CO Capture Characteristics of Hyperbranched Poly(alkylene imine): A Molecular Dynamics Simulation Approach.

This study explores the CO capture characteristics of hyperbranched poly(ethylenimine) (HB-PEI) and poly(propyleneimine) (HB-PPI) through molecular dynamics simulations using density functional theory-calibrated force fields. Key features such as density, free volume, glass transition temperature, CO/HO distribution, and molecular diffusion are systematically investigated to elucidate structure-function relationships under dry and hydrated conditions. HB-PEI demonstrates a slightly higher density and lower free volume compared to HB-PPI yet shows superior CO capture due to the high amine concentration. Glass transition analysis indicates a higher thermal mobility in HB-PEI, enhancing the CO diffusivity. Pair correlation and coordination analyses confirm a stronger affinity of CO with primary and secondary amines, particularly in hydrated environments where water competes with CO for binding sites. Despite its more compact structure, HB-PEI outperformed HB-PPI in CO and HO transport, as confirmed by higher diffusion coefficients across all hydration levels. These findings highlight a critical balance among polymer architecture, amine accessibility, and hydration in designing next-generation solid amine sorbents for efficient direct air capture applications.