Adsorption Mechanism of Nitrogen in CNT-Reinforced Silica Aerogels: A Molecular Dynamics Insight

Silica aerogels are ideal candidates for gas adsorption due to their exceptional porosity and high specific surface area; however, the inherent mechanical fragility of their skeletal framework significantly compromises their operational stability in engineering applications. While the incorporation of carbon nanomaterials effectively enhances the mechanical robustness of aerogels, the specific microscopic mechanisms by which filler microstructure and surface chemistry dictate gas adsorption behavior remain insufficiently understood. In this study, we employed all-atom molecular dynamics (MD) simulations to develop a model of silicon-based porous composites synergistically doped with carbon nanotubes (CNTs) and graphene. The adsorption and diffusion characteristics of nitrogen (N2) were systematically investigated across a CNT doping concentration range of 5% to 20%, and the influence of surface hydrophilicity/hydrophobicity on adsorption performance was quantitatively analyzed by modulating potential energy parameters. Our results demonstrate that the introduction of CNTs reconfigures the porous architecture, leading to an approximately 18.25% increase in the normalized specific surface area, which subsequently drives a 15% enhancement in the overall adsorption capacity of the composite. Nevertheless, analysis reveals that the weight-specific adsorption efficiency of the CNT component itself exhibits a declining trend as the doping concentration increases. This phenomenon is primarily attributed to the convex curvature of the CNTs, which restricts the effective contact area and weakens the adsorption potential, alongside the steric hindrance effects arising from local filler agglomeration at higher concentrations. Furthermore, surface chemical properties exert a significant regulatory influence on adsorption; a strongly hydrophilic modified surface (λ = 1.5) achieved an adsorption capacity approximately 98% higher than the baseline condition—an improvement that exceeds the gains provided by purely physical volume expansion. This research elucidates the synergistic mechanism between physical architecture and surface chemical modification in the adsorption process, suggesting that while the physical architecture determines the abundance of potential adsorption sites, the surface chemistry governs the actual efficiency of site utilization. These findings provide critical theoretical insights for the future design of composite aerogel materials that balance structural stability with superior adsorption performance.