Separation of<scp>CH<sub>4</sub></scp>/<scp>N<sub>2</sub></scp>by an ultra‐stable metal–organic framework with the highest breakthrough selectivity

Miao, Chang; Wang, Fei; Yan, Wei; Yang, Qingyuan; Wang, Jie‐Xin; Liu, Dahuan; Chen, Jianfeng

doi:10.1002/aic.17794

Cited by 36 publications

(20 citation statements)

References 90 publications

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“…Considering the moderate IAST and kinetic selectivity of MIL‐120Al at 298 K, we believe that the excellent separation of CH 4 /N 2 on MIL‐120Al was controlled by the synergistic effect of the thermodynamic and kinetic factors (Scheme 1). From the calculations using these breakthrough results (Figure 6D and Table S8), the loading of CH 4 enriched from the mixture was ~19.6 cm 3 /g, which is comparable to that of the best materials reported in the literature, for example, NKMOF‐8‐Me (20.8 cm 3 /g), 53 and higher than that of all previously reported MOFs. For a low concentration of CH 4 inlet gas (20/80 and 10/90 CH 4 /N 2 ), it is also feasible to realize the good separation of CH 4 from N 2 using MIL‐120Al (Figures S12 and S13).…”

Section: Resultssupporting

confidence: 73%

“…It is noteworthy that the faster diffusion rate of CH 4 than N 2 has been observed for the first time in MOFs. This phenomenon is contrary to that of conventional MOF adsorbents, such as NKMOF-8-Me and Al-CDC, 53 in which N 2 always preferentially reaches equilibrium. To quantify the kinetic selectivity of MIL-120Al, the kinetic selectivity [D 0 (CH 4 )/D 0 (N 2 )] was obtained, and the value was up to 1.8 at 298 K (Table S2).…”

Section: Kinetic and Equilibrium Adsorptioncontrasting

confidence: 64%

“…The corresponding CH 4 volume adsorption uptake of MIL-120Al based on the framework density was calculated to be 52.91 cm 3 /cm 3 , which also exceeds other previously reported materials (Figure S6 and Table S3) with the exception of NKMOF-8-Me (54.11 cm 3 /cm 3 ). 53 In contrast, MIL-120Al only adsorbs a small amount of N 2 (10.5 cm 3 /g) under the same conditions. The repeatability of the adsorption performance was also tested using a cycling experiment.…”

Section: Characterization Of Mil-120almentioning

confidence: 94%

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Thermodynamic‐kinetic synergistic separation of CH₄/N₂ on a robust aluminum‐based metal‐organic framework

et al. 2023

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A robust aluminum-based metal-organic framework (Al-MOF) MIL-120Al with 1D rhombic ultra-microporous was reported. The nonpolar porous walls composed of para-benzene rings with a comparable pore size to the kinetic diameter of methane allow it to exhibit a novel thermodynamic-kinetic synergistic separation of CH 4 /N 2 mixtures. The CH 4 adsorption capacity was as high as 33.7 cm 3 /g (298 K, 1 bar), which is the highest uptake value among the Al-MOFs reported to date. The diffusion rates of CH 4 were faster than N 2 in this structure as confirmed by timedependent kinetic adsorption profiles. Breakthrough experiments confirm that this MOF can completely separate the CH 4 /N 2 mixture and the separation performance is not affected in the presence of H 2 O. Theoretical calculations reveal that pore centers with more energetically-favorable binding sites for CH 4 than N 2 . The results of pressure swing adsorption (PSA) simulations indicate that MIL-120Al is a potential candidate for selective capture coal-mine methane.

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Section: Resultssupporting

confidence: 73%

Section: Kinetic and Equilibrium Adsorptioncontrasting

confidence: 64%

Section: Characterization Of Mil-120almentioning

confidence: 94%

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Thermodynamic‐kinetic synergistic separation of CH₄/N₂ on a robust aluminum‐based metal‐organic framework

et al. 2023

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“…Furthermore, as the concentration of CH 4 decreases, the adsorbent theoretically requires a longer time to reach adsorption saturation, leading to an extension of CH 4 breakthrough time, which is beneficial for adsorption separation. In addition, this concentration ratio is also the most widely used in other reported studies. ,,− As indicated in Figure a, N 2 is first eluted through the breakthrough column (∼11 min) to yield a high-purity outlet N 2 effluent (≥99.99%) covering an undetectable CH 4 amount (until ∼16 min). The residence time interval is about 5 min, appreciably proving the utter CH 4 /N 2 separation under dynamic flow conditions.…”

