CO₂-Induced Reverse Lattice Oxygen Spillover on Pt/CeO₂ Enables Sulfur-Resistant Dry Reforming of Methane

Overcoming sulfur poisoning in dry reforming of methane (DRM), which is a critical process for biogas upgrading, is particularly challenging. In this study, we illustrate that a reverse lattice oxygen spillover (RLOS) from CeO₂ to Pt on the Pt-O-Ce interface, induced by CO₂, can oxidize S into SO₂, aiding in the removal of S deposits. A low oxygen migration barrier at the Pt-O-Ce interface and Pt's high activity for oxidizing sulfur to SO₂ make Pt/CeO₂ uniquely effective at self-recovering after H₂S poisoning. Furthermore, the atomically dispersed Pt/CeO₂ catalyst undergoes reaction driven adaptive restructuring, which amplifies the RLOS effect and enables dynamic S deposition and removal. As a result, the catalysts maintain constant DRM activity for 100 h, even in the presence of H₂S. This discovery paves the way for designing catalysts that resist sulfur poisoning in H₂S-containing streams.