The hyper-crosslinked aniline polymer@MOFs hybrid materials reinforced with active ionic sites for efficient and fast Cr(VI) removal

Abstract

The adsorption of toxic metal ions by composite materials of metal–organic frameworks (MOFs) has attracted significant attention in recent years. In this work, a series of hybrid materials HPAN@M−x consisting of protonated hyper-crosslinked aniline polymer (HPAN) and MOFs were synthesized via the Friedel-Crafts reaction between aniline and dimethoxymethane in the presence of MIL-101(Cr), followed by protonation with hydrogen bromide. These hybrid materials exhibited enhanced adsorption rate and capacity for Cr(VI) ions compared to both individual MIL-101(Cr) and HPAN. The effects of the ratio of aniline to MIL-101(Cr), solution pH, adsorption temperature, impurity ions on the removal of Cr(VI) ions were systematically investigated. Notably, HPAN@M−b not only achieved an adsorption capacity up to 290.9 mg·g−1 in 7 min but also exhibited excellent cycling stability by maintaining a high Cr(VI) removal efficiency of 95.6 % after five cycles. The enhanced adsorption performance is attributed to the synergistic effect between MIL-101(Cr) and HPAN. Mechanism studies indicated that the removal for Cr(VI) ions involved a combination of ion exchange and electrostatic adsorption processes. Additionally, the desorbed Cr(VI) ions were transformed into added-value barium chromate (BaCrO4) precipitates, allowing for resource utilization of Cr(VI) ions. This study represents a significant advancement towards developing MOFs-based hybrid materials for practical treatment of chromium-containing wastewater.