Thermally Crosslinked Hydrogen-Bonded Organic Framework Membranes for Highly Selective Ion Separation

The weak bonding energy and flexibility of hydrogen bonds can hinder the long-term use of hydrogen-bonded organic framework (HOF) materials under harsh conditions. Here we invented a thermal-crosslinking method to form polymer materials based on a diamino triazine (DAT) HOF (FDU-HOF-1), containing high-density hydrogen bonding of N-H⋯N. With the increase of temperature to 648 K, the formation of -NH- bonds between neighboring HOF tectons by releasing NH₃ was observed based on the disappearance of the characteristic peaks of amino groups on FDU-HOF-1 in the Fourier transform infrared (FTIR) and solid-state nuclear magnetic resonance (ss-NMR). The variable temperature PXRD indicated the formation of a new peak at 13.2° in addition to the preservation of the original diffraction peaks of FDU-HOF-1. The water adsorption, acid-base stability (12 M HCl to 20 M NaOH) and solubility experiments concluded that the thermally crosslinked HOFs (TC-HOFs) are highly stable. The membranes fabricated by TC-HOF demonstrate the permeation rate of K⁺ ions as high as 270 mmol m^-2 h^-1 as well as high selectivity of K⁺/Mg²⁺ (50) and Na⁺/Mg²⁺ (40), which was comparable to Nafion membranes. This study provides guidance for the future design of highly stable crystalline polymer materials based on HOFs.