Proton Conduction in Tröger's Base-Linked Poly(crown ether)s

Hasmukh A. Patel; John Selberg; Dhafer Salah; Haoyuan Chen; Yijun Liao; Siva Krishna Mohan Nalluri; Omar K. Farha; Randall Q. Snurr; Marco Rolandi; J. Fraser Stoddart

doi:10.1021/acsami.8b05532

Proton Conduction in Tröger's Base-Linked Poly(crown ether)s

Hasmukh A. Patel, John Selberg, Dhafer Salah, Haoyuan Chen, Yijun Liao, Siva Krishna Mohan Nalluri, Omar K. Farha, Randall Q. Snurr, Marco Rolandi^*, J. Fraser Stoddart

^*Corresponding author for this work

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

33 Scopus citations

Abstract

Exactly 50 years ago, the ground-breaking discovery of dibenzo[18]crown-6 (DB18C6) by Charles Pedersen led to the use of DB18C6 as a receptor in supramolecular chemistry and a host in host-guest chemistry. We have demonstrated proton conductivity in Tröger's base-linked polymers through hydrogen-bonded networks formed from adsorbed water molecules on the oxygen atoms of DB18C6 under humid conditions. Tröger's base-linked polymers - poly(TBL-DB18C6)-t and poly(TBL-DB18C6)-c - synthesized by the in situ alkylation and cyclization of either trans- or cis-di(aminobenzo) [18]crown-6 at room temperature have been isolated as high-molecular-weight polymers. The macromolecular structures of the isomeric poly(TBL-DB18C6)s have been established by spectroscopic techniques and size-exclusion chromatography. The excellent solubility of these polymers in chloroform allows the formation of freestanding membranes, which are thermally stable and also show stability under aqueous conditions. The hydrophilic nature of the DB18C6 building blocks in the polymer facilitates retention of water as confirmed by water vapor adsorption isotherms, which show a 23 wt % water uptake. The adsorbed water is retained even after reducing the relative humidity to 25%. The proton conductivity of poly(TBL-DB18C6)-t, which is found to be 1.4 × 10^-4 mS cm^-1 in a humid environment, arises from the hydrogen bonding and the associated proton-hopping mechanism, as supported by a modeling study. In addition to proton conductivity, the Tröger's base-linked polymers reported here promise a wide range of applications where the sub-nanometer-sized cavities of the crown ethers and the robust film-forming ability are the governing factors in dictating their properties.

Original language	English (US)
Pages (from-to)	25303-25310
Number of pages	8
Journal	ACS Applied Materials and Interfaces
Volume	10
Issue number	30
DOIs	https://doi.org/10.1021/acsami.8b05532
State	Published - Aug 1 2018

Funding

This research is part (project #34-948) of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). J.F.S. would like to thank both KACST and NU for their continued support of this research. Characterization of materials made use of the IMSERC facility at NU, which receives support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). This research used resources of the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under contract no. DE-AC02-05CH11231, and the Quest high performance computing facility at Northwestern University. M.R. acknowledges support from the National Science Foundation (NSF, 1648815). O.K.F. and R.Q.S. acknowledge support from the U.S. Department of Energy (DE-FG02-08ER15967). This research is part (project #34-948) of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). J.F.S. would like to thank both KACST and NU for their continued support of this research. Characterization of materials made use of the IMSERC facility at NU, which receives support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). This research used resources of the National Energy Research Scientific Computing Center (NERSC) a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under contract no. DE-AC02-05CH11231 and the Quest high performance computing facility at Northwestern University. M.R. acknowledges support from the National Science Foundation (NSF, 1648815). O.K.F. and R.Q.S. acknowledge support from the U.S. Department of Energy (DE-FG02-08ER15967).

Keywords

Tröger's base
fuel cell
membrane
poly(crown ether)
proton conduction
water uptake

ASJC Scopus subject areas

General Materials Science

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/acsami.8b05532

Cite this

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title = "Proton Conduction in Tr{\"o}ger's Base-Linked Poly(crown ether)s",

abstract = "Exactly 50 years ago, the ground-breaking discovery of dibenzo[18]crown-6 (DB18C6) by Charles Pedersen led to the use of DB18C6 as a receptor in supramolecular chemistry and a host in host-guest chemistry. We have demonstrated proton conductivity in Tr{\"o}ger's base-linked polymers through hydrogen-bonded networks formed from adsorbed water molecules on the oxygen atoms of DB18C6 under humid conditions. Tr{\"o}ger's base-linked polymers - poly(TBL-DB18C6)-t and poly(TBL-DB18C6)-c - synthesized by the in situ alkylation and cyclization of either trans- or cis-di(aminobenzo) [18]crown-6 at room temperature have been isolated as high-molecular-weight polymers. The macromolecular structures of the isomeric poly(TBL-DB18C6)s have been established by spectroscopic techniques and size-exclusion chromatography. The excellent solubility of these polymers in chloroform allows the formation of freestanding membranes, which are thermally stable and also show stability under aqueous conditions. The hydrophilic nature of the DB18C6 building blocks in the polymer facilitates retention of water as confirmed by water vapor adsorption isotherms, which show a 23 wt \% water uptake. The adsorbed water is retained even after reducing the relative humidity to 25\%. The proton conductivity of poly(TBL-DB18C6)-t, which is found to be 1.4 × 10-4 mS cm-1 in a humid environment, arises from the hydrogen bonding and the associated proton-hopping mechanism, as supported by a modeling study. In addition to proton conductivity, the Tr{\"o}ger's base-linked polymers reported here promise a wide range of applications where the sub-nanometer-sized cavities of the crown ethers and the robust film-forming ability are the governing factors in dictating their properties.",

keywords = "Tr{\"o}ger's base, fuel cell, membrane, poly(crown ether), proton conduction, water uptake",

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AU - Patel, Hasmukh A.

AU - Selberg, John

AU - Salah, Dhafer

AU - Chen, Haoyuan

AU - Liao, Yijun

AU - Mohan Nalluri, Siva Krishna

AU - Farha, Omar K.

AU - Snurr, Randall Q.

AU - Rolandi, Marco

AU - Stoddart, J. Fraser

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AB - Exactly 50 years ago, the ground-breaking discovery of dibenzo[18]crown-6 (DB18C6) by Charles Pedersen led to the use of DB18C6 as a receptor in supramolecular chemistry and a host in host-guest chemistry. We have demonstrated proton conductivity in Tröger's base-linked polymers through hydrogen-bonded networks formed from adsorbed water molecules on the oxygen atoms of DB18C6 under humid conditions. Tröger's base-linked polymers - poly(TBL-DB18C6)-t and poly(TBL-DB18C6)-c - synthesized by the in situ alkylation and cyclization of either trans- or cis-di(aminobenzo) [18]crown-6 at room temperature have been isolated as high-molecular-weight polymers. The macromolecular structures of the isomeric poly(TBL-DB18C6)s have been established by spectroscopic techniques and size-exclusion chromatography. The excellent solubility of these polymers in chloroform allows the formation of freestanding membranes, which are thermally stable and also show stability under aqueous conditions. The hydrophilic nature of the DB18C6 building blocks in the polymer facilitates retention of water as confirmed by water vapor adsorption isotherms, which show a 23 wt % water uptake. The adsorbed water is retained even after reducing the relative humidity to 25%. The proton conductivity of poly(TBL-DB18C6)-t, which is found to be 1.4 × 10-4 mS cm-1 in a humid environment, arises from the hydrogen bonding and the associated proton-hopping mechanism, as supported by a modeling study. In addition to proton conductivity, the Tröger's base-linked polymers reported here promise a wide range of applications where the sub-nanometer-sized cavities of the crown ethers and the robust film-forming ability are the governing factors in dictating their properties.

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KW - proton conduction

KW - water uptake

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Proton Conduction in Tröger's Base-Linked Poly(crown ether)s

Abstract

Funding

Keywords

ASJC Scopus subject areas

UN SDGs

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