AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Th-MOF showing six-fold imide-sealed pockets for middle-size-separation of propane from natural gas

Li Wang1, Wenhui Zhang1, Jie Ding1, Lele Gong1, Rajamani Krishna2, Youyuan Ran1, Lan Chen1, Feng Luo1( )
Jiangxi Province Key Laboratory of Synthetic Chemistry, School of Chemistry, Biology and Material Science, East China University of Technology, Nanchang 330013, China
Van’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands
Show Author Information

Graphical Abstract

A novel Th-metal-organic framework (MOF) that takes UiO-66-type structure, but with the pocket sealed by six-fold imide groups was synthesized and proved to be potential material for middle-size-separation of propane from natural gas.

Abstract

Separation of propane from natural gas is of great importance to industry. However, in light of size-based separation, there still lacks effective method to directly separate propane from natural gas, due to the comparable physical properties for these light alkanes (C1–C4) and the middle size of propane. In this work, we found that a new Th-metal-organic framework (MOF) could be an ideal solution for this issue. The Th-MOF takes UiO-66-type structure, but with the pocket sealed by six-fold imide groups; this not only precisely reduces the size of pocket to exactly match propane, but also enhances the host–guest interactions through multiple (C)H(δ+)∙∙∙(δ−)O(C) interactions. As a result, highly selective adsorption of propane over methane, ethane, and butane was observed, implying unique middle-size separation. The actual separation was confirmed by breakthrough experiments of simulated natural gas, confirming its superior application in direct separation of propane from natural gas. The separation mechanism, as unveiled by both theoretical calculation and comparative experiments, is due to the six-fold imide-sealed pocket that could effectively distinguish propane from other light alkanes through both size effect and host–guest interactions.

Keywords

Th-metal-organic framework (MOF)intermediate-size-separationnatural gasselectivity

Electronic Supplementary Material

Download File(s)
12274_2022_4915_MOESM1_ESM.pdf (2.9 MB)
12274_2022_4915_MOESM2_ESM.cif (20.4 KB)

References

[1]

Zhang, Y. B.; Yang, L. F.; Wang, L. Y.; Cui, X. L.; Xing, H. B. Pillar iodination in functional boron cage hybrid supramolecular frameworks for high performance separation of light hydrocarbons. J. Mater. Chem. A 2019, 7, 27560–27566.
Crossref Google Scholar
[2]

Wu, Y. F.; Sun, Y. W.; Xiao, J.; Wang, X.; Li, Z. Glycine-modified HKUST-1 with simultaneously enhanced moisture stability and improved adsorption for light hydrocarbons separation. ACS Sustainable Chem. Eng. 2019, 7, 1557–1563.
Crossref Google Scholar
[3]

Wang, J.; Krishna, R.; Yang, T.; Deng, S. G. Nitrogen-rich microporous carbons for highly selective separation of light hydrocarbons. J. Mater. Chem. A 2016, 4, 13957–13966.
Crossref Google Scholar
[4]

He, Y. B.; Krishna, R.; Chen, B. L. Metal-organic frameworks with potential for energy-efficient adsorptive separation of light hydrocarbons. Energy Environ. Sci. 2012, 5, 9107–9120.
Crossref Google Scholar
[5]

Peng, Y. L.; Wang, T.; Jin, C. N.; Li, P. F.; Suepaul, S.; Beemer, G.; Chen, Y.; Krishna, R.; Cheng, P.; Pham, T. et al. A robust heterometallic ultramicroporous MOF with ultrahigh selectivity for propyne/propylene separation. J. Mater. Chem. A 2021, 9, 2850–2856.
Crossref Google Scholar
[6]

Borah, B.; Zhang, H. D.; Snurr, R. Q. Diffusion of methane and other alkanes in metal-organic frameworks for natural gas storage. Chem. Eng. Sci. 2015, 124, 135–143.
Crossref Google Scholar
[7]

Wu, Y. Q.; Weckhuysen, B. M. Separation and purification of hydrocarbons with porous materials. Angew. Chem., Int. Ed. 2021, 60, 18930–18949.
Crossref Google Scholar
[8]

Wang, Y. T.; Fan, W. D.; Wang, X.; Han, Y. F.; Zhang, L. L.; Liu, D.; Dai, F. N.; Sun, D. F. Solvent-induced framework-interpenetration isomers of Cu MOFs for efficient light hydrocarbon separation. Inorg. Chem. Front. 2018, 5, 2408–2412.
Crossref Google Scholar
[9]

Li, L.; Yin, Q.; Li, H. F.; Liu, T. F.; Cao, R. Rational design of phosphonocarboxylate metal-organic frameworks for light hydrocarbon separations. Mater. Chem. Front. 2018, 2, 1436–1440.
Crossref Google Scholar
[10]

Chen, Y. W.; Qiao, Z. W.; Lv, D. F.; Wu, H. X.; Shi, R. F.; Xia, Q. B.; Wang, H. H.; Zhou, J.; Li, Z. Selective adsorption of light alkanes on a highly robust indium based metal-organic framework. Ind. Eng. Chem. Res. 2017, 56, 4488–4495.
Crossref Google Scholar
[11]
Chen, J. J. In-depth Report on Propylene Industry: Downstream Domestic Substitution Accelerates, Propylene Profits May Increase [Online]. Northeast Securities Co., Ltd., 2021; pp 31–32. https://www.vzkoo.com/read/92d998da7fa309e2d6020c667c9de79e.html.
[12]

Geng, D. T.; Zhang, M.; Hang, X. X.; Xie, W. J.; Qin, Y. C.; Li, Q.; Bi, Y. F.; Zheng, Z. P. A 2D metal-thiacalix[4]arene porous coordination polymer with 1D channels: Gas absorption/separation and frequency response. Dalton Trans. 2018, 47, 9008–9013.
Crossref Google Scholar
[13]

Li, J. R.; Kuppler, R. J.; Zhou, H. C. Selective gas adsorption and separation in metal-organic frameworks. Chem. Soc. Rev. 2009, 38, 1477–1504.
Crossref Google Scholar
[14]

Wu, T. Y.; Shu, C. J.; Liu, S.; Xu, B. S.; Zhong, S. L.; Zhou, R. F. Separation performance of Si-CHA zeolite membrane for a binary H2/CH4 mixture and ternary and quaternary mixtures containing impurities. Energy Fuels 2020, 34, 11650–11659.
Crossref Google Scholar
[15]

Lin, J. Y. S. Molecular sieves for gas separation. Science 2016, 353, 121–122.
Crossref Google Scholar
[16]

Shi, R. F.; Lv, D. F.; Chen, Y. W.; Wu, H. X.; Liu, B. Y.; Xia, Q. B.; Li, Z. Highly selective adsorption separation of light hydrocarbons with a porphyrinic zirconium metal-organic framework PCN-224. Sep. Purif. Technol. 2018, 207, 262–268.
Crossref Google Scholar
[17]

Wang, Y.; Huang, N. Y.; Zhang, X. W.; He, H.; Huang, R. K.; Ye, Z. M.; Li, Y.; Zhou, D. D.; Liao, P. Q.; Chen, X. M. et al. Selective aerobic oxidation of a metal-organic framework boosts thermodynamic and kinetic propylene/propane selectivity. Angew. Chem., Int. Ed. 2019, 131, 7774–7778.
Crossref Google Scholar
[18]

Cadiau, A.; Adil, K.; Bhatt, P. M.; Belmabkhout, Y.; Eddaoudi, M. A metal-organic framework-based splitter for separating propylene from propane. Science 2016, 353, 137–140.
Crossref Google Scholar
[19]

Zeng, H.; Xie, M.; Wang, T.; Wei, R. J.; Xie, X. J.; Zhao, Y. F.; Lu, W. G.; Li, D. Orthogonal-array dynamic molecular sieving of propylene/propane mixtures. Nature 2021, 595, 542–548.
Crossref Google Scholar
[20]

Zhou, D. D.; Chen, P.; Wang, C.; Wang, S. S.; Du, Y. F.; Yan, H.; Ye, Z. M.; He, C. T.; Huang, R. K.; Mo, Z. W. et al. Intermediate-sized molecular sieving of styrene from larger and smaller analogues. Nat. Mater. 2019, 18, 994–998.
Crossref Google Scholar
[21]

Furukawa, S.; Reboul, J.; Diring, S.; Sumida, K.; Kitagawa, S. Structuring of metal-organic frameworks at the mesoscopic/macroscopic scale. Chem. Soc. Rev. 2014, 43, 5700–5734.
Crossref Google Scholar
[22]

Adil, K.; Belmabkhout, Y.; Pillai, R. S.; Cadiau, A.; Bhatt, P. M.; Assen, A. H.; Maurin, G.; Eddaoudi, M. Gas/vapour separation using ultra-microporous metal-organic frameworks: Insights into the structure/separation relationship. Chem. Soc. Rev. 2017, 46, 3402–3430.
Crossref Google Scholar
[23]

Duan, J. G.; Pan, Y. C.; Liu, G. P.; Jin, W. Q. Metal-organic framework adsorbents and membranes for separation applications. Curr. Opin. Chem. Eng. 2018, 20, 122–131.
Crossref Google Scholar
[24]

Ying, Y. P.; Zhang, Z. Q.; Peh, S. B.; Karmakar, A.; Cheng, Y. D.; Zhang, J.; Xi, L. F.; Boothroyd, C.; Lam, Y. M.; Zhong, C. L. et al. Pressure-responsive two-dimensional metal-organic framework composite membranes for CO2 separation. Angew. Chem., Int. Ed. 2021, 60, 11318–11325.
Crossref Google Scholar
[25]

Wang, Y. T.; Hao, C. L.; Fan, W. D.; Fu, M. Y.; Wang, X. K.; Wang, Z. K.; Zhu, L.; Li, Y.; Lu, X. Q.; Dai, F. N. et al. One-step ethylene purification from an acetylene/ethylene/ethane ternary mixture by cyclopentadiene cobalt-functionalized metal-organic frameworks. Angew. Chem., Int. Ed. 2021, 60, 11350–11358.
Crossref Google Scholar
[26]

Lin, R. B.; Zhang, Z. J.; Chen, B. L. Achieving high performance metal-organic framework materials through pore engineering. Acc. Chem. Res. 2021, 54, 3362–3376.
Crossref Google Scholar
[27]

Li, B.; Cui, X. L.; O’Nolan, D.; Wen, H. M.; Jiang, M. D.; Krishna, R.; Wu, H.; Lin, R. B.; Chen, Y. S.; Yuan, D. Q. et al. An ideal molecular sieve for acetylene removal from ethylene with record selectivity and productivity. Adv. Mater. 2017, 29, 1704210.
Crossref Google Scholar
[28]

Assen, A. H.; Belmabkhout, Y.; Adil, K.; Bhatt, P. M.; Xue, D. X.; Jiang, H.; Eddaoudi, M. Ultra-tuning of the rare-earth fcu-MOF aperture size for selective molecular exclusion of branched paraffins. Angew. Chem., Int. Ed. 2015, 54, 14353–14358.
Crossref Google Scholar
[29]

Hamon, L.; Llewellyn, P. L.; Devic, T.; Ghoufi, A.; Clet, G.; Guillerm, V.; Pirngruber, G. D.; Maurin, G.; Serre, C.; Driver, G. et al. Co-adsorption and separation of CO2-CH4 mixtures in the highly flexible MIL-53(Cr) MOF. J. Am. Chem. Soc. 2009, 131, 17490–17499.
Crossref Google Scholar
[30]

Lin, R. B.; Li, L. B.; Zhou, H. L.; Wu, H.; He, C. H.; Li, S.; Krishna, R.; Li, J. P.; Zhou, W.; Chen, B. L. Molecular sieving of ethylene from ethane using a rigid metal-organic framework. Nat. Mater. 2018, 17, 1128–1133.
Crossref Google Scholar
[31]

Liang, B.; Zhang, X.; Xie, Y.; Lin, R. B.; Krishna, R.; Cui, H.; Li, Z. Q.; Shi, Y. S.; Wu, H.; Zhou, W. et al. An ultramicroporous metal-organic framework for high sieving separation of propylene from propane. J. Am. Chem. Soc. 2020, 142, 17795–17801.
Crossref Google Scholar
[32]

Zhang, Z. Q.; Yang, Q. W.; Cui, X. L.; Yang, L. F.; Bao, Z. B.; Ren, Q. L.; Xing, H. B. Sorting of C4 olefins with interpenetrated hybrid ultramicroporous materials by combining molecular recognition and size-sieving. Angew. Chem., Int. Ed. 2017, 56, 16282–16287.
Crossref Google Scholar
[33]

Ding, Q.; Zhang, Z. Q.; Yu, C.; Zhang, P. X.; Wang, J.; Cui, X. L.; He, C. H.; Deng, S. G.; Xing, H. B. Exploiting equilibrium-kinetic synergetic effect for separation of ethylene and ethane in a microporous metal-organic framework. Sci. Adv. 2020, 6, eaaz4322.
Crossref Google Scholar
[34]

Chen, X. Y.; Plonka, A. M.; Banerjee, D.; Krishna, R.; Schaef, H. T.; Ghose, S.; Thallapally, P. K.; Parise, J. B. Direct observation of Xe and Kr adsorption in a Xe-selective microporous metal-organic framework. J. Am. Chem. Soc. 2015, 137, 7007–7010.
Crossref Google Scholar
[35]

Gan, L.; Chidambaram, A.; Fonquernie, P. G.; Light, M. E.; Choquesillo-Lazarte, D.; Huang, H. L.; Solano, E.; Fraile, J.; Vinas, C.; Teixidor, F. et al. A Highly water-stable meta-carborane-based copper metal-organic framework for efficient high-temperature butanol separation. J. Am. Chem. Soc. 2020, 142, 8299–8311.
Crossref Google Scholar
[36]

Li, L. Y.; Guo, L. D.; Zhang, Z. G.; Yang, Q. W.; Yang, Y. W.; Bao, Z. B.; Ren, Q. L.; Li, J. A robust squarate-based metal-organic framework demonstrates record-high affinity and selectivity for xenon over krypton. J. Am. Chem. Soc. 2019, 141, 9358–9364.
Crossref Google Scholar
[37]

Andreo, J.; Priola, E.; Alberto, G.; Benzi, P.; Marabello, D.; Proserpio, D. M.; Lamberti, C.; Diana, E. Autoluminescent metal-organic frameworks (MOFs): Self-photoemission of a highly stable thorium MOF. J. Am. Chem. Soc. 2018, 140, 14144–14149.
Crossref Google Scholar
[38]

Xu, H.; Cao, C. S.; Hu, H. S.; Wang, S. B.; Liu, J. C.; Cheng, P.; Kaltsoyannis, N.; Li, J.; Zhao, B. High uptake of ReO4− and CO2 conversion by a radiation-resistant thorium-nickle [Th48Ni6] nanocage-based metal-organic framework. Angew. Chem., Int. Ed. 2019, 58, 6022–6027.
Crossref Google Scholar
[39]

Roztocki, K.; Formalik, F.; Krawczuk, A.; Senkovska, I.; Kuchta, B.; Kaskel, S.; Matoga, D. Collective breathing in an eightfold interpenetrated metal-organic framework: From mechanistic understanding towards threshold sensing architectures. Angew. Chem., Int. Ed. 2020, 59, 4491–4497.
Crossref Google Scholar
[40]

Yang, H. J.; Trieu, T. X.; Zhao, X.; Wang, Y. X.; Wang, Y.; Feng, P. Y.; Bu, X. H. Lock-and-key and shape-memory effects in an unconventional synthetic path to magnesium metal-organic frameworks. Angew. Chem., Int. Ed. 2019, 58, 11757–11762.
Crossref Google Scholar
[41]

Taylor, M. K.; Runčevski, T.; Oktawiec, J.; Gonzalez, M. I.; Siegelman, R. L.; Mason, J. A.; Ye, J. X.; Brown, C. M.; Long, J. R. Tuning the adsorption-induced phase change in the flexible metal-organic framework Co(bdp). J. Am. Chem. Soc. 2016, 138, 15019–15026.
Crossref Google Scholar
[42]

Luo, F.; Yan, C. S.; Dang, L. L.; Krishna, R.; Zhou, W.; Wu, H.; Dong, X. L.; Han, Y.; Hu, T. L.; O’Keeffe, M. et al. UTSA-74: A MOF-74 isomer with two accessible binding sites per metal center for highly selective gas separation. J. Am. Chem. Soc. 2016, 138, 5678–5684.
Crossref Google Scholar
[43]

Zhang, H. P.; Fan, Y. L.; Krishna, R.; Feng, X. F.; Wang, L.; Luo, F. Robust metal-organic framework with multiple traps for trace Xe/Kr separation. Sci. Bull. 2021, 66, 1073–1079.
Crossref Google Scholar
[44]

Wang, L.; Yang, L. X.; Gong, L. L.; Krishna, R.; Gao, Z.; Tao, Y.; Yin, W. H.; Xu, Z. Z.; Luo, F. Constructing redox-active microporous hydrogen-bonded organic framework by imide-functionalization: Photochromism, electrochromism, and selective adsorption of C2H2 over CO2. Chem. Eng. J. 2020, 383, 123117.
Crossref Google Scholar
[45]

Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti, C.; Bordiga, S.; Lillerud, K. P. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. J. Am. Chem. Soc. 2008, 130, 13850–13851.
Crossref Google Scholar
Nano Research
Volume 16 Issue 2,
February 2023
Pages 3287-3293
DOI: 10.1007/s12274-022-4915-0
Cite this article:
Wang L, Zhang W, Ding J, et al. Th-MOF showing six-fold imide-sealed pockets for middle-size-separation of propane from natural gas. Nano Research, 2023, 16(2): 3287-3293. https://doi.org/10.1007/s12274-022-4915-0
Topics:
Organic frameworks

792

Views

18

Crossref

18

Web of Science

15

Scopus

2

CSCD

Altmetrics
Received: 17 June 2022
Revised: 30 July 2022
Accepted: 16 August 2022
Published: 02 September 2022
© Tsinghua University Press 2022
Return