On the Selectivity and Self-Diffusion of CO₂ and H₂ in Mixed-Layer Zeolitic-Imidazolate Frameworks

Abstract:

Zeolitic-imidazolate frameworks (ZIFs) have shown promise in gas separation through membranes. Nevertheless, the potential of mixed-layer ZIFs to be tailored for targeted gas separation remains largely unexplored. This study aims to fill this research gap through a Molecular Dynamics (MD) study by proposing two molecular models for mixed-layer ZIFs and evaluating their effectiveness in H₂ and CO₂ separation. MD simulations are conducted to validate and assess the diffusion properties of H₂ and CO₂ within the mixed-layered ZIF models. The results demonstrate that H₂ has higher diffusivity than CO₂ within the proposed ZIF models. Mixed-layer ZIF-8/ZIF-7 exhibits higher diffusion coefficients for both H₂ (4.79 × 10^-9 m²/s) and CO₂ (8.13 × 10^-11 m²/s) compared to pure ZIF-8, attributed to increased pore flexibility from the ZIF-7 layer. However, this enhancement in diffusion comes at the cost of reduced selectivity due to broader pore size distribution. In contrast, mixed-layer ZIF-8(Zn)/ZIF-8(Co) demonstrates a substantial increase in H₂ diffusion (5.17 × 10^-9 m²/s) and an exceptional selectivity of 310.00 for H₂ over CO₂, owing to the altered framework flexibility from incorporating different metal ions. The study further explores the effect of different adsorbate molecular models, revealing that the H₂_COMPASS and CO₂_TRAPPE combination yields the highest H₂/CO₂ selectivity. Additionally, increased molecular loading enhances diffusion. These findings underscore the critical role of structural modifications and molecular model selection in optimizing ZIF-based materials for gas separation applications. The proposed models and simulation results offer a foundation for future studies and the development of efficient and sustainable gas capture technologies.

• Periodical: Materials Science Forum (Volume 1153)
• Pages: 123-135
• DOI: https://doi.org/10.4028/p-zbdGN9
• Online since: June 2025
• Authors: Krsna Anand, Mohamad Rezi Abdul Hamid, Mohd Farid Ismail, Wan Azlina Wan Abdul Karim Ghani, Musab Abdul Razak*
• Keywords: Gas Diffusion, Mixed-Layer, Molecular Dynamics, Selectivity, ZIFs

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