Density functional theory insights into the solvent effect on the binding energies of Cd2+in functionalized MOFs

Abstract

The clean-up of cadmium-contaminated waters is a significant environmental issue, and metal–organic frameworks (MOFs) have been shown to be effective adsorbents with great potential. Yet, the basic principles driving Cd2+binding in multiple solvent environments remain enigmatic and hinder rational adsorbent design. In this work, the solvent effects on the binding energies of Cd2+, referring to (M = –NH2, –OH, –COOH, and –NO2), are systematically investigated using DFT in four solvents (water, ethanol, methanol, and acetonitrile). Using the SMD implicit solvation model and the M06-2X functional with def2-TZVP basis set, we demonstrate that solvent polarity significantly affects binding thermodynamics, with aqueous systems demonstrating 68–72% weaker binding than acetonitrile. With binding energies of −156.8 kcal mol−1(water), −187.3 kcal mol−1(ethanol), −181.4 kcal mol−1(methanol), and −198.5 kcal mol−1(acetonitrile), the carboxyl-functionalized MOF exhibits exceptional performance in all solvents. Protic solvents (1.18–1.24|e|) exhibit greater charge transfer than aprotic acetonitrile (0.94–1.08|e|), according to natural bond orbital analysis. This is explained by hydrogen bonding networks stabilizing charge-separated coordination states. Predictive relationships for mixed-solvent industrial wastewater applications are established by the significant linear correlation between binding energies and inverse solvent polarity (R2= 0.96–0.98). These results directly address the pressing need for efficient cadmium remediation technologies in a variety of aqueous-organic media by offering crucial theoretical guidance for the design of solvent-adaptive MOF adsorbents optimized for particular industrial effluent compositions.