Hierarchical Affinity Engineering in Amine-Functionalized Silica Membranes for Enhanced CO₂ Separation: A Combined Experimental and Theoretical Study

Excessive carbon dioxide (CO₂) emissions represent a critical challenge in mitigating global warming, necessitating advanced separation technologies for efficient carbon capture. Silica-based membranes have attracted significant attention due to their exceptional chemical, thermal, and mechanical stability under harsh operating conditions. In this study, we introduce a novel layered hybrid membrane designed based on amine-functionalized silica precursors, where a distinct affinity gradient is engineered by incorporating two types of amine-functionalized materials. The top layer was composed of high-affinity amine species to maximize CO₂ sorption, while a sublayer with milder affinity facilitated smooth CO₂ diffusion, thereby establishing a continuous solubility gradient across the membrane. A dual approach, combining comprehensive experimental testing and rigorous theoretical modeling, was employed to elucidate the underlying CO₂ transport mechanisms. Our results reveal that the hierarchical structure significantly enhances the intrinsic driving force for CO₂ permeation, leading to superior separation performance compared to conventional homogeneous facilitated transport membranes. This study not only provides critical insights into the design principles of affinity gradient membranes but also demonstrates their potential for scalable, high-performance CO₂ separation in industrial applications.