RESUMO
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.
RESUMO
Functional neutral metal-organic frameworks (MOFs) {[M(5OH-IP)(L)]}n [M = Zn(II) for ADES-4; Cd(II) for ADES-5; 5OH-IP = 5-hydroxyisophthalate; L = (E)-N'-(pyridin-3-ylmethylene)nicotinohydrazide) have been synthesized by a diffusion/conventional reflux/mechanochemical method and characterized by various analytical techniques. Crystals were harvested by a diffusion method, and single-crystal X-ray diffraction (SXRD) analysis revealed that an adjacent [M2(COO)2]n ladder chain generates isostructural two-dimensional network motifs by doubly pillaring via L. The bulk-phase purity of ADES-4 and ADES-5 synthesized by a versatile synthetic approach has been recognized by the decent match of powder X-ray diffraction patterns with the simulated one. Both ADES-4 and ADES-5 showed selective adsorption of cationic dyes methylene blue (MB), methyl violet (MV), and rhodamine B (RhB) over anionic dye methyl orange (MO) from water with good uptake and rapid adsorption. Utilization of ADES-4 as a chromatographic column filler for adsorptive removal of individual cationic dyes as well as a mixture of dyes has been demonstrated from the aqueous phase. Interestingly, ADES-4 is reusable with good stability, and it showed a dye desorption phenomenon in methanol. The probable mechanism of cationic dye removal based on insight from structural information and plausible supramolecular interactions has also been explored. Both MOFs also showed efficient catalytic transformation of fructose and glucose into the high-value chemical intermediate 5-hydroxymethylfurfural of industrial significance.
