Active Palladium Structures on Ceria Obtained by Tuning Pd–Pd Distance for Efficient Methane Combustion

Abstract

Efficiently removing/converting methane via methane combustion imposes challenges on catalyst design: how to design local structures of a catalytic site so that it has both high intrinsic activity and atomic efficiency? By manipulating the atomic distance of isolated Pd atoms, herein we show that the intrinsic activity of Pd catalysts can be significantly improved for methane combustion via a stable Pd₂ structure on a ceria nanorod support. Guided by theory and confirmed by experiment, we find that the turnover frequency (TOF) of the Pd₂ structure with the Pd–Pd distance of 2.99 Å is higher than that of the Pd₂ structure with the Pd–Pd distance of 2.75 Å; at least 26 times that of ceria supported Pd single atoms and 4 times that of ceria supported PdO nanoparticles. The high intrinsic activity of the 2.99 Å Pd–Pd structure is attributed to the conductive local redox environment from the two O atoms bridging the two Pd²⁺ ions, which facilitates both methane adsorption and activation as well as the production of water and carbon dioxide during the methane oxidation process. This work highlights the sensitivity of catalytic behavior on the local structure of active sites and the fine-tuning of the metal–metal distance enabled by a support local environment for guiding the design of efficient catalysts for reactions that highly rely on Pt-group metals.