Topological effects on separation of alkane isomers in metal−organic frameworks

N. Scott Bobbitt; Andrew S. Rosen; Randall Q. Snurr

doi:10.1016/j.fluid.2020.112642

Topological effects on separation of alkane isomers in metal−organic frameworks

N. Scott Bobbitt, Andrew S. Rosen, Randall Q. Snurr^*

^*Corresponding author for this work

Chemical and Biological Engineering

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

Polymorphism in metal−organic frameworks (MOFs) means that the same chemical building blocks (nodes and linkers) can be used to construct isomeric MOFs with different topological networks. The choice of topology can substantially impact the pore network of the MOF, changing the sizes and shapes of the pores, which has implications for adsorption and separation applications. In this work, we look at the influence of topology in 38 polymorphic MOFs on the separation of linear and branched C4–C6 alkane isomers, a separation of great importance to the petrochemical industry. We find that the MOF Cu₂(1,4-benzenedicarboxylate) in nbo topology (nbo-Cu₂BDC) has particularly high affinity for linear alkanes due to its small pore size, which excludes the branched isomers. Upon studying this MOF in further detail, we find that it can take either of two conformations: a cubic conformation, which is typical of nbo MOFs, and a unique star conformation that contains 1D triangular and hexagonal channels. The determination of which conformation the MOF will adopt depends on steric effects between the nodes and linkers.

Original language	English (US)
Article number	112642
Journal	Fluid Phase Equilibria
Volume	519
DOIs	https://doi.org/10.1016/j.fluid.2020.112642
State	Published - Sep 1 2020

Funding

This work was supported by the Defense Threat Reduction Agency (Grant HDTRA1-19-1-0007). A.S.R. was supported in part by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program, sponsored by the Air Force Research Laboratory (AFRL), the Office of Naval Research (ONR) and the Army Research Office (ARO). A.S.R. also gratefully acknowledges support from a Ryan Fellowship and the International Institute for Nanotechnology at Northwestern University. This research was supported in part through the computational resources and staff contributions provided for the Quest high performance computing facility at Northwestern University which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC. a wholly owned subsidiary of Honeywell International, Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. This work was supported by the Defense Threat Reduction Agency (Grant HDTRA1-19-1-0007 ). A.S.R. was supported in part by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program , sponsored by the Air Force Research Laboratory (AFRL) , the Office of Naval Research (ONR) and the Army Research Office (ARO) . A.S.R. also gratefully acknowledges support from a Ryan Fellowship and the International Institute for Nanotechnology at Northwestern University . This research was supported in part through the computational resources and staff contributions provided for the Quest high performance computing facility at Northwestern University which is jointly supported by the Office of the Provost , the Office for Research, and Northwestern University Information Technology . Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government.

Keywords

Alkane separation
GCMC simulation
MOF
Metal-organic framework
Polymorphism

ASJC Scopus subject areas

General Chemical Engineering
General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1016/j.fluid.2020.112642

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title = "Topological effects on separation of alkane isomers in metal−organic frameworks",

abstract = "Polymorphism in metal−organic frameworks (MOFs) means that the same chemical building blocks (nodes and linkers) can be used to construct isomeric MOFs with different topological networks. The choice of topology can substantially impact the pore network of the MOF, changing the sizes and shapes of the pores, which has implications for adsorption and separation applications. In this work, we look at the influence of topology in 38 polymorphic MOFs on the separation of linear and branched C4–C6 alkane isomers, a separation of great importance to the petrochemical industry. We find that the MOF Cu2(1,4-benzenedicarboxylate) in nbo topology (nbo-Cu2BDC) has particularly high affinity for linear alkanes due to its small pore size, which excludes the branched isomers. Upon studying this MOF in further detail, we find that it can take either of two conformations: a cubic conformation, which is typical of nbo MOFs, and a unique star conformation that contains 1D triangular and hexagonal channels. The determination of which conformation the MOF will adopt depends on steric effects between the nodes and linkers.",

keywords = "Alkane separation, GCMC simulation, MOF, Metal-organic framework, Polymorphism",

author = "Bobbitt, {N. Scott} and Rosen, {Andrew S.} and Snurr, {Randall Q.}",

note = "Publisher Copyright: {\textcopyright} 2020 Elsevier B.V.",

year = "2020",

month = sep,

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doi = "10.1016/j.fluid.2020.112642",

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AU - Bobbitt, N. Scott

AU - Rosen, Andrew S.

AU - Snurr, Randall Q.

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N2 - Polymorphism in metal−organic frameworks (MOFs) means that the same chemical building blocks (nodes and linkers) can be used to construct isomeric MOFs with different topological networks. The choice of topology can substantially impact the pore network of the MOF, changing the sizes and shapes of the pores, which has implications for adsorption and separation applications. In this work, we look at the influence of topology in 38 polymorphic MOFs on the separation of linear and branched C4–C6 alkane isomers, a separation of great importance to the petrochemical industry. We find that the MOF Cu2(1,4-benzenedicarboxylate) in nbo topology (nbo-Cu2BDC) has particularly high affinity for linear alkanes due to its small pore size, which excludes the branched isomers. Upon studying this MOF in further detail, we find that it can take either of two conformations: a cubic conformation, which is typical of nbo MOFs, and a unique star conformation that contains 1D triangular and hexagonal channels. The determination of which conformation the MOF will adopt depends on steric effects between the nodes and linkers.

AB - Polymorphism in metal−organic frameworks (MOFs) means that the same chemical building blocks (nodes and linkers) can be used to construct isomeric MOFs with different topological networks. The choice of topology can substantially impact the pore network of the MOF, changing the sizes and shapes of the pores, which has implications for adsorption and separation applications. In this work, we look at the influence of topology in 38 polymorphic MOFs on the separation of linear and branched C4–C6 alkane isomers, a separation of great importance to the petrochemical industry. We find that the MOF Cu2(1,4-benzenedicarboxylate) in nbo topology (nbo-Cu2BDC) has particularly high affinity for linear alkanes due to its small pore size, which excludes the branched isomers. Upon studying this MOF in further detail, we find that it can take either of two conformations: a cubic conformation, which is typical of nbo MOFs, and a unique star conformation that contains 1D triangular and hexagonal channels. The determination of which conformation the MOF will adopt depends on steric effects between the nodes and linkers.

KW - Alkane separation

KW - GCMC simulation

KW - MOF

KW - Metal-organic framework

KW - Polymorphism

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Topological effects on separation of alkane isomers in metal−organic frameworks

Abstract

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Keywords

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