X-ray absorption near-edge spectroscopy investigation of the oxidation state of Pd species in nanoporous SnO2 gas sensors for methane detection

We report the correlation of the aging of Pd-doped SnO2 methane sensors with the change of the oxidation state of Pd. Mesoporous SnO2 doped with palladium species was prepared and exposed to different gas mixtures at high temperature (600 degrees C) to simulate long term usage. After each exposure step a fraction of the sample was cooled down to freeze the current oxidation state of Pd which was then analyzed by X-ray Absorption Near-Edge Spectroscopy (XANES) using the 'white line' (i.e. the absorption peak corresponding to the transition from the 2p(3/2) core level to unoccupied 4 d states) intensity of the L(III) edge as a probe for the oxidation state. The Pd oxidation state correlates with the response of the resistive SnO2 sensor to methane gas, as determined by measuring the gas response to different concentrations of methane. Samples treated with 5000 ppm methane in air show a significant reduction of Pd(II) to Pd(0), depending clearly on the carrier gas (synthetic air, pure nitrogen) and on the temperature (600 degrees C vs. 300 degrees C). (C) 2011 Elsevier B.V. All rights reserved.