Highly propylene-selective asymmetric mixed-matrix membranes by polymer phase-inversion in sync with in-situ ZIF-8 formation

Hua, Yinying; Park, Sung-Hwan; Choi, Gyeong Min; Jung, Hwanyup; Cho, Kie Yong; Jeong, Hae‐Kwon

doi:10.1016/j.cej.2023.143048

Cited by 10 publications

(12 citation statements)

References 43 publications

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“…3.7 μm of PIMOF_0.6SF). The enhanced C3 gas separation performance of PIMOF_0.6SF can be attributed to (1) increased filler loading and (2) more restricted linker swing motion, reducing the effective aperture of the ZIF-8-like fillers as compared to the PIMOF_MMMs without additives . Due to the accelerated nucleation, a large number of small amorphous/poorly crystalline ZIF-8-like particles form in the skin layers of the PIMOF_SF MMMs.…”

Section: Resultsmentioning

confidence: 99%

“…This is mainly due to the considerable challenges of producing asymmetric MMMs in either hollow fiber or flat sheet forms by the conventional blending methods . Recently, our group has reported two novel in situ MMM processing methods, the first-generation polymer-modification-enabled in situ MOF formation (PMMOF) , and second-generation phase-inversion in sync with MOF formation (PIMOF) . The PMMOF, based on the chemical modification of polyimide, not only facilitated the in situ formation of asymmetric MMMs but also led to the creation of the first MMM hollow fiber modules .…”

Section: Introductionmentioning

confidence: 99%

“…106.9 and C 3 H 6 permeance of ca. 7.5 GPU) . Though impressive, further enhancements are highly desirable to augment the recovery and purity of propylene through membrane-based C3 separation processes.…”

Section: Introductionmentioning

confidence: 99%

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Unexpectedly High Propylene/Propane Separation Performance of Asymmetric Mixed-Matrix Membranes through Additive-Assisted In Situ ZIF-8 Filler Formation: Experimental and Computational Studies

Hua,

Mohamed,

Choi

et al. 2024

ACS Appl. Mater. Interfaces

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Zeolitic-imidazolate framework-8 (ZIF-8), composed of a zinc center tetrahedrally coordinated with 2methylimidazolate 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 C 3 H 6 /C 3 H 8 separation factor of 222.5 ± 1.8 with a C 3 H 6 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.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Unexpectedly High Propylene/Propane Separation Performance of Asymmetric Mixed-Matrix Membranes through Additive-Assisted In Situ ZIF-8 Filler Formation: Experimental and Computational Studies

Hua,

Mohamed,

Choi

et al. 2024

ACS Appl. Mater. Interfaces

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“…Polymers are predominantly employed as membrane materials due to their cost-effectiveness and moderate selectivity, but they exhibit a permeability–selectivity trade-off known as the Robeson upper bound . To address this limitation, ongoing research explores diverse polymer modifications. , A promising approach involves incorporating filler materials, resulting in composite membranes, so-called mixed-matrix membranes (MMMs). , These composite membranes consist of a polymer matrix integrated with fillers like metal–organic frameworks (MOFs) and zeolite nano/microparticles. The strategic combination of these porous materials with high permeability and selectivity holds the potential to surpass the upper bound and achieve commercially appealing outcomes.…”

Section: Introductionmentioning

confidence: 99%

“…6 To address this limitation, ongoing research explores diverse polymer modifications. 7,8 A promising approach involves incorporating filler materials, resulting in composite membranes, so-called mixed-matrix membranes (MMMs). 9,10 These composite membranes consist of a polymer matrix integrated with fillers like metal−organic frameworks (MOFs) and zeolite nano/microparticles.…”

Section: ■ Introductionmentioning

confidence: 99%

2D MOFs and Zeolites for Composite Membrane and Gas Separation Applications: A Brief Review

Kim,

Choi,

Lee

et al. 2023

ACS Mater. Au

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Commercial membranes have predominantly been fabricated from polymers due to their economic viability and processability. This choice offers significant advantages in energy efficiency, cost-effectiveness, and operational simplicity compared to conventional separation techniques like distillation. However, polymeric membranes inherently exhibit a trade-off between their permeability and selectivity, which is summarized in the Robeson upper bound. To potentially surpass these limitations, mixed-matrix membranes (MMMs) can be an alternative solution, which can be constructed by combining polymers with inorganic additives such as metal−organic frameworks (MOFs) and zeolites. Incorporating high-aspect-ratio fillers like MOF nanosheets and zeolite nanosheets is of significant importance. This incorporation not only enhances the efficiency of separation processes but also reinforces the mechanical robustness of the membranes. We outline synthesis techniques for producing two-dimensional (2D) crystals (including nanocrystals with high aspect ratio) and provide examples of their integration into membranes to customize separation performances. Moreover, we propose a potential trajectory for research in the area of high-aspect-ratio materials-based MMMs, supported by a mathematical-model-based performance prediction.

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Advancing Membrane Technology: Ordered Macroporous ZIF‐67 as a Filler in Mixed Matrix Membranes for Enhanced Propylene/Propane Separation

Poloneeva,

Datta,

Sicat

et al. 2024

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Conventional separation technologies for valuable commodities require substantial energy, accounting for 10%–15% of global consumption. Mixed‐matrix membranes (MMMs) offer a promising solution by combining processable polymers with selective inorganic fillers. Here, the potential of using ordered microporous structured materials is demonstrated as MMM fillers. The use of ordered macroporous ZIF‐67 in combination with the well‐known 6FDA‐DAM polymer leads to superior performance in the important separation of propylene from propane. The enhanced performance can be rationalized with the help of advanced microscopy, which demonstrates that the polymer is able to penetrate the macroporous network around which the MOF (Metal‐Organic Framework) is synthesized, resulting in a much better interphase between the two components and the homogeneous distribution of the filler, even at high loadings.

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Highly propylene-selective asymmetric mixed-matrix membranes by polymer phase-inversion in sync with in-situ ZIF-8 formation

Cited by 10 publications

References 43 publications

Unexpectedly High Propylene/Propane Separation Performance of Asymmetric Mixed-Matrix Membranes through Additive-Assisted In Situ ZIF-8 Filler Formation: Experimental and Computational Studies

Unexpectedly High Propylene/Propane Separation Performance of Asymmetric Mixed-Matrix Membranes through Additive-Assisted In Situ ZIF-8 Filler Formation: Experimental and Computational Studies

2D MOFs and Zeolites for Composite Membrane and Gas Separation Applications: A Brief Review

Advancing Membrane Technology: Ordered Macroporous ZIF‐67 as a Filler in Mixed Matrix Membranes for Enhanced Propylene/Propane Separation

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