On the effect of metal loading on the reducibility and redox chemistry of ceria supported Pd catalysts

• Published in: Physical chemistry chemical physics : PCCP Vol. 24; no. 4; pp. 2387 - 2395
• Main Authors: Clark, Adam H, Marchbank, Huw R, Thompsett, David, Fisher, Janet M, Longo, Alessandro, Beyer, Kevin A, Hyde, Timothy I, Sankar, Gopinathan
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 26.01.2022
• Subjects: Cerium oxides; Chemical Sciences; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Oxidation; Palladium; Passivity; Room temperature; Temperature; OXIDATION; NANOPARTICLES; CHEMICAL-STATE; WATER-GAS SHIFT; TEMPERATURE; SUBSTITUTED CEO2; RH; PROMOTION; CO; SCATTERING
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d1cp04654c

The effect of Pd loading on the redox characteristics of a ceria support was examined using Pd K-edge XAS, Ce L -edge XAS and X-ray diffraction techniques. Analysis of the data obtained from these techniques indicates that the onset temperature for the partial reduction of Ce(IV) to Ce(III), by exposure to H , varies inversely with the loading of Pd. Whilst the onset and completion temperatures of the reduction of Ce(IV) to Ce(III) are different, both samples yield the same maximal fraction of Ce(III) formation independent of Pd loading. Furthermore, the partial reduction of Ce is found to be concurrent with the reduction of PdO and demonstrated that the presence of metallic Pd is necessary for the reduction of the CeO support. Upon passivation by room temperature oxidation, a full oxidation of the reduced ceria support was observed. However, only a mild surface oxidation of Pd was identified. The mild passivation of the Pd is found to lead to a highly reactive sample upon a second reduction by H . The onset of the reduction of Pd and Ce has been demonstrated to be independent of the Pd loading after a mild passivation with both samples exhibiting near room temperature reduction in the presence of H .