There have been many works analyzing thermionic currents and chemicurrents generated on various electrolyte-free metal/semiconductor nanostructures. More recently, the chemicurrent phenomenon was reported for mesoporous Pt/semiconductor systems adept at converting surface-released chemical energy into a stationary electrical signal at room-temperature conditions. The present work points out the existence of an entire class of such surface-driven functional nanosystems. Here, the reaction current generation of Pt/ZrO2 systems was studied at room temperature under exposure to oxyhydrogen environments for mesoporous zirconia; this nanostructure was capable of the continuous oxidation of hydrogen, producing a long-standing stationary current. Synthesis parameters during the anodization process were manipulated to control sample pore density and the average pore diameter. Deposited via wide-angle PVD sputtering, the Pt phase forms an electrically continuous topographical nanomesh layer, and thus the Pt/ZrO2/gas interface is regulated through the manipulation of zirconia porosity. We observed reaction current enhancements with increasing porosity due to the lengthening of the Pt/ZrO2 interface. The most porous sample was significantly more sensitive to initial hydrogen additions, pointing toward the spillover of positive ionic charge across the Pt/ZrO2 interface as the origin of the observed electromotive force.
Keywords: electrolytic oxidation; hydrogen spillover; mesoporous zirconia; oxyhydrogen; reaction current.