A Bipyridyl Covalent Organic Framework with Coordinated Cu(I) for Membrane C3 H6 /C3 H8 Separation

Small. 2023 Jul;19(30):e2300438. doi: 10.1002/smll.202300438. Epub 2023 Apr 8.

Abstract

Covalent organic frameworks (COFs) mixed matrix membranes (MMMs) combining individual attributes of COFs and polymers are promising for gas separation. However, applying COF MMMs for propylene/propane (C3 H6 /C3 H8 ) separation remains a big challenge due to COF inert pores and C3 H6 /C3 H8 similar molecular sizes. Herein, the designed synthesis of a Cu(I) coordinated COF for membrane C3 H6 /C3 H8 separation is reported. A platform COF is synthesized from 5,5'-diamino-2,2'-bipyridine and 2-hydroxybenzene-1,3,5-tricarbaldehyde. This COF possesses a porous 2D structure with high crystallinity. Cu(I) is coordinated to bipyridyl moieties in the COF framework, acting as recognizable sites for C3 H6 gas, as shown by the adsorption measurements. Cu(I) COF is blended with 6FDA-DAM polymer to yield MMMs. This COF MMM exhibits selective and permeable separation of C3 H6 from C3 H8 (C3 H6 permeability of 44.7 barrer, C3 H6 /C3 H8 selectivity of 28.1). The high porosity and Cu(I) species contribute to the great improvement of separation performance by virtue of 2.3-fold increase in permeability and 2.2-fold increase in selectivity compared to pure 6FDA-DAM. The superior performance to those of most relevant reported MMMs demonstrates that the Cu(I) coordinated COF is an excellent candidate material for C3 H6 separation membranes.

Keywords: covalent organic frameworks; cuprous coordination; mixed matrix membranes; propylene separation.