Paired Framework Charges Enable Cationic Ptδ+ Sites for Ultralow-Loading Propane Dehydrogenation

Abstract Propane dehydrogenation (PDH) requires platinum (Pt) sites that couple high intrinsic activity with propylene selectivity, yet most Pt-based strategies that enhance selectivity rely on electronically modified metallic Pt and can compromise intrinsic rates. This paper describes a discovery that atomically dispersed, cationic Ptδ+ sites can be anchored on zincosilicate *BEA (CIT-6) via ion exchange at framework-derived paired negative charge environments. Transient measurements, (in situ) spectroscopic studies, kinetic analysis, and density functional theory calculations collectively show that Ptδ+ exhibits higher dehydrogenation activity than metallic Pt0, consistent with enhanced C–H bond polarization and facilitated C–H cleavage on electron-deficient centers. As a result, a 0.01 wt. % Ptδ+/CIT-6 catalyst achieves PDH activity comparable to a commercial (mimic) PtSnK/Al2O3 catalyst while using ∼30-fold less Pt. The same design concept extends to zincosilicate CHA and MFI frameworks, establishing framework-anchored positively charged Ptδ+ species as an active motif for Pt-efficient PDH catalysis.