Built‐In Electric Field in Charge‐Intercalated Catalysts: Excessive Electron Migration Stabilizes Zinc Active Sites for Propane Dehydrogenation

ABSTRACT Propane dehydrogenation (PDH) to propylene is constrained by the trade‐off between catalyst activity, selectivity, and stability, especially for non‐precious metals. Herein, a ZnAl‐layered double oxide/montmorillonite (ZnAl‐LDO/MMT) heterojunction catalyst is designed via interfacial electrostatic self‐assembly. A built‐in electric field (BIEF) is constructed at the heterointerface, which drives directional electron transfer. This unique configuration effectively inhibits the over‐reduction of Zn 2+ to volatile Zn 0 , thereby stabilizing the active centers. The optimal catalyst delivers a propane conversion of 69.61% with a propylene selectivity of 88.5% at 575°C, achieving a propylene space‐time yield (2.06 mmol·g −1 ·h −1 , normalized to the active component) that is ten times higher than that of the ZnAl‐LDO reference. Remarkably, it maintains stable performance over 55 reaction‐regeneration cycles. In situ characterizations, combined with density functional theory (DFT), reveal that the enhanced performance is consistent with the computational result of a 0.97 eV upshift in the d‐band center of ZnAl‐LDO upon compositing with MMT, which strengthens propane adsorption. In situ FT‐IR and Raman results suggest that interfacial engineering via the BIEF, likely promotes the formation of specific Zn─O X ─Si active sites, thereby selectively producing propylene while suppressing CO 2 formation at 300°C. This work reports a BIEF engineering strategy for designing non‐precious metal PDH catalysts, which demonstrates enhanced activity and stability.