A mechanochemically synthesized Schiff-base engineered 2D mixed-linker MOF for CO2 capture and cationic dye removal

Abstract

Developing synthetic strategies for smart materials for the adsorption and separation of toxic chemicals is of great importance. Metal–organic frameworks (MOFs) have been proven to be outstanding adsorbent materials that possess excellent pollutant removal performances in wastewater treatment, including dye recycling. In this work, a neutral Cd(II) based 2D framework with a dual ligand strategy involving –OH functionalized 5-hydroxyisophthalic acid (5-OH-H₂IPA) and the amide decorated Schiff base ligand (E)-N′-(pyridin-4-ylmethylene)isonicotinohydrazide (L) has been synthesized by different synthetic routes and characterized by various analytical methods. Thus, crystals of {[Cd(5-OH-IPA)(L)]·CH₃OH}_n synthesized via diffusion (ADES-7D) and the phase pure bulk product synthesized by conventional reflux (ADES-7C) and the mechanochemical grinding method (ADES-7M) have been established using PXRD data of the respective product showing identical simulated SXRD data to those of ADES-7D. The mechanochemically synthesized ADES-7M possesses a better surface area and CO₂ adsorption capability compared to ADES-7C, which is also supported by electron microscopy and particle size measurements. Furthermore, ADES-7 can be used as an efficient adsorbent material for the reversible, selective adsorption (42–99%) and separation of the cationic dyes malachite green (MG), methyl violet (MV), methylene blue (MB), and rhodamine B (RhB) from the mixture of cationic/anionic dyes (methyl orange (MO) and bromocresol green (BCG)) in the aqueous phase. Specifically, ADES-7M possesses better dye capture capability compared to ADES-7C, even in the case of the bigger dye RhB with adsorption differences of 2.38 to 1.01 mg g⁻¹, respectively. The dye adsorption kinetics follows pseudo-second-order kinetics, and the dye adsorption isotherm fits well with the Langmuir/Freundlich adsorption isotherm models. The probable mechanism of adsorption involving the supramolecular interaction between the host MOF and the guest dye has also been proposed.