Synthesis of a 2D copper(II)-carboxylate framework having ultrafast adsorption of organic dyes

Abstract

Two-dimensional (2D) coordination polymers are very interesting materials for their attractive applications. A novel 2D metal-organic framework (MOF) was derived from copper(II) and amino benzoic acid under both room temperature and solvothermal reaction conditions using different solvents. From both of the synthesis methods, an identical MOF was crystalized with monoclinic crystal system having P21/c space group. Hirshfeld surface analysis is carried out to explore the non-covalent interactions obtained from single crystal XRD investigation in terms of percentage contribution of each interatomic contact involved in packing of molecules into MOF structure. The microstructure analysis and surface morphology studies revealed the 2D layered regular pattern of rhombus disks of ~5 μm thickness throng together via clustering of these rhombic shaped flakes as flowers (ranging 50–100 μm in size) having uniform elemental composition. This 2D MOF efficiently adsorbed organic dyes (methylene blue, methyl orange, and methyl red) from their aqueous solutions. The 2D copper-carboxylate framework (1.2 g/L) exhibited high adsorption rates for organic dyes (0.15–0.19 mM), and >90% of these dyes could be captured as soon as they are exposed to MOF suspension (1 min) in each case. The dye removal efficiency is credited to synergy among structure, ionic strength, shapes and dimensions of dyes with respect to MOF structure. The microstructure of MOF along with electronic interactions like electrostatic, hydrogen bonding, π-π interactions and coordination to open metal sites, might contribute to the ultrafast dye adsorption process by MOF. The adsorption phenomenon is spontaneous and followed the pseudo-second order kinetic mechanism. DFT calculations revealed important electronic parameters of the dyes and model MOF systems, and novel insights with respect to possible dye-MOF interactions. The MOF remained quite stable during the dye adsorption and was regenerated easily for the successful subsequent use.