Single‐Atom Pt with Significantly Boosted Performance by Mesoporous Hollow Ceria Support for Dehydrogenation of Methylcyclohexane

Methylcyclohexane/toluene (MCH/TOL) is a promising liquid organic hydrogen carrier (LOHC) due to their low toxicity and compatibility with existing fossil fuel infrastructure. Developing high-performance and economical catalysts for H₂ release from MCH is crucial for practical applications. Previously reported Pt single-atom catalysts (SACs) with loading up to 0.15 wt% are either nearly inactive or exhibit limited cycloalkane dehydrogenation conversions under realistic space velocities. Here, we successfully synthesized mesoporous hollow ceria-supported Pt SACs (Pt₁/mh-CeO₂) with tunable Pt loadings of 0.1-0.75 wt%, which operate efficiently under carrier-gas-free industrial conditions. At 0.25 wt% Pt loading, an exceptionally high hydrogen evolution rate of 4705 mmol·g_Pt ^-1·min^-1 can be obtained near the kinetic region (25% MCH conversion). Under a more realistic condition with 94% conversion, the same catalyst still affords high apparent hydrogen evolution rate of 3106 mmol·g_Pt ^-1·min^-1 with good stability, markedly surpassing previously reported Pt catalysts. The significantly boosted performance of Pt SACs by mesoporous hollow ceria is attributed to (i) accessible Pt single-sites, (ii) enhanced mass transfer for large C₆-ring molecules with kinetic sizes smaller than the pore dimensions, and (iii) promoted MCH adsorption/activation on isolated Pt sites anchored on ceria with rich oxygen vacancies, as evidenced by vapor diffusion experiment and dynamics simulations.