Author affiliations
* Corresponding authors
a
State Key Laboratory of Materials-Oriented Chemical Engineering, Jiangsu National Synergetic Innovation Center for Advanced Material (SICAM), College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, China
E-mail:
[email protected]
b Advanced Materials Research Center and Department of Chemistry and Materials Science, School of Science, Xi'an Jiaotong-Liverpool University, Suzhou 215123, China
c Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore
Abstract
Crystalline supramolecular frameworks (SMFs) with high porosity are advantageous for propylene (C3H6) uptake and thus methanol to olefin (MTO) product separation. However, SMFs tend to transform into amorphous states and lose porosity upon activation, which limits the exploration of their performance. Herein, we for the first time report a new SMF, NUT-161 of high porosity, constructed from tri-nuclear zirconium clusters and 4,4′-(ethyne-1,2-diyl)dibenzoic acid (H2-EDBA), and reinforce its stability through a surface-confined polymerization of isophorone diisocyanate (IDI) on its crystal surface. The obtained NUT-161@PolyIDI maintained a significantly improved crystallinity, showing a 324% increment in specific surface area (2213 vs. 522 m2 g−1) compared to the activated pristine NUT-161. More importantly, the retention of high porosity enables NUT-161@PolyIDI to achieve better C3H6 adsorption performance with an increment of 249% at 273 K, and its separation potential has been conspicuously improved. Besides, the dynamic breakthrough studies demonstrate that NUT-161@PolyIDI exhibits well-maintained separation capacity over three cycles. Grand Canonical Monte Carlo simulation was used to illustrate the separation mechanism of NUT-161@PolyIDI, and the results suggest the framework exhibits multiple C–H⋯π interactions with C3H6, preferentially binding to C3H6 over ethylene (C2H4). This strategy may provide a solution to improve the crystallinity of porous materials for applications in various scenarios.
