Flexible Zn-MOF with Rare Underlying scu Topology for Effective Separation of C6 Alkane Isomers

Velasco, Ever; Xian, Shikai; Wang, Hao; Teat, Simon J.; Olson, David H.; Tan, Kui; Ullah, Saif; Osborn Popp, Thomas M.; Bernstein, Ashley D.; Oyekan, Kolade A.; Nieuwkoop, Andrew J.; Thonhauser, Timo; Li, Jing

doi:10.1021/acsami.1c08678

Title: Flexible Zn-MOF with Rare Underlying scu Topology for Effective Separation of C6 Alkane Isomers

Journal Article · 19 July 2021 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.1c08678 · OSTI ID:1963425

Velasco, Ever ^[1]; Xian, Shikai ^[2]; Wang, Hao ^[3]; Teat, Simon J. ^[4]; Olson, David H. ^[1];

^[5];

^[6]; Osborn Popp, Thomas M. ^[1]; Bernstein, Ashley D. ^[1];

^[5]; Nieuwkoop, Andrew J. ^[7];

^[6];

^[7]

Rutgers University, New Brunswick, NJ (United States)
Rutgers University, New Brunswick, NJ (United States); Shenzhen Polytechnic (China)
Shenzhen Polytechnic (China)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
University of Texas at Dallas, Richardson, TX (United States)
Wake Forest University, Winston-Salem, NC (United States)
Rutgers University, Piscataway, NJ (United States)

Adsorptive separation by porous solids provides an energy-efficient alternative for the purification of important chemical species compared to energy-intensive distillations. Particularly, the separation of linear hexane isomers from its branched counterparts is crucial to produce premium grade gasoline with high research octane number (RON). Herein, we report the synthesis of a new, flexible zinc-based metal-organic framework, [Zn₅(μ₃-OH)₂(adtb)₂(H₂O)₅·5 DMA] (Zn-adtb), constructed from a butterfly shaped carboxylate linker with underlying (4,8)-connected scu topology capable of separating the C6 isomers nHEX, 3MP, and 23DMB. The sorbate-sorbent interactions and separation mechanisms were investigated and analyzed through in situ FTIR, solid state NMR measurements and computational modeling. Here these studies reveal that Zn-adtb discriminates the nHEX/3MP isomer pair through a kinetic separation mechanism and the nHEX/23DMB isomer pair through a molecular sieving mechanism. Column breakthrough measurements further demonstrate the efficient separation of linear nHEX from the mono- and dibranched isomers.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231; SC0019902

OSTI ID:: 1963425

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 44 Vol. 13; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (55)

Tailor-Made Microporous Metal-Organic Frameworks for the Full Separation of Propane from Propylene Through Selective Size Exclusion Wang, Hao; Dong, Xinglong; Colombo, Valentina Advanced Materials, Vol. 30, Issue 49 https://doi.org/10.1002/adma.201805088	journal	October 2018
Designer Metal–Organic Frameworks for Size‐Exclusion‐Based Hydrocarbon Separations: Progress and Challenges Wang, Hao; Liu, Yunling; Li, Jing Advanced Materials, Vol. 32, Issue 44 https://doi.org/10.1002/adma.202002603	journal	July 2020
A Microporous Metal–Organic Framework for Gas-Chromatographic Separation of Alkanes Chen, Banglin; Liang, Chengdu; Yang, Jun Angewandte Chemie International Edition, Vol. 45, Issue 9, p. 1390-1393 https://doi.org/10.1002/anie.200502844	journal	February 2006
Separation of Hydrocarbons with a Microporous Metal-Organic Framework Pan, Long; Olson, David H.; Ciemnolonski, Lauren R. Angewandte Chemie International Edition, Vol. 45, Issue 4 https://doi.org/10.1002/anie.200503503	journal	January 2006
Rapid Guest Exchange and Ultra-Low Surface Tension Solvents Optimize Metal-Organic Framework Activation Ma, Jialiu; Kalenak, Andre P.; Wong-Foy, Antek G. Angewandte Chemie International Edition, Vol. 56, Issue 46 https://doi.org/10.1002/anie.201709187	journal	October 2017
Crystal Flexibility Design through Local and Global Motility Cooperation Wang, Ping; Otake, Ken‐ichi; Hosono, Nobuhiko Angewandte Chemie International Edition, Vol. 60, Issue 13 https://doi.org/10.1002/anie.202015257	journal	February 2021
High‐Efficiency Separation of n ‐Hexane by a Dynamic Metal‐Organic Framework with Reduced Energy Consumption Chen, Qiang; Xian, Shikai; Dong, Xinglong Angewandte Chemie International Edition, Vol. 60, Issue 19 https://doi.org/10.1002/anie.202100707	journal	March 2021
Precise Control of Molecular Self‐Diffusion in Isoreticular and Multivariate Metal‐Organic Frameworks Osborn Popp, Thomas M.; Plantz, Ariel Z.; Yaghi, Omar M. ChemPhysChem, Vol. 21, Issue 1 https://doi.org/10.1002/cphc.201901043	journal	December 2019
Conductive Metal–Organic Frameworks: Design, Synthesis, and Applications Meng, Haibing; Han, Ying; Zhou, Chenhui Small Methods, Vol. 4, Issue 10 https://doi.org/10.1002/smtd.202000396	journal	July 2020
Luminescent metal–organic frameworks and coordination polymers as alternative phosphors for energy efficient lighting devices Lustig, William P.; Li, Jing Coordination Chemistry Reviews, Vol. 373 https://doi.org/10.1016/j.ccr.2017.09.017	journal	October 2018
Two-dimensional MOF and COF nanosheets for next-generation optoelectronic applications Ren, Xiaohui; Liao, Gengcheng; Li, Zhongjun Coordination Chemistry Reviews, Vol. 435 https://doi.org/10.1016/j.ccr.2021.213781	journal	May 2021
Adsorption equilibrium and kinetics of branched hexane isomers in pellets of BETA zeolite Bárcia, Patrick S.; Silva, José A. C.; Rodrigues, Alírio E. Microporous and Mesoporous Materials, Vol. 79, Issue 1-3 https://doi.org/10.1016/j.micromeso.2004.10.037	journal	April 2005
Microporous Metal–Organic Frameworks for Adsorptive Separation of C5–C6 Alkane Isomers Wang, Hao; Li, Jing Accounts of Chemical Research, Vol. 52, Issue 7 https://doi.org/10.1021/acs.accounts.8b00658	journal	March 2019
Direct Capture of CO₂ from Ambient Air Sanz-Pérez, Eloy S.; Murdock, Christopher R.; Didas, Stephanie A. Chemical Reviews, Vol. 116, Issue 19, p. 11840-11876 https://doi.org/10.1021/acs.chemrev.6b00173	journal	August 2016
Tuning the Connectivity, Rigidity, and Functionality of Two-Dimensional Zr-Based Metal–Organic Frameworks Jia, Shuping; Xiao, Xue; Li, Qiyang Inorganic Chemistry, Vol. 58, Issue 19 https://doi.org/10.1021/acs.inorgchem.9b01666	journal	September 2019
NMR Spectroscopy Reveals Adsorbate Binding Sites in the Metal–Organic Framework UiO-66(Zr) Nandy, Aditya; Forse, Alexander C.; Witherspoon, Velencia J. The Journal of Physical Chemistry C, Vol. 122, Issue 15 https://doi.org/10.1021/acs.jpcc.7b12628	journal	March 2018
Electrically Conductive Coordination Polymers for Electronic and Optoelectronic Device Applications Liu, Hao; Wang, Yongshuai; Qin, Zhengsheng The Journal of Physical Chemistry Letters, Vol. 12, Issue 6 https://doi.org/10.1021/acs.jpclett.0c02988	journal	February 2021
Highly Efficient Luminescent Metal–Organic Framework for the Simultaneous Detection and Removal of Heavy Metals from Water Rudd, Nathan D.; Wang, Hao; Fuentes-Fernandez, Erika M. A. ACS Applied Materials & Interfaces, Vol. 8, Issue 44 https://doi.org/10.1021/acsami.6b10890	journal	October 2016
Functionalizing Luminescent Metal–Organic Frameworks for Enhanced Photoluminescence Liu, Xiao-Yuan; Lustig, William P.; Li, Jing ACS Energy Letters, Vol. 5, Issue 8 https://doi.org/10.1021/acsenergylett.0c01148	journal	July 2020
Metal Organic Frameworks (MOFs) as Photocatalysts for the Degradation of Agricultural Pollutants in Water Wen, Yinghao; Feng, Mingbao; Zhang, Peng ACS ES&T Engineering, Vol. 1, Issue 5 https://doi.org/10.1021/acsestengg.1c00051	journal	March 2021
Hydrocarbon Separations in Metal–Organic Frameworks Herm, Zoey R.; Bloch, Eric D.; Long, Jeffrey R. Chemistry of Materials, Vol. 26, Issue 1 https://doi.org/10.1021/cm402897c	journal	September 2013
Kinetics of Cross-Polarization in Solid-State NMR: A Guide for Chemists Kolodziejski, Waclaw; Klinowski, Jacek Chemical Reviews, Vol. 102, Issue 3 https://doi.org/10.1021/cr000060n	journal	March 2002
Carbon Dioxide Capture in Metal–Organic Frameworks Sumida, Kenji; Rogow, David L.; Mason, Jarad A. Chemical Reviews, Vol. 112, Issue 2, p. 724-781 https://doi.org/10.1021/cr2003272	journal	September 2011
Separation of C ₆ Paraffins Using Zeolitic Imidazolate Frameworks: Comparison with Zeolite 5A Peralta, David; Chaplais, Gérald; Simon-Masseron, Angélique Industrial & Engineering Chemistry Research, Vol. 51, Issue 12 https://doi.org/10.1021/ie202995g	journal	March 2012
Elaboration of Diaryl Ketones into Naphthalenes Fused on Two or Four Sides: A Naphthoannulation Procedure Donovan, Patrick M.; Scott, Lawrence T. Journal of the American Chemical Society, Vol. 126, Issue 10 https://doi.org/10.1021/ja038254i	journal	February 2004
Solution Processable MOF Yellow Phosphor with Exceptionally High Quantum Efficiency Gong, Qihan; Hu, Zhichao; Deibert, Benjamin J. Journal of the American Chemical Society, Vol. 136, Issue 48 https://doi.org/10.1021/ja509446h	journal	November 2014
Splitting Mono- and Dibranched Alkane Isomers by a Robust Aluminum-Based Metal–Organic Framework Material with Optimal Pore Dimensions Yu, Liang; Dong, Xinglong; Gong, Qihan Journal of the American Chemical Society, Vol. 142, Issue 15 https://doi.org/10.1021/jacs.0c01769	journal	March 2020
Porous Ti-MOF-74 Framework as a Strong-Binding Nitric Oxide Scavenger Jensen, Stephanie; Tan, Kui; Feng, Liang Journal of the American Chemical Society, Vol. 142, Issue 39 https://doi.org/10.1021/jacs.0c02772	journal	September 2020
Crystallizing Atomic Xenon in a Flexible MOF to Probe and Understand Its Temperature-Dependent Breathing Behavior and Unusual Gas Adsorption Phenomenon Wang, Hao; Warren, Mark; Jagiello, Jacek Journal of the American Chemical Society, Vol. 142, Issue 47 https://doi.org/10.1021/jacs.0c09475	journal	November 2020
Effective Detection of Mycotoxins by a Highly Luminescent Metal–Organic Framework Hu, Zhichao; Lustig, William P.; Zhang, Jingming Journal of the American Chemical Society, Vol. 137, Issue 51 https://doi.org/10.1021/jacs.5b10308	journal	December 2015
A Robust Squarate-Based Metal–Organic Framework Demonstrates Record-High Affinity and Selectivity for Xenon over Krypton Li, Liangying; Guo, Lidong; Zhang, Zhiguo Journal of the American Chemical Society, Vol. 141, Issue 23 https://doi.org/10.1021/jacs.9b03422	journal	May 2019
Three Models To Encapsulate Multicomponent Dyes into Nanocrystal Pores: A New Strategy for Generating High-Quality White Light Liu, Xiao-Yuan; Xing, Kai; Li, Yang Journal of the American Chemical Society, Vol. 141, Issue 37 https://doi.org/10.1021/jacs.9b07236	journal	August 2019
Kinetic Separation of Hexane Isomers by Fixed-Bed Adsorption with a Microporous Metal−Organic Framework Bárcia, Patrick S.; Zapata, Fatima; Silva, José A. C. The Journal of Physical Chemistry B, Vol. 111, Issue 22 https://doi.org/10.1021/jp0721898	journal	June 2007
Ring Current Effects: Factors Affecting the NMR Chemical Shift of Molecules Adsorbed on Porous Carbons Forse, Alexander C.; Griffin, John M.; Presser, Volker The Journal of Physical Chemistry C, Vol. 118, Issue 14 https://doi.org/10.1021/jp502387x	journal	March 2014
Separation of Alkane Isomers by Exploiting Entropy Effects during Adsorption on Silicalite-1: A Configurational-Bias Monte Carlo Simulation Study Schenk, M.; Vidal, S. L.; Vlugt, T. J. H. Langmuir, Vol. 17, Issue 5 https://doi.org/10.1021/la001189v	journal	March 2001
Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework Yang, Sihai; Ramirez-Cuesta, Anibal J.; Newby, Ruth Nature Chemistry, Vol. 7, Issue 2 https://doi.org/10.1038/nchem.2114	journal	December 2014
Mercury nano-trap for effective and efficient removal of mercury(II) from aqueous solution Li, Baiyan; Zhang, Yiming; Ma, Dingxuan Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6537	journal	November 2014
Capture of organic iodides from nuclear waste by metal-organic framework-based molecular traps Li, Baiyan; Dong, Xinglong; Wang, Hao Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00526-3	journal	September 2017
Topologically guided tuning of Zr-MOF pore structures for highly selective separation of C6 alkane isomers Wang, Hao; Dong, Xinglong; Lin, Junzhong Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04152-5	journal	May 2018
Cooperative copper centres in a metal–organic framework for selective conversion of CO2 to ethanol An, Bing; Li, Zhe; Song, Yang Nature Catalysis, Vol. 2, Issue 8 https://doi.org/10.1038/s41929-019-0308-5	journal	July 2019
Progress in adsorption-based CO ₂ capture by metal–organic frameworks Liu, Jian; Thallapally, Praveen K.; McGrail, B. Peter Chem. Soc. Rev., Vol. 41, Issue 6 https://doi.org/10.1039/C1CS15221A	journal	January 2012
Achieving exceptionally high luminescence quantum efficiency by immobilizing an AIE molecular chromophore into a metal–organic framework Hu, Zhichao; Huang, Guangxi; Lustig, William P. Chemical Communications, Vol. 51, Issue 15 https://doi.org/10.1039/C4CC07642G	journal	January 2015
Luminescent metal–organic frameworks for chemical sensing and explosive detection Hu, Zhichao; Deibert, Benjamin J.; Li, Jing Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C4CS00010B	journal	January 2014
Metal–organic frameworks: functional luminescent and photonic materials for sensing applications Lustig, William P.; Mukherjee, Soumya; Rudd, Nathan D. Chemical Society Reviews, Vol. 46, Issue 11 https://doi.org/10.1039/C6CS00930A	journal	January 2017
One-of-a-kind: a microporous metal–organic framework capable of adsorptive separation of linear, mono- and di-branched alkane isomers via temperature- and adsorbate-dependent molecular sieving Wang, Hao; Dong, Xinglong; Velasco, Ever Energy & Environmental Science, Vol. 11, Issue 5 https://doi.org/10.1039/C8EE00459E	journal	January 2018
Planarization of tetracarboxamides: tuning the self-assembly of polycyclic aromatic hydrocarbons Dorca, Yeray; Naranjo, Cristina; Delgado-Martínez, Patricia Chemical Communications, Vol. 55, Issue 43 https://doi.org/10.1039/C9CC02000D	journal	January 2019
Ionic liquid lubricants: designed chemistry for engineering applications Zhou, Feng; Liang, Yongmin; Liu, Weimin Chemical Society Reviews, Vol. 38, Issue 9 https://doi.org/10.1039/b817899m	journal	January 2009
Adsorptive Bulk Separations by Zeolite Molecular Sieves Jasra, R. V.; Bhat, S. G. T. Separation Science and Technology, Vol. 23, Issue 10-11 https://doi.org/10.1080/01496398808058436	journal	August 1988
van der Waals forces in density functional theory: a review of the vdW-DF method Berland, Kristian; Cooper, Valentino R.; Lee, Kyuho Reports on Progress in Physics, Vol. 78, Issue 6 https://doi.org/10.1088/0034-4885/78/6/066501	journal	May 2015
A density functional for sparse matter Langreth, D. C.; Lundqvist, B. I.; Chakarova-Käck, S. D. Journal of Physics: Condensed Matter, Vol. 21, Issue 8 https://doi.org/10.1088/0953-8984/21/8/084203	journal	January 2009
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond Thonhauser, T.; Cooper, Valentino R.; Li, Shen Physical Review B, Vol. 76, Issue 12 https://doi.org/10.1103/PhysRevB.76.125112	journal	September 2007
Spin Signature of Nonlocal Correlation Binding in Metal-Organic Frameworks Thonhauser, T.; Zuluaga, S.; Arter, C. A. Physical Review Letters, Vol. 115, Issue 13 https://doi.org/10.1103/PhysRevLett.115.136402	journal	September 2015
Fluorescent Detection of Carbon Disulfide by a Highly Emissive and Robust Isoreticular Series of Zr-Based Luminescent Metal Organic Frameworks (LMOFs) Velasco, Ever; Osumi, Yuki; Teat, Simon J. Chemistry, Vol. 3, Issue 1 https://doi.org/10.3390/chemistry3010024	journal	March 2021

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
MOF
alkane isomers
flexible structure
hydrocarbon
kinetic separation
metal−organic framework
molecular sieving

Title: Flexible Zn-MOF with Rare Underlying scu Topology for Effective Separation of C6 Alkane Isomers

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