Precise molecular sieving of ethylene from ethane using triptycene-derived submicroporous carbon membranes

Hazazi, Khalid; Wang, Yingge; Ghanem, Bader; Hu, Xiaofan; Puspasari, Tiara; Chen, Cailing; Han, Yu; Pinnau, Ingo

doi:10.1038/s41563-023-01629-7

Cited by 37 publications

(6 citation statements)

References 59 publications

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“…All three CMS membranes show a molecular cut-off between 3.3 and 3.64 Å. Gas transport in CMS materials is usually described using the solution-diffusion model, where permeability is decoupled into gas solubility and diffusivity 5 , 18 . CO 2 and C 2 H 6 sorption isotherms were determined at 100 °C (Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

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Hierarchically porous and single Zn atom-embedded carbon molecular sieves for H2 separations

Hu,

Lee,

Roy

et al. 2024

Nat Commun

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Hierarchically porous materials containing sub-nm ultramicropores with molecular sieving abilities and microcavities with high gas diffusivity may realize energy-efficient membranes for gas separations. However, rationally designing and constructing such pores into large-area membranes enabling efficient H2 separations remains challenging. Here, we report the synthesis and utilization of hybrid carbon molecular sieve membranes with well-controlled nano- and micro-pores and single zinc atoms and clusters well-dispersed inside the nanopores via the carbonization of supramolecular mixed matrix materials containing amorphous and crystalline zeolitic imidazolate frameworks. Carbonization temperature is used to fine-tune pore sizes, achieving ultrahigh selectivity for H2/CO2 (130), H2/CH4 (2900), H2/N2 (880), and H2/C2H6 (7900) with stability against water vapor and physical aging during a continuous 120-h test.

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Section: Resultsmentioning

confidence: 99%

“…Pore structures of CMS membranes depend on precursor structures 2 , 5 , 18 , carbonization temperature ( T c ) 19 , and carbonization atmosphere 20 , 21 . The ultramicropore sizes can be reduced to precisely separate H 2 from other gases, which, however, lowers the H 2 permeability 5 , 13 , 20 , 22 .…”

Section: Introductionmentioning

confidence: 99%

Hierarchically porous and single Zn atom-embedded carbon molecular sieves for H2 separations

Hu,

Lee,

Roy

et al. 2024

Nat Commun

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“…Remarkably, increasing the fluorination time reduces the sizes of the micropores and ultramicropores, leading to an increase in membrane diffusivity selectivity. Additionally, the He/H 2 solubility disadvantage induced by H 2 ’s higher polarizability is overcome for the fluorinated HFMs, as the total amount of sorption and solubility coefficients of H 2 are reduced by excluding it from the submicropores [19a,e] …”

Section: Resultsmentioning

confidence: 99%

“…Fluorination of the CMS membranes benefits He/H 2 separation performance in three key ways: 1) It enhances molecular sieving and diffusivity selectivity. CMS membranes possess a hierarchically microporous architecture, with numerous micropores interconnected by ultramicropores and submicropores [19a–c,e] . Fluorination near or at the bottlenecks results in a substantial reduction in pore sizes and a dramatic improvement in entropically enabled diffusivity selectivity.…”

Section: Resultsmentioning

confidence: 99%

Precise Helium Sieving from Hydrogen Using Fluorine‐Decorated Carbon Hollow Fiber Membranes

Wu,

Liu,

Jiao

et al. 2024

Angew Chem Int Ed

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Separating helium (He) and hydrogen (H2), two gases that are extremely similar in molecular size and condensation properties, presents a formidable challenge in the helium industry. The development of membranes capable of precisely differentiating between these gases is crucial for achieving large‐scale, energy‐efficient He/H2 separation. However, the limited selectivity of current membranes has hindered their practical application. In this study, we propose a novel approach to overcome this challenge by engineering submicroporous membranes through the fluorination of partially carbonized hollow fibers. We demonstrate that the fluorine substitution on the inner rim of the micropore walls within the carbon hollow fibers enables tunability of the microporous architecture. Furthermore, it enhances interactions between H2 molecules and the micropore walls through the polarization and hydrogen bonding induced by C‐F bonds, resulting in simultaneous improvements in both He/H2 diffusivity and solubility selectivities. The fluorinated HFM‐550‐F‐1min membrane exhibits exceptional mixed‐gas separation performance, with a binary mixed‐gas He/H2 selectivity of 10.5 and a ternary mixed‐gas He/(H2+CO2) selectivity of 20.8, at 40 bar feed pressure and 35 oC, surpassing all previously reported polymer‐based gas separation membranes, and remarkable plasticization resistance and long‐term continuous stability over 30 days.

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“…The investigation of gas solubility behavior is a significant topic in several application fields like biological drug engineering, chemical engineering, and material science. − …”

Section: Introductionmentioning

confidence: 99%

Gas Solubility Modeling of Ethylene in Semicrystalline Polyethylenes with Different Macromolecular Architectures Based on a Thermomechanics Approach

Zimmermann,

Enders,

Fischlschweiger

2023

J. Chem. Eng. Data

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The solubility of gases in semicrystalline polymers is a significant property with numerous applications, such as gasphase polymerization. Although thermodynamic modeling has successfully determined gas solubility in glassy polymers or polymer melts without crystallites, predicting gas solubility in polymers with a semicrystalline morphology remains challenging. This study presents a novel multiscale modeling approach based on thermomechanics to predict gas solubility in semicrystalline polymers across different temperatures, pressures, and various grades of polyethylene. The thermomechanical framework incorporates the SL-EOS and continuum mechanics, utilizing a mechanical homogenization method to consider the semicrystalline morphology and obtain local mechanical material information. Additionally, the temperature dependence of the degree of crystallinity of polyethylene is considered. By employing this approach, the solubility of ethylene in different polyethylene grades in the semicrystalline state can be accurately predicted, demonstrating good agreement with experimental data with a relative error below 3%.

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Precise molecular sieving of ethylene from ethane using triptycene-derived submicroporous carbon membranes

Cited by 37 publications

References 59 publications

Hierarchically porous and single Zn atom-embedded carbon molecular sieves for H2 separations

Hierarchically porous and single Zn atom-embedded carbon molecular sieves for H2 separations

Precise Helium Sieving from Hydrogen Using Fluorine‐Decorated Carbon Hollow Fiber Membranes

Gas Solubility Modeling of Ethylene in Semicrystalline Polyethylenes with Different Macromolecular Architectures Based on a Thermomechanics Approach

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