Atomic Layer Deposition Overcoating Improves Catalyst Selectivity and Longevity in Propane Dehydrogenation

Propylene, a precursor for commodity chemicals and plastics, is produced by propane dehydrogenation (PDH). An increase in PDH yield via added catalyst activity, lifetime, or selectivity represents significant energy and economic savings. Using Pt dispersed on Al2O3 extrudate supports as a commercially relevant model system, we demonstrate that atomic layer deposition (ALD) metal oxide overcoats, used to tailor metal-active sites, can increase PDH yield and selectivity. We investigate the interplay of Pt loading, ALD overcoat thickness, and Al2O3 support surface area on PDH activity, selectivity, and catalyst stability to show that applying a 6-8 Å thick layer of Al2O3 on low-surface area Al2O3 supports of ∼90 m2/g surface area yields the optimal combination of stability and activity, while increasing propylene selectivity from 91 to 96%. Increased stability upon steaming deactivation occurs because the Al2O3 overcoat prevents the Pt nanoparticles from sintering. We speculate that the ALD overcoat selectively binds to the undercoordinated sites on the Pt nanoparticles, while leaving the more selective terrace sites available for dehydrogenation.