Highly enhanced cationic dye adsorption from water by nitro-functionalized Zn-MOF nano/microparticles and a biomolecular binder for improving the reusability

Abstract

Zinc metal–organic frameworks (Zn-MOFs) of phthalic acid (ZnPA) and nitro-phthalic acid (ZnNPA) microcrystalline particles were fabricated and utilized for the removal of organic cationic dyes (crystal violet (CV), methylene blue (MB) and rhodamine B (RhB)) from water. PXRD studies confirmed the formation of crystalline materials, and BET indicated the mesoporous structure. HR-SEM studies showed the rod and plate morphologies for ZnPA and ZnNPA, respectively. ZnPA revealed low adsorption of dyes (CV, 20%) whereas ZnNPA showed significantly enhanced dye adsorption (CV, 99%). In particular, ZnNPA exhibited higher adsorption of CV (99%) and MB dye (83%) compared to RhB (54%). Nevertheless, ZnNPA could not be reused due to strong adsorption of dyes. Hence, a natural binder was introduced by dipping ZnNPA into tea extract, which also showed high adsorption of CV and MB dyes. Kinetics of adsorption exhibited best fitting with the pseudo-second-order model, indicating strong interactions between the dyes and adsorbent. Adsorption isotherm fitting suggested a good correlation coefficient (R²) with the Freundlich model, suggesting multi-layer adsorption. Interestingly, ZnNPA showed high adsorption of CV and MB dyes across the pH range between 3.0 and 11.0. The binder-introduced ZnNPA adsorbent was easily regenerated and demonstrated three cycles of reusability without significant change in the dye adsorption. Thus, the present work indicated the role of functional groups in the ligand and binder for improving the dye adsorption characteristics of MOFs.