Abstract
Understanding the adsorption mechanism is essential for developing efficient technologies to capture carbon dioxide from industrial flue gases. In this work, laboratory measurements, density functional theory calculations, and molecular dynamics simulations were employed to study CO(2) adsorption and diffusion behavior in LTA-type zeolites. The CO(2) adsorption isotherms measured in zeolite 5A are best described by the Toth model. Thermodynamic analysis indicates that the adsorption process is spontaneous and exothermic, with an enthalpy change of -44.04 kJ/mol, an entropy change of -115.23 J/(mol·K), and Gibbs free energy values ranging from -9.68 to -1.03 kJ/mol over the temperature range of 298-373 K. The isosteric heat of CO(2) adsorption decreases from 40.35 to 21.75 kJ/mol with increasing coverage, reflecting heterogeneous interactions at Ca(2+) and Na(+) sites. The adsorption kinetics follow a pseudo-first-order model, with an activation energy of 2.24 kJ/mol, confirming a physisorption mechanism. The intraparticle diffusion model indicates that internal diffusion is the rate-limiting step, supported by a significant reduction in the diffusion rate. The DFT calculations demonstrated that CO(2) exhibited a -35 kJ/mol more negative adsorption energy in zeolite 5A than in zeolite ITQ-29, attributable to strong interactions with Ca(2+)/Na(+) cations in 5A that were absent in the pure silica ITQ-29 framework. The molecular dynamics simulations based on molecular force fields indicate that CO(2) diffuses more rapidly in ITQ-29, with a diffusion coefficient measuring 2.54 × 10(-9) m(2)/s at 298 K, whereas it was 1.02 × 10(-9) m(2)/s in zeolite 5A under identical conditions. The activation energy for molecular diffusion reaches 5.54 kJ/mol in zeolite 5A, exceeding the 4.12 kJ/mol value in ITQ-29 by 33%, which accounts for the slower diffusion kinetics in zeolite 5A. There is good agreement between experimental measurements and molecular simulation results for zeolite 5A across the studied temperature and pressure ranges. This confirms the accuracy and reliability of the selected simulation parameters and allows for the study of zeolite ITQ under similar simulation conditions. This research provides insights into CO(2) adsorption energetics and diffusion within LTA-type zeolite frameworks, supporting the rational design of high-performance adsorbents for industrial gas separation.