Molecular‐Level Insights into Interfacial Adsorption Mechanisms of PFOA on Functional Dolomite Surfaces via AIMD and Spectroscopy

ABSTRACT Understanding interfacial adsorption mechanisms at the molecular level is essential for designing next‐generation functional materials. Herein, we engineer thermally modified dolomite (DL) surfaces to enable selective capture of perfluorooctanoic acid (PFOA) and uncover the atomistic basis of interaction using a synergistic combination of ab initio molecular dynamics (AIMD) simulations and experimental spectroscopy. Calcination induces structural transformations in DL, yielding Ca(OH) ₂ and Mg(OH) ₂ surface phases that promote hydrogen bonding‐driven adsorption despite electrostatic repulsion. AIMD simulations reveal that post‐calcination surfaces exhibit enhanced electrostatic anchoring and charge‐mediated complexation, validating a previously unresolved interfacial adsorption mechanism. Experimental results corroborate these findings, with PFOA uptake following pseudo‐second‐order kinetics and Langmuir behavior, achieving equilibrium within 4–5 h and removal efficiencies of up to 94%. While the adsorption capacity remains moderate (2.16–2.58 mg g ^{− 1} ), the study demonstrates how natural minerals can be functionally tuned at the atomic scale to enhance interfacial reactivity. These insights advance the rational design of mineral‐based functional interfaces for selective molecular capture.