squares fitting method. The rate constants for Ni n O m + with NO have been reported by Vann et al 31 Hence, the rate constants for Rh n + with NO were calibrated by measuring the rate constant of Ni 7 O 8 + with NO in the same experiment. As shown in Figure 6, the rate constant tends to increase for small values of m, and decrease for large values of m with an increase in m. (See Table S1 in the SI.)…”

Formation, Structure, and Reactivity of Gaseous Ni2O2+

“…The average formal oxidation state of +2.5 adopted by the metals in M 2 O 2 + is energetically more favorable for iron, whereas nickel strongly prefers an oxidation state of +2 in its compounds 34. Vann et al also investigated the reactivity of Ni m O n + clusters towards NO, but could not clearly establish the occurrence of oxygen‐transfer processes 35…”

Mass Spectroscopy of Chemical Reaction of 3d Metal Clusters Involved in Chemical Vapor Deposition Synthesis of Carbon Nanotubes

“…On the other hand, there are a large number of studies being conducted on these clusters in the gas phase. [18][19][20][21][22][23][24] However, most of the present research is restricted to small clusters (less than 10 atoms) because the generation of large clusters is quite difficult. Generally, in a catalytic reaction, because a certain number of atoms or a local structure of a small particle has a catalytic activity, clusters with less than 10 atoms are slightly insufficient for specifying the catalytic reaction.…”