Intermediate-sized molecular sieving of styrene from larger and smaller analogues

Zhou, Dong‐Dong; Chen, Pin; Wang, Chao; Wang, Shasha; Du, Yunfei; Yan, Hui; Ye, Zi‐Ming; He, Chun‐Ting; Huang, Rui‐Kang; Mo, Zong‐Wen; Huang, Ning‐Yu; Zhang, Wei‐Xiong

doi:10.1038/s41563-019-0427-z

Cited by 145 publications

(109 citation statements)

References 58 publications

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“…Metal–organic frameworks (MOFs) or porous coordination polymers have emerged as promising adsorbents for gas separation and purification owing to their powerful predictability and tunability on pore size/shape and functionality. [ 7–9 ] Since C 2 H 2 (kinetic diameter: 3.3 Å) has a relatively large size or polarity difference with C 2 H 4 (4.2 Å) and CH 4 (3.8 Å), highly efficient separation of C 2 H 2 /C 2 H 4 or C 2 H 2 /CH 4 has been fulfilled in some reported MOFs with benchmark selectivities by pore tuning and pore functionalization strategies. [ 10,11 ] However, compared with the separation of C 2 H 2 /C 2 H 4 and C 2 H 2 /CH 4 , C 2 H 2 /CO 2 separation is much more difficult and challenging because of their very close molecular size/shape (3.3 Å for both C 2 H 2 and CO 2 ) and physical properties.…”

Section: Figurementioning

confidence: 99%

A Chemically Stable Hofmann‐Type Metal−Organic Framework with Sandwich‐Like Binding Sites for Benchmark Acetylene Capture

et al. 2020

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The realization of porous materials for highly selective separation of acetylene (C2H2) from various other gases (e.g., carbon dioxide and ethylene) by adsorption is of prime importance but challenging in the petrochemical industry. Herein, a chemically stable Hofmann‐type metal−organic framework (MOF), Co(pyz)[Ni(CN)4] (termed as ZJU‐74a), that features sandwich‐like binding sites for benchmark C2H2 capture and separation is reported. Gas sorption isotherms reveal that ZJU‐74a exhibits by far the record C2H2 capture capacity (49 cm3 g−1 at 0.01 bar and 296 K) and thus ultrahigh selectivity for C2H2/CO2 (36.5), C2H2/C2H4 (24.2), and C2H2/CH4 (1312.9) separation at ambient conditions, respectively, of which the C2H2/CO2 selectivity is the highest among all the robust MOFs reported so far. Theoretical calculations indicate that the oppositely adjacent nickel(II) centers together with cyanide groups from different layers in ZJU‐74a can construct a sandwich‐type adsorption site to offer dually strong and cooperative interactions for the C2H2 molecule, thus leading to its ultrahigh C2H2 capture capacity and selectivities. The exceptional separation performance of ZJU‐74a is confirmed by both simulated and experimental breakthrough curves for 50/50 (v/v) C2H2/CO2, 1/99 C2H2/C2H4, and 50/50 C2H2/CH4 mixtures under ambient conditions.

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Section: Figurementioning

confidence: 99%

A Chemically Stable Hofmann‐Type Metal−Organic Framework with Sandwich‐Like Binding Sites for Benchmark Acetylene Capture

et al. 2020

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“…Owing to their inherent diversity, these materials enable precise control of pore shape, pore chemistry and pore size, thereby providing a versatile platform for separation processes [8][9][10][11][12][13][14][15] . In terms of trace gas removal, numerous studies have focused on the rational design of three-dimensional (3D) MOFs with uniform sub-nanometer pores [16][17][18][19][20][21][22][23][24][25] . Despite significant achievements, designing new materials that outperform existing benchmark adsorbents remains a formidable challenge.…”

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confidence: 99%

Simultaneous interlayer and intralayer space control in two-dimensional metal−organic frameworks for acetylene/ethylene separation

Shen

Tian

et al. 2020

Nat Commun

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Three-dimensional metal−organic frameworks (MOFs) are cutting-edge materials in the adsorptive removal of trace gases due to the availability of abundant pores with specific chemistry. However, the development of ideal adsorbents combining high adsorption capacity with high selectivity and stability remains challenging. Here we demonstrate a strategy to design adsorbents that utilizes the tunability of interlayer and intralayer space of two-dimensional fluorinated MOFs for capturing acetylene from ethylene. Validated by X-ray diffraction and modeling, a systematic variation of linker atom oxidation state enables fine regulation of layer stacking pattern and linker conformation, which affords a strong interlayer trapping of molecules along with cooperative intralayer binding. The resultant robust materials (ZUL-100 and ZUL-200) exhibit benchmark capacity in the pressure range of 0.001–0.05 bar with high selectivity. Their efficiency in acetylene/ethylene separation is confirmed by breakthrough experiments, giving excellent ethylene productivities (121 mmol/g from 1/99 mixture, 99.9999%), even when cycled under moist conditions.

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“…However, the separation selectivity and the capacity of zeolites are still limited by the nature of cationic binding sites and their pore topologies. Porous materials with designable pore topology and selective binding sites open up unexpected possibilities for recognition of xylene isomers [13][14][15][16][17][18][19][20] . Different kinds of metal-organic frameworks (MOFs) or porous coordination polymers, including MIL (Materials of Institut Lavoisier) series and MOFs with coordinatively unsaturated metal sites (CUSs), have been investigated for the separation of xylene isomers, both in vapor and liquid phases [21][22][23][24][25][26][27][28][29][30][31] .…”

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confidence: 99%

Efficient separation of xylene isomers by a guest-responsive metal–organic framework with rotational anionic sites

et al. 2020

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The separation of xylene isomers (para-, meta-, orth-) remains a great challenge in the petrochemical industry due to their similar molecular structure and physical properties. Porous materials with sensitive nanospace and selective binding sites for discriminating the subtle structural difference of isomers are urgently needed. Here, we demonstrate the adaptively molecular discrimination of xylene isomers by employing a NbOF52−-pillared metal–organic framework (NbOFFIVE-bpy-Ni, also referred to as ZU-61) with rotational anionic sites. Single crystal X-ray diffraction studies indicate that ZU-61 with guest-responsive nanospace/sites can adapt the shape of specific isomers through geometric deformation and/or the rotation of fluorine atoms in anionic sites, thereby enabling ZU-61 to effectively differentiate xylene isomers through multiple C–H···F interactions. ZU-61 exhibited both high meta-xylene uptake capacity (3.4 mmol g−1) and meta-xylene/para-xylene separation selectivity (2.9, obtained from breakthrough curves), as well as a favorable separation sequence as confirmed by breakthrough experiments: para-xylene elute first with high-purity (≥99.9%), then meta-xylene, and orth-xylene. Such a remarkable performance of ZU-61 can be attributed to the type anionic binding sites together with its guest-response properties.

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Intermediate-sized molecular sieving of styrene from larger and smaller analogues

Cited by 145 publications

References 58 publications

A Chemically Stable Hofmann‐Type Metal−Organic Framework with Sandwich‐Like Binding Sites for Benchmark Acetylene Capture

A Chemically Stable Hofmann‐Type Metal−Organic Framework with Sandwich‐Like Binding Sites for Benchmark Acetylene Capture

Simultaneous interlayer and intralayer space control in two-dimensional metal−organic frameworks for acetylene/ethylene separation

Efficient separation of xylene isomers by a guest-responsive metal–organic framework with rotational anionic sites

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