Correction to: Catalytic oxidation of hydrogen on platinum

Abstract

Using the thermochemical approach to interpret the kinetics of heterogeneous reactions and the mechanism of congruent dissociative decomposition of solids developed in the 1980s and (re)analyzing the experimental data avail- able in the literature over the last 90 years, a novel mecha- nism for the catalytic oxidation ofH2 by PtO2 is proposed. In place of the conventional Langmuir–Hinshelwood and Eley–Rideal adsorption reaction mechanisms, our model is based on the reactions: PtO2(s) ? 2H2 $ Pt(g) ? 2H2O and Pt(g) ? O2 $ PtO2(g) ? PtO2(s). The first reaction determines the kinetics of H2 oxidation and the second determines the kinetics of restoration of the PtO2 layer. Thermochemical consideration of kinetic features of this model enables (for first time in the history of this reaction) the enthalpy and equilibrium constants for H2 oxidation on platinumto be calculated. The results are in good agreement with experimental data. In addition, the proposed mecha- nism explains the origin of the surface-retexturing effect, the impact of autocatalysis, the influence of H2O vapor on oxidation rate, and the three-fold variation of the Arrhenius E parameter with temperature. This all convincingly dem- onstrates the value of the thermochemical approach in interpreting heterogeneous reactions. B.