Sorption mechanisms and enhancement of selected organochlorine pollutants in water on zeolites

Abstract

Tis study investigates the adsorption capacities of selected organochlorines on zeolites, focusing on hexachlorobenzene (HCB), hexachlorotetradecane (HCTD), hexachlorodecane (HCD), hexachlorocyclohexane (HCH), heptachlorodecane (HPCD), octachlorodecane (OCD), dichlorodiphenyltrichloroethane (DDT), and octachlorotetradecane (OCTD). Te structures of the organochlorines were optimized and their Frontier molecular orbitals were calculated. Te analysis of HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energies provided insights into the molecules’ electron-donating and -accepting capabilities. Te present research identifed the universal force feld as suitable for the investigation and used it to evaluate the adsorption capacities of the pollutants on various zeolites. It was found that CLO (a cubic microporous gallophosphate) demonstrated the highest adsorption capacity for HCB among 245 zeolites, with a loading capacity of 65.84 wt%. In terms of molecules adsorbed per cell, CLO remained the highest with 120 molecules per cell for HCB, 113 molecules per cell for HCH, 43 molecules per cell for DDT, 21 molecules per cell for HCTD, 19 molecules per cell for OCTD, 47 molecules per cell for HCD, 30 molecules per cell for HPCD, and 22 molecules per cell for OCD. Te analysis revealed correlations between the structural parameters of zeolites (mass, density, HVF, APV, VSA, GSA, DPS, and Di) and their adsorption capacities. Te investigation delved into cluster models to understand the interaction of organochlorines with the zeolite framework. Te study explored the impact of doping CLO zeolite with diferent atoms (Al, Si, and Na) on adsorption capacity. Te results showed that doping with aluminum improved both loading capacity and adsorption energy and dissociate the chlorinated compounds during adsorption. Quantum chemical calculations show that hydrogen-based bonding of the organochlorides on the CLO is thermodynamically favorable compared to dissociative adsorption. In addition, oxygen atoms in the zeolites provide active adsorption sites. In the present work, laboratory adsorption experiments were performed, treating zeolites with heat at 400 °C. Surprisingly, untreated zeolites outperformed treated ones, adsorbing up to 91% of HCB, while treated zeolites reached saturation after the third run. Te study attributed the better performance of untreated zeolites to the presence of interstitial water and hydrogen atoms, which are critical for electrostatic interactions with organic compounds. In general, this research provides a comprehensive analysis of the adsorption capacities of organochlorines on zeolites, combining computational simulations and laboratory experiments. Tis work’s distinctive quality is its methodology that combines molecular simulations, experimental verifcation, doping, and interstitial water efects. Te fndings emphasize the importance of zeolite (a high-porosity nanostructured material) structure, composition, and treatment methods in determining their efectiveness as adsorbents for environmental pollutants.