Roles of Chemical Functionality and Pore Curvature in the Design of Nanoporous Proton Conductors
Abstract
Nanoporous proton-transporting media are critical components in fuel cells and other electrochemical devices, yet general molecular design criteria for new materials with enhanced performance remain obscure. Aqueous lyotropic liquid crystals (LLCs) comprise a platform for detailed studies of the molecular-level features governing proton transport in monodisperse, water-filled nanopores lined with well-defined chemical functionalities. Here, we report new alkylsulfonic acid LLCs that exhibit H+ conductivities as high as σ = 380 mS/cm at 80°C, which rival those of more acidic, perfluorinated polymers, thus demonstrating that the acidity of the pore functionality is not the sole determinant of proton transport. Direct experimental comparisons of LLCs with convex and concave nanopores of similar dimensions indicate that H+ conductivities therein sensitively depend on the hydration state of the acid functionalities and the pore curvature. These experiments suggest that judicious manipulation of pore curvature provides a new means for optimizing the activities of proton-exchange membranes and nanoporous solid acid catalysts.
- Authors:
-
[1];
[3]
- Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry
- Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry; Schlumberger Technology Center, Sugar Land, TX (United States)
- Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering and Materials Science
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOD; National Science Foundation (NSF)
- OSTI Identifier:
- 1434037
- Grant/Contract Number:
- SC0010328; AC02-06CH11357; GUP-37637; GUP-50116; CHE-9974839; CHE-1048642; DMR-0832760; DMR-1121288
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 40; Journal ID: ISSN 1520-6106
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Jackson, Grayson L., Perroni, Dominic V., and Mahanthappa, Mahesh K. Roles of Chemical Functionality and Pore Curvature in the Design of Nanoporous Proton Conductors. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcb.7b06366.
Jackson, Grayson L., Perroni, Dominic V., & Mahanthappa, Mahesh K. Roles of Chemical Functionality and Pore Curvature in the Design of Nanoporous Proton Conductors. United States. https://doi.org/10.1021/acs.jpcb.7b06366
Jackson, Grayson L., Perroni, Dominic V., and Mahanthappa, Mahesh K. Tue .
"Roles of Chemical Functionality and Pore Curvature in the Design of Nanoporous Proton Conductors". United States. https://doi.org/10.1021/acs.jpcb.7b06366. https://www.osti.gov/servlets/purl/1434037.
@article{osti_1434037,
title = {Roles of Chemical Functionality and Pore Curvature in the Design of Nanoporous Proton Conductors},
author = {Jackson, Grayson L. and Perroni, Dominic V. and Mahanthappa, Mahesh K.},
abstractNote = {Nanoporous proton-transporting media are critical components in fuel cells and other electrochemical devices, yet general molecular design criteria for new materials with enhanced performance remain obscure. Aqueous lyotropic liquid crystals (LLCs) comprise a platform for detailed studies of the molecular-level features governing proton transport in monodisperse, water-filled nanopores lined with well-defined chemical functionalities. Here, we report new alkylsulfonic acid LLCs that exhibit H+ conductivities as high as σ = 380 mS/cm at 80°C, which rival those of more acidic, perfluorinated polymers, thus demonstrating that the acidity of the pore functionality is not the sole determinant of proton transport. Direct experimental comparisons of LLCs with convex and concave nanopores of similar dimensions indicate that H+ conductivities therein sensitively depend on the hydration state of the acid functionalities and the pore curvature. These experiments suggest that judicious manipulation of pore curvature provides a new means for optimizing the activities of proton-exchange membranes and nanoporous solid acid catalysts.},
doi = {10.1021/acs.jpcb.7b06366},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 40,
volume = 121,
place = {United States},
year = {Tue Oct 03 00:00:00 EDT 2017},
month = {Tue Oct 03 00:00:00 EDT 2017}
}
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Works referenced in this record:
Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation
journal, October 2007
- Borup, Rod; Meyers, Jeremy; Pivovar, Bryan
- Chemical Reviews, Vol. 107, Issue 10
Block Copolymers for Fuel Cells
journal, January 2011
- Elabd, Yossef A.; Hickner, Michael A.
- Macromolecules, Vol. 44, Issue 1
Finding the Way to Solar Fuels with Dye-Sensitized Photoelectrosynthesis Cells
journal, September 2016
- Brennaman, M. Kyle; Dillon, Robert J.; Alibabaei, Leila
- Journal of the American Chemical Society, Vol. 138, Issue 40
Designing electronic/ionic conducting membranes for artificial photosynthesis
journal, January 2011
- McFarlane, Shaune L.; Day, Brittney A.; McEleney, Kevin
- Energy & Environmental Science, Vol. 4, Issue 5
Transport in Proton Conductors for Fuel-Cell Applications: Simulations, Elementary Reactions, and Phenomenology
journal, October 2004
- Kreuer, Klaus-Dieter; Paddison, Stephen J.; Spohr, Eckhard
- Chemical Reviews, Vol. 104, Issue 10
Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers
journal, February 2014
- Li, Nanwen; Guiver, Michael D.
- Macromolecules, Vol. 47, Issue 7
Enhancement of anhydrous proton transport by supramolecular nanochannels in comb polymers
journal, April 2010
- Chen, Yangbin; Thorn, Michael; Christensen, Scott
- Nature Chemistry, Vol. 2, Issue 6
Interplay between Structure and Relaxations in Perfluorosulfonic Acid Proton Conducting Membranes
journal, December 2012
- Giffin, Guinevere A.; Haugen, Gregory M.; Hamrock, Steven J.
- Journal of the American Chemical Society, Vol. 135, Issue 2
Parallel cylindrical water nanochannels in Nafion fuel-cell membranes
journal, December 2007
- Schmidt-Rohr, Klaus; Chen, Qiang
- Nature Materials, Vol. 7, Issue 1
Polymer Electrolytes
journal, July 2013
- Hallinan, Daniel T.; Balsara, Nitash P.
- Annual Review of Materials Research, Vol. 43, Issue 1
Morphology of Hydrated As-Cast Nafion Revealed through Cryo Electron Tomography
journal, December 2014
- Allen, Frances I.; Comolli, Luis R.; Kusoglu, Ahmet
- ACS Macro Letters, Vol. 4, