Onset of High Methane Combustion Rates over Supported Palladium Catalysts: From Isolated Pd Cations to PdO Nanoparticles

[Image: see text] Industrial low-temperature methane combustion catalyst Pd/Al(2)O(3) suffers from H(2)O-induced deactivation. It is imperative to design Pd catalysts free from this deactivation and with high atomic efficiency. Using a small-pore zeolite SSZ-13 as support, herein we report well-defined Pd catalysts with dominant active species as finely dispersed Pd cations, uniform PdO particles embedded inside the zeolite framework, or PdO particles decorating the zeolite external surface. Through detailed reaction kinetics and spectroscopic and microscopic studies, we show that finely dispersed sites are much less active than PdO nanoparticles. We further demonstrate that H(2)O-induced deactivation can be readily circumvented by using zeolite supports with high Si/Al ratios. Finally, we provide a few rational catalyst design suggestions for methane oxidation based on the new knowledge learned in this study.