Insights into the Adsorption of Carbon Dioxide in Zeolites ITQ-29 and 5A Based on Kinetic Measurements and Molecular Simulations

作者：Magdy Abdelghany Elsayed, Shixue Zhou, Xiaohui Zhao, Gumawa Windu Manggada, Zhongyuan Chen, Fang Wang, Zhijuan Tang · 发表于：Nanomaterials · 年份：2025 · DOI：10.3390/nano15141077 · 被引用次数：13 · 研究领域：Carbon Dioxide Capture Technologies、Zeolite Catalysis and Synthesis、Metal-Organic Frameworks: Synthesis and Applications

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 CO2 adsorption and diffusion behavior in LTA-type zeolites. The CO2 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 CO2 adsorption decreases from 40.35 to 21.75 kJ/mol with increasing coverage, reflecting heterogeneous interactions at Ca2+ 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 CO2 exhibited a −35 kJ/mol more negative adsorption energy in zeolite 5A than in zeolite ITQ-29, attributable to strong interactions with Ca2+/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 ...