Insights into the Mechanism of Methanol Steam Reforming Tandem Reaction over CeO₂ Supported Single-Site Catalysts

We demonstrated how the special synergy between a noble metal single site and neighboring oxygen vacancies provides an "ensemble reaction pool" for high hydrogen generation efficiency and carbon dioxide (CO₂) selectivity of a tandem reaction: methanol steam reforming. Specifically, the hydrogen generation rate over single site Ru₁/CeO₂ catalyst is up to 9360 mol H₂ per mol Ru per hour (579 mL_H2 g_Ru^-1 s^-1) with 99.5% CO₂ selectivity. Reaction mechanism study showed that the integration of metal single site and O vacancies facilitated the tandem reaction, which consisted of methanol dehydrogenation, water dissociation, and the subsequent water gas shift (WGS) reaction. In addition, the strength of CO adsorption and the reaction activation energy difference between methanol dehydrogenation and WGS reaction play an important role in determining the activity and CO₂ selectivity. Our study paves the way for the further rational design of single site catalysts at the atomic scale. Furthermore, the development of such highly efficient and selective hydrogen evolution systems promises to deliver highly desirable economic and ecological benefits.