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

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} 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.