Water formation reaction on Pt(111): Near edge x-ray absorption fine structure experiments and kinetic Monte Carlo simulations

Abstract

The catalytic water formation reaction was investigated by the energy dispersive near-edge x-ray absorption fine structure (dispersive NEXAFS) spectroscopy. An oxygen covered Pt(111) surface with the (2×2) structure was exposed to gaseous hydrogen (5.0×10−9 Torr) at constant surface temperatures (120–140 K). O K-edge NEXAFS spectra were measured during the reaction with a time interval of 35 s. Quantitative analyses of the spectra provided the coverage changes of the adsorbed species (O, OH, and H2O). The reaction is composed of three steps, which are characterized by an induction period (I), fast increase in coverage of OH and H2O with consuming O (II), and slow conversion of OH to H2O after the complete consumption of O (III). It was also found that the maximum OH coverage becomes smaller at a higher temperature. The kinetic Monte Carlo simulation has reproduced the three characteristic reaction steps; in the first step OH domains are created through two-dimensional aggregation of H2O (I), after the nucleation process the second step sets in where the OH domains propagate by the autocatalytic cycle until they contact with each other (II), and finally the merged OH domains convert to H2O (III). The reaction diffusion method was also applied to this system. It explained the reaction behavior in a wide surface area.