Exsolution of Metallic Ru Nanoparticles from Defective, Fluorite-Type Solid Solutions Sm₂Ru_xCe_2–xO₇ To Impart Stability on Dry Reforming Catalysts

A key challenge in the catalytic conversion of CH₄ and CO₂ into a synthesis gas (CO and H₂) via the dry reforming of methane (DRM) is the development of stable catalysts. We demonstrate that the reductive exsolution of metallic Ru from fluorite-type solid solutions Sm₂Ru_xCe_2–xO₇ (x = 0, 0.1, 0.2, 0.4) yields catalysts with high activity and remarkable stability for the DRM. The catalysts feature Ru(0) nanoparticles about 1–2 nm in diameter that are uniformly dispersed on the surface of the resulting oxide support. The exsolved material was investigated by synchrotron X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS at Ru, Sm, and Ce K-edges), Raman spectroscopy, and transmission electron microscopy. In situ XAS-XRD experiments revealed that the exsolution of metallic ruthenium is accompanied by a rearrangement of the oxygen vacancies within the lattice. The catalysts derived through exsolution outperform (stable over 4 days) the reference catalysts prepared by wetness impregnation and sodium borohydride reduction. The superior performance of the exsolved catalysts is explained by their high resistance to sintering-induced deactivation owing to the stabilizing metal–support interaction in this class of materials. It is also demonstrated that the Ru nanoparticles can undergo redissolution (in air at 700 °C)–exsolution cycles.