DMF‐Mediated Diffusion Regulation in Pyridine–Carboxylate Metal–Organic Frameworks Enables Efficient CHF 3 Capture

ABSTRACT The development of efficient, stable, and easily scalable adsorbents, which are designed for the recovery of high‐purity trifluoromethane (CHF 3 ) from industrial waste gas, faces significant challenges. Here, we present a solvent‐docking strategy for synthesizing a new metal–organic framework, PAIF‐101 (Pyridine–carboxylic acid‐based frameworks). This approach utilizes DMF molecular coordination to achieve sub‐angstrom precision in pore‐aperture tuning while simultaneously generating additional adsorption sites. The two methyl groups on the DMF molecule function like molecular vises, firmly anchoring CHF 3 and achieving benchmark CHF 3 /N 2 separation. PAIF‐101 shows the highest reported CHF 3 uptake (3.54 mmol g −1 ) to date, pronounced affinity at low pressures, and exceptional IAST selectivity (140). Density functional theory (DFT) calculations and molecular dynamics (MD) simulations revealed that modified DMF molecules within the pores play a crucial role in enhancing performance. Breakthrough experiments validate practical feasibility, producing high‐purity (≥ 99.5%) CHF 3 with a productivity of 1.53 mmol g −1 and sustaining excellent separation even at 60%RH. Notably, PAIF‐101 can be rapidly synthesized in scalable quantities via a simple reflux method, yielding around 5 grams per batch. Taken together, the outstanding separation performance, robust stability, and scalable synthesis of PAIF‐101 demonstrate its great potential for this challenging industrial separation.