Controlling the Selectivity of Conjugated Microporous Polymer Membrane for Efficient Organic Solvent Nanofiltration

To realize selective separation of important small molecules in organic solvents with high permeability is highly desired but not attained yet, because it requires stringent control over selectivity in nanofiltration membranes. Here, a thiophene‐containing conjugated microporous polymer membrane, in which the pore size is finely tuned at the angstrom scale through postoxidation of the thiophene moieties, is reported. The successful modification is confirmed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and water contact angle, leading to obvious pore size reduction evidenced by nitrogen adsorption. Upon postmodification, the selectivity of the membrane can be effectively controlled. In the pristine membrane, the methanol permeance reaches 32 liters per square meter per hour per bar (L m−2 h−1 bar−1) with a molecular weight cut‐off (MWCO) of 800 g mol−1. Significantly, after in situ postmodification of thiophene moieties, the largest pore size is reduced from 1.73 to 1.48 nm, giving rise to a remarkable decrease of MWCO from 800 to 500 g mol−1, while the permeance of methanol still maintains as high as 21 L m−2 h−1 bar−1.