CO ₂ ‐Induced Reverse Lattice Oxygen Spillover on Pt/CeO ₂ Enables Sulfur‐Resistant Dry Reforming of Methane

Abstract

ABSTRACT 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 CeO 2 to Pt on the Pt‐O‐Ce interface, induced by CO 2 , can oxidize S into SO 2 , 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 SO 2 make Pt/CeO 2 uniquely effective at self‐recovering after H 2 S poisoning. Furthermore, the atomically dispersed Pt/CeO 2 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 H 2 S. This discovery paves the way for designing catalysts that resist sulfur poisoning in H 2 S‐containing streams.