Reactions of laser-ablated platinum and palladium atoms with dioxygen. Matrix infrared spectra and density functional calculations of platinum oxides and complexes and palladium complexes

Journal Article · Thu Jul 15 04:00:00 EDT 1999 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp990823e· OSTI ID:682159

Bare, W D; Citra, A; Chertihin, G V; Andrews, L ^[1]

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1. Univ. of Virginia, Charlottesville, VA (United States). Dept. of Chemistry

The interaction of small gas molecules with bulk platinum and palladium is currently an area of intensive research. Much of this research has focused on the adsorption of these species (specifically O{sub 2}, N{sub 2}, and CO) on noble metal surfaces or on the catalytic reactions of such adsorbed species. Also important are the reactions of dissolved gases on platinum and palladium surfaces, specifically the reduction of dissolved dioxygen on electrodes in fuel cells. In the case of dioxygen, adsorption on platinum surfaces often leads to catalytic dissociation of the dioxygen molecule. Platinum and palladium atoms produced by laser ablation were reacted with dioxygen diluted in argon during condensation at 10 K. Reaction products, including the M(O{sub 2}) and (O{sub 2})M(O{sub 2}) complexes prepared with thermal metal atoms, and the platinum oxides PtO, OPtO, PtO{sub 3}, OOPtO, and (O{sub 2})PtO, were analyzed by matrix infrared spectroscopy. Absorptions due to PdO and OPdO were not identified. Density functional theory (B3LYP) calculations were performed on product molecules, which were identified on the basis of isotopic frequency shifts and correlation with density functional calculations. The most interesting new molecule produced here, linear OPtO, can also be produced by photolysis of the cyclic Pu(O{sub 2}) complex.

• OSTI ID: 682159
• Journal Information: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 28 Vol. 103; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

Related Subjects

30 DIRECT ENERGY CONVERSION
ADSORPTION
DISSOCIATION
ELECTRODES
FUEL CELLS
OXYGEN
PALLADIUM
PLATINUM
PLATINUM OXIDES
SORPTIVE PROPERTIES