Section: Resultsmentioning

confidence: 99%

Discovery of a Scalable Metal–Organic Framework with a Switchable Structure for Efficient CH₄/N₂ Separation

et al. 2023

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Discovering optimum materials to realize an efficient CH 4 /N 2 mixture is of vital industrial significance but scientifically challenging. To solve this key obstacle, an efficient strategy from theoretical screening to scalable synthesis was thus proposed. A large-scale computational screening was first executed to identify high-performance adsorbents for CH 4 /N 2 separation from the experimental copper metal−organic framework (Cu-MOF) libraries. A series of MOFs with kagome-type lattice characteristics were computationally defined as candidates with good CH 4 /N 2 selectivity. As a proof-of-concept example, one of the candidates (SIWPAS) was further prepared in an experiment. Intriguingly, the pore sizes can be precisely regulated by altering the degassing temperature to induce the dynamic switch of the initial two-dimensional (2D) framework, further enhancing the separation performance for CH 4 /N 2 . The obtained selectivity of 15.0 at 298 K and 1.0 bar is consistent with the simulation prediction value, which is also one of the highest values presently. Meanwhile, the CH 4 /N 2 uptake ratio of 7.5 (298 K and 1.0 bar) and comprehensive separation performance index sorbent selection parameter (Ssp) of 283.0 are higher than those of all materials as yet. Significantly, the scalable continuous synthesis of this MOF was finally realized with the highest space-time yield (STY) of 18982 kg m −3 day −1 for all 2D MOFs with the aid of the process intensification approach based on high gravity technology. As a foremost finding, this work not only greatly shortens the discovery period of high-performance MOF materials but also effectively promotes their practical applications.

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“…Designing highly perm‐selective membranes is crucial to gas separation. Various nanoporous membranes, made by carbons, 7 zeolites, 8,9 metal–organic frameworks (MOFs), 10–14 and covalent organic frameworks, 15,16 are prepared for outperforming trade‐off upper bounds. Polymers of intrinsic microporosity (PIMs), for example, PIM‐1, have rigid and ladder‐like backbones.…”

Section: Introductionmentioning

confidence: 99%

Post‐synthesis amination of polymer of intrinsic microporosity membranes for CO₂ separation

Chen

Liu

et al. 2023

AIChE Journal

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Membrane separation is an energy-saving technology for carbon capture. However, it is subjected to permeability-selectivity trade-off limitation. Although chemical functionalization is proposed to boost separation efficiency, controlling sorptiondiffusion process remains extremely challenging. In this study, a facile, controllable, and versatile chemical vapor amination strategy is reported to simultaneously tune gas sorption and diffusion in polymer of intrinsic microporosity (PIM)-based membranes for improving carbon capture performance. Through simple exposure in amine vapors under mild conditions, nucleophilic substitution of amines toward ether and halogen groups induce grafting, ring-opening, terminal replacement, chain-scission, and crosslinking of PIM-1, thereby underpinning CO 2 -philicity and tailoring passageway. The prepared CO 2 -philic membranes exhibit substantially improved CO 2 /N 2 selectivity over 30.8, about 226% as that of original one, accompanied by high CO 2 permeability of 2590 Barrer, which can surpass the trade-off upper bound of polymer membranes. Our results reveal that post-synthesis amination is an effective route to obtain high-performance membranes.

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Separation ofCH₄/N₂by an ultra‐stable metal–organic framework with the highest breakthrough selectivity

Cited by 36 publications

References 90 publications

Thermodynamic‐kinetic synergistic separation of CH₄/N₂ on a robust aluminum‐based metal‐organic framework

Thermodynamic‐kinetic synergistic separation of CH₄/N₂ on a robust aluminum‐based metal‐organic framework

Discovery of a Scalable Metal–Organic Framework with a Switchable Structure for Efficient CH₄/N₂ Separation

Post‐synthesis amination of polymer of intrinsic microporosity membranes for CO₂ separation

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Separation ofCH4/N2by an ultra‐stable metal–organic framework with the highest breakthrough selectivity

Cited by 36 publications

References 90 publications

Thermodynamic‐kinetic synergistic separation of CH4/N2 on a robust aluminum‐based metal‐organic framework

Thermodynamic‐kinetic synergistic separation of CH4/N2 on a robust aluminum‐based metal‐organic framework

Discovery of a Scalable Metal–Organic Framework with a Switchable Structure for Efficient CH4/N2 Separation

Post‐synthesis amination of polymer of intrinsic microporosity membranes for CO2 separation

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Product

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Separation ofCH₄/N₂by an ultra‐stable metal–organic framework with the highest breakthrough selectivity

Thermodynamic‐kinetic synergistic separation of CH₄/N₂ on a robust aluminum‐based metal‐organic framework

Thermodynamic‐kinetic synergistic separation of CH₄/N₂ on a robust aluminum‐based metal‐organic framework

Discovery of a Scalable Metal–Organic Framework with a Switchable Structure for Efficient CH₄/N₂ Separation

Post‐synthesis amination of polymer of intrinsic microporosity membranes for CO₂ separation