title: Revealing the dynamic structure of complex solid catalysts using modulated excitation X-ray diffraction.
abstract: X-ray diffraction (XRD) is typically silent towards information on low loadings of precious metals on solid catalysts because of their finely dispersed nature. When combined with a concentration modulation approach, time-resolved high-energy XRD is able to provide the detailed redox dynamics of palladium nanoparticles with a diameter of 2 nm in 2 wt % Pd/CZ (CZ = ceria-zirconia), which is a difficult sample for extended X-ray absorption fine structure (EXAFS) measurements because of the cerium component. The temporal evolution of the Pd(111) and Ce(111) reflections together with surface information from synchronous diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements reveals that Ce maintains Pd oxidized in the CO pulse, whereas reduction is detected at the beginning of the O2 pulse. Oxygen is likely transferred from Pd to Ce(3+) before the onset of Pd re-oxidation. In this context, adsorbed carbonates appear to be the rate-limiting species for re-oxidation.
authors.affiliation: Paul Scherrer Institut, 5232 Villigen PSI (Switzerland). davide.ferri@psi.ch.
authors.forename: Davide
authors.initials: D
authors.lastname: Ferri
authors.forename: Mark A
authors.initials: MA
authors.lastname: Newton
authors.forename: Marco
authors.initials: M
authors.lastname: Di Michiel
authors.forename: Gian Luca
authors.initials: GL
authors.lastname: Chiarello
authors.forename: Songhak
authors.initials: S
authors.lastname: Yoon
authors.forename: Ye
authors.initials: Y
authors.lastname: Lu
authors.forename: Jérôme
authors.initials: J
authors.lastname: Andrieux
keywords: X-ray diffraction; ceria; modulation; palladium; time-resolved studies