Temperature-dependent gas-surface chemical kinetic model for methane ignition catalyzed by in situ generated palladium nanoparticles

A temperature-dependent gas-surface kinetic model for methane oxidation over palladium is proposed. Thermodynamic data for the surface species (O, H, OH, H2O, and CO) are derived from statistical mechanic analysis using literature heats of desorption and vibrational frequencies. The rate parameters in the model also satisfy thermo-kinetic constraints. The hydrogen oxidation submodel is validated against literature stagnation flow reactor experiments at 1300 K and 13 Pa. The current model is further tested against catalytic methane ignition in a laminar flow reactor at atmospheric pressure, and with time-resolved measurements of the size distribution of palladium nanoparticles generated in situ from an aerosol containing palladium acetate. The improved gas-surface model predicts closely the experimental data. The role of palladium nanoparticles in enhancing methane ignition is attributed to heat release due to catalytic methane oxidation over distributed nanoparticle surfaces, leading to a temperature rise and thus an accelerated gas-phase chain-branching process.