CO ₂ ‐Driven Synthesis of Holey Edge‐Carboxylated Graphene for Tunable Electronic Interactions in Cu–CeO ₂ ‐Catalyzed Water‐Gas Shift Reaction

Graphene, notable for its high specific surface area, is ideal for catalyst support but faces challenges under harsh thermal catalytic conditions. Here, edge‐carboxylated graphene with a controlled specific surface area was synthesized from graphite and CO 2 via ball‐milling and applied to the water‐gas shift reaction, aiming to expand its applicability in thermal catalysis. CO 2 thermal treatment produced functionalized holey graphene, adjusting specific surface area and enhancing active material dispersion. Experimental results revealed that catalytic activity depends on Cu dispersion and its valence state, which can be controlled through electronic metal–support–carbon interactions facilitated by C=O functional groups. Furthermore, control over Cu + species, acting as reaction mediators due to surface‐exposed Ce, was vital for catalyst stability and performance improvement. This study offers key insights into the use of carbon‐based materials for thermal catalysis and helps clarify the mechanisms of multicomponent catalyst systems combining metal and carbon.