Direct control of electron transfer to the surface-CO bond on a Pt/TiO2 catalytic diode

We study CO adsorption on a multilayer catalytic diode in which electron transfer at the metal-semiconductor (Pt/TiO(2)) junction is controlled by an applied external voltage. The multilayer diode structure enhances infrared absorption signals from CO molecules adsorbed on the small area Pt surface. We find that the diode behaves like a Schottky junction and that changes in electron transfer at the junction are directly correlated with reversible shifts in the vibrational frequency of adsorbed CO. Infrared polarization and incidence angle dependent studies show that the magnitude of vibrational frequency shift varies with orientation of the molecules being probed and increases with proximity to the Pt/TiO(2) interface. The results demonstrate the ability to control the metal-adsorbate bond through external electronic modifications of a metal-support junction. The catalytic diode can potentially provide control of the surface chemical bond by an external voltage, providing a new approach for investigations in heterogeneous catalysis, sensors, and plasmonic devices.