Preparation of isoreticular MIL-101(Cr) based on pre- and post-synthetic strategy and study for carbon dioxide capture

Abstract

The functionalization of MIL-101(Cr) presents a formidable challenge when employing covalent bonds, due to the inherent difficulty of incorporating reactive organic groups into its structure. In this work, we have successfully synthesized MIL-101-CHO tagged with formyl by adopting a pre-synthetic strategy, utilizing 3‑hydroxy-1-oxo-1,3-dihydroisobenzofuran-5-carboxylic acid as the key ligand. Then the integrity of the formyl group and the phase purity of the resulting MIL-101-CHO were rigorously confirmed through FT-IR and 1H NMR characterization. Employing post-synthetic strategy, four amine-MOFs were prepared through cascade reaction of Schiff-base condensation and NaBH4 reduction. The CO2 adsorption properties of all isoreticular MIL-101(Cr) materials were thoroughly investigated. Notably, MIL-101-TAEA demonstrated exceptional performance, with the highest Qst 70.1 kJ/mol at low coverage, the best adsorption capability 2.34 mmol/g at 298 K under 1 bar CO2, and the selectivity 172 for CO2/N2. Furthermore, the good regenerability of MIL-101-TAEA was proved by the CO2 temperature swing adsorption tests. Ultimately, MIL-101-TAEA maintain 60 % performance for trace CO2 capture after 16 cycles under the mimic atmosphere conditions, showing its potential for practical applications in gas separation and capture technologies.