Synthesis of mesoporous-structured MIL-68(Al)/MCM-41-NH2 for methyl orange adsorption: Optimization and Selectivity

Abstract

Here, we report a novel amino-modified mesoporous-structured aluminum-based metal-organic framework adsorbent, MIL-68(Al)/MCM-41-NH₂, for dye sewage treatment. The introduction of molecular sieves overcomes the inherent defects of microporous MOFs in contaminant transfer and provides more active sites to enhance adsorption efficiency. Compared with using organic amino ligands directly, this strategy is ten times cheaper. The composite was well characterized and analyzed in terms of morphology, structure and chemical composition. Batch experiments were carried out to study the influences of essential factors on the process, such as pH and temperature. In addition, their interactions and the optimum conditions were examined using response surface methodology (RSM). The adsorption kinetics, isotherms and thermodynamics were systematically elucidated. In detail, the adsorption process conforms to pseudo-second-order kinetics and follows the Sips and Freundlich isothermal models. Moreover, the maximum adsorption capacity Q_s of methyl orange (MO) was 477 mg g^-1. It could be concluded that the process was spontaneous, exothermic, and entropy-reducing. Several binary dye systems have been designed for selective adsorption research. Our material has an affinity for anionic pigments. The adsorption mechanisms were discussed in depth. The electrostatic interaction might be the dominant effect. Meanwhile, hydrogen bonding, π-π stacking, and pore filling might be important driving forces. The excellent thermal stability and recyclability of the adsorbent are readily noticed. After five reuse cycles, the composite still possesses a removal efficiency of 90% for MO. Overall, the efficient and low-cost composite can be regarded as a promising adsorbent for the selective adsorption of anionic dyes from wastewater.

Keywords: Adsorption mechanism; Dye removal; Metal-organic framework; Response surface methodology; Selective adsorption.