A Layered Hydrogen-Bonded Organic Framework with C₃H₆-Preferred Pores for Efficient One-Step Purification of Methanol-to-Olefins (MTO) Products

Separation of methanol-to-olefins (MTO) products to obtain high-purity C₂H₄ and C₃H₆ is of great importance, since it provides an alternative process for such important industrial raw materials. However, developing adsorbents with high C₂H₄/C₃H₆ selectivity and productivity remains challenging. Herein, we report an ultrastable layered hydrogen-bonded framework (HOF-NBDA), which features C₃H₆ preferred pore with multiple interlaminar interactions with C₃H₆. It delivers an ultrahigh C₃H₆ uptake (3.6 mmol g^–1) at 10 kPa, while absorbs only 0.3 mmol g^–1 C₂H₄ and shows a high C₂H₄/C₃H₆ selectivity (11.1). Experimental breakthroughs show that HOF-NBDA can efficiently separate C₃H₆/C₂H₄ (50/50, v/v) at different flow rates, temperatures, as well as relative humidities and provides a high C2H4 productivity (5.7 mol kg^–1, purity ≥99.95%). Meanwhile, 4.5 mol kg^–1 C₃H₆ (purity ≥99.5%) can also be collected during the desorption process. Additionally, thanks to ultrahigh stability, good scalability, and easy regeneration, HOF-NBDA is considered as a promising material for one-step energy-efficient separation of MTO products.