Adaptive Interfacial Recognition Through Proton‐Coupled Force Reconfiguration in MOF@COF Composites

ABSTRACT Achieving dynamic, in situ switchable molecular recognition in porous composites remains challenging due to the difficulty of precisely modulating interfacial noncovalent interactions at the atomic level. Here, we demonstrated that proton‐coupled interfacial force reconstruction served as a general and efficient regulatory strategy to control adsorption‐desorption behaviors in a metal‐organic framework (MOFs)‐based covalent organic framework (COF) composite, NH 2 ‐UiO‐66@COF‐TpDBA (NU@FC). Reversible protonation‐deprotonation at carboxyl sites induced precise redistribution of the interfacial noncovalent force field, thereby endowing switchable molecular capture and markedly improving the utilization efficiency of interfacial active sites, constructing a stimuli‐responsive adsorption platform featuring molecular capture and release. This atomic‐scale regulation, coupled with solvent‐ triggered microenvironment modulation, allowed adaptive recognition of polychlorinated biphenyls (PCBs) under diverse environments. Combined with the mechanically reinforced sheath‐tube‐protected solid‐phase microextraction device (STP‐SPME), this proton‐responsive interfacial regulation strategy was extended to an in situ, low‐cost, anti‐interference sample pretreatment system, achieving reliable identification and efficient extraction of trace organic pollutants from complex environmental matrices. Beyond device‐level performance, this study established proton‐coupled force reconstruction as a general design principle for constructing intelligently responsive MOF‐COF composites, bridging atomic‐scale interfacial modulation with expansive environmental analysis.