Nanoplasmonic Probes of Catalytic Reactions

Plasmonic Probing of Catalysis An understanding of catalytic reactions on surfaces, such as those used in industrial processes, often requires some measure of reactant concentration on the surface. Often this is expressed as the surface coverage of metal particles that are dispersed on oxide supports. Although optical probes of surface coverage would be convenient, they usually lack sufficient sensitivity to detect the small number of molecules on the surface. Larsson et al. (p. 1091, published online 22 October) have used shifts in plasmon resonances to measure surface coverages. They grow oxide coatings, decorated with metal catalyst particles, on a nanoscale gold disk, and find that these model catalysts are within the region of plasmon sensitivity. Reactions such as CO oxidation on platinum can be followed for different ratios of reactant gases with a sensitivity of 0.1 monolayer of surface coverage. Reactant concentrations can be measured as plasmon frequency shifts for model catalysts grown on nanoscale gold disks. Optical probes of heterogeneous catalytic reactions can be valuable tools for optimization and process control because they can operate under realistic conditions, but often probes lack sensitivity. We have developed a plasmonic sensing method for such reactions based on arrays of nanofabricated gold disks, covered by a thin (~10 nanometer) coating (catalyst support) on which the catalyst nanoparticles are deposited. The sensing particles monitor changes in surface coverage of reactants during catalytic reaction through peak shifts in the optical extinction spectrum. Sensitivities to below 10−3 monolayers are estimated. The capacity of the method is demonstrated for three catalytic reactions, CO and H2 oxidation on Pt, and NOx conversion to N2 on Pt/BaO.