Dynamic‐FLPs Enabled by Orbital Hybridization Tuning: Boosting 100% CO Selectivity for Dilute CO 2 ‐to‐CO Conversion

ABSTRACT Frustrated Lewis pairs (FLPs) are ideal sites in catalytic reactions due to their acid‐base synergistic advantages. However, traditional static FLPs are prone to deactivation by active site occupation, coupled with insufficient synergistic effects and charge separation, making performance optimization challenging. Herein, a “p‐p orbital hybridization regulation” strategy is proposed to construct dynamic‐FLPs (DFLPs) via N‐doping in BiOBr, which synchronously induces local weak crystallinity and lattice asymmetry, significantly enhancing the built‐in electric field (B‐IEF). Synchrotron radiation, X‐ray photoelectron spectroscopy, and density functional theory calculations confirm that N substitutes O to form N–BiO 2 units, weakening the p‐p hybridization of Bi–O bonds and reducing the oxygen vacancy (Vo) formation energy from 1.80 eV to 0.31 eV. A dynamic cycle is constructed to stabilize dynamic‐FLPs (Bi 2 ⁺ acid sites‐O 2 − /Vo base sites); together, they synergistically disrupt lattice symmetry, increasing the B‐IEF intensity by 2.45 times (ΔE = 4.76 eV) and accelerating charge separation. Under 15% CO 2 atmosphere (simulating industrial exhaust gas), the BiOBr‐N 1 catalyst achieves a CO yield of 51.3 μmol·g − 1 ·h − 1 (7.1 times that of pure BiOBr) without sacrificial agents, maintaining 100% selectivity and 100 h long‐term stability. This study addresses the static deactivation issue of traditional FLPs, provides a new approach for the design of high‐performance catalysts, and holds great significance for the resource utilization of industrial exhaust gas.