Distribution and Transport of CO2 in Hyperbranched Poly(ethylenimine)-Loaded MCM-41: A Molecular Dynamics Simulation Approach.

Abstract

Fossil fuel use is accelerating climate change, driving the need for efficient CO2 capture technologies. Solid adsorption-based direct air capture (DAC) of CO2 has emerged as a promising mode for CO2 removal from the atmosphere due to its potential for scalability. Sorbents based on porous supports incorporating oligomeric amines in their pore spaces are widely studied. In this study, we investigate the intermolecular interactions and adsorption of CO2 and H2O molecules in hyperbranched poly(ethylenimine) (HB-PEI) functionalized MCM-41 systems to understand the distribution and transport of CO2 and H2O molecules. Density Functional Theory (DFT) is employed to compute the binding energies of CO2 and H2O molecules with HB-PEI and MCM-41 and to develop force field parameters for molecular dynamics (MD) simulations. The MD simulations are performed to examine the distribution and transport of CO2 and H2O molecules as a function of the HB-PEI content. The study finds that an HB-PEI content of approximately 34 wt % is thermodynamically favorable, with an upper limit of HB-PEI loading between 45 and 50 wt %. The distribution of CO2 and H2O molecules is primarily determined by their adsorptive binding energies, for which H2O molecules dominate the occupation of binding sites due to their strong affinity with silanol groups on MCM-41 and amine groups of HB-PEI. The HB-PEI content has a considerable impact on the diffusion of CO2 and H2O molecules. Furthermore, a larger number of water molecules (higher relative humidity) reduces the correlation of CO2 with the MCM-41 pore surface while enhancing the correlation of CO2 with the amine groups of the HB-PEI. Overall, the presence of H2O molecules increases the CO2 correlation with the amine groups and also the CO2 transport within HB-PEI-loaded MCM-41, meaning that the presence of H2O enhances the CO2 capture in the HB-PEI-loaded MCM-41. These findings are consistent with experimental observations of the impact of increasing humidity on CO2 capture while providing new, molecular-level explanations for the macroscopic experimental findings.