ABSTRACT
Metal-organic frameworks (MOFs) are revolutionizing a spectrum of industries, from groundbreaking gas storage solutions to transformative biological system applications. The intricate architecture of these materials necessitates the use of advanced computational techniques for a comprehensive understanding of their molecular structure and prediction of their physical properties. Coarse-grained (CG) simulations shine a spotlight on the often-neglected influences of defects, pressure effects, and spatial disorders on the performance of MOFs. These simulations are not just beneficial but indispensable for high-demand applications, such as mixed matrix membranes and intricate biological system interfaces. In this work, we propose an optimized CG force field tailored for ZIF-8. Our work provides a deep dive into sorption isotherms and diffusion coefficients of small molecules. We demonstrate the structural dynamics of ZIF-8, particularly how it responds to pressurization, which affects its crystal structure and leads to local changes in aperture size and area. Emphasizing the game-changing potential of CG simulations, we explore the characteristics of amorphization in ZIF-8. Through computational exploration, we aim to bridge the knowledge gap, enhancing the potential applications of nanoporous materials for various applications.
ABSTRACT
Zeolitic-imidazolate framework-8 (ZIF-8), composed of a zinc center tetrahedrally coordinated with 2-methylimidazolate linkers, has garnered extensive attention as a selective filler for propylene-selective mixed-matrix membranes (MMMs). Recently, we reported an innovative and scalable MMM fabrication approach, termed "phase-inversion in sync with in situ MOF formation" (PIMOF), aimed at addressing the prevailing challenges in MMM processing. In this study, we intend to investigate the effect of additives, specifically sodium formate and 1,4-butanediol, on the modification of ZIF-8 filler formation within the polymer matrix in order to further improve the separation performance of the asymmetric MMMs prepared by the PIMOF. Remarkably, MMMs prepared with sodium formate as an additive in the coagulation bath exhibited an unprecedented C3H6/C3H8 separation factor of 222.5 ± 1.8 with a C3H6 permeance of 10.1 ± 0.3 GPU, surpassing that of MMMs prepared without additives (a C3 separation factor of 57.7 ± 11.2 with a C3 permeance of 22.5 ± 4.5 GPU). Our computational work complements the experimental investigation by studying the effect of ZIF-8 nanoparticle size on the specific surface interaction energy and apertures of ZIF-8. Calculations indicate that by having smaller ZIF-8 nanoparticles, stronger interactions are present with the polymer affecting the aperture of ZIF-8 nanoparticles. This reduction in aperture size is expected to improve selectivity toward propylene by reducing the permeability of propylene. These results represent a significant advancement, surpassing the performance of all previously reported propylene-selective MMMs and most high-quality polycrystalline ZIF-8 membranes. The notably enhanced separation performance primarily arises from the formation of exceedingly small ZIF-8-like particles with an amorphous or poorly crystalline structure, corroborated by our computational work.
