Journal of Chemical Physics, Vol.103, No.18, 7897-7906, 1995
Chemisorption and Oxidation Reactions of Nickel Group Cluster Anions with N-2, O-2, CO2, and N2O
Reactions of nickel (Ni-n(-), n =3-10), palladium (Pd-n(-), n = 3-8), and platinum (Pt-n(-), n=3-7) cluster anions are investigated in a flow tube reactor. Rate coefficients are measured for reactions with N-2, O-2, CO2, and N2O. Reactions with O-2, CO2, and N2O have rates that are greater than 10% of the collision rate for most clusters of four atoms or larger, while N-2 reactions generally exhibit much lower reaction efficiencies. All the reactions studied show a strong dependence on cluster elemental composition. Many of the palladium cluster reactions are significantly faster than the corresponding nickel and platinum cluster reactions, while Ni-n(-) and Pt-n(-) have similar rate coefficients. Pt-6(-) is observed to have anomalously low rate constants for reactions with N-2, CO2, and N2O compared to neighboring platinum clusters sizes and the nickel and palladium hexamers. N-2, CO2, and O-2 reactions are generally association reactions with varying degrees of cluster fragmentation observed. N2O reactions result in sequential addition of O atoms to the cluster. The extent of cluster fragmentation for the various reagents can be correlated with the estimated exothermicities of the adsorption processes.
Keywords:TRANSITION-METAL CLUSTERS;ICOSAHEDRAL STRUCTURE;BINDING-ENERGIES;CHEMICAL CHARACTERIZATION;ELECTRONIC PROPERTIES;HYDROGENATED COBALT;INORGANIC OLIGOMERS;PALLADIUM CLUSTERS;PT(111) SURFACE;MOLECULAR-BEAM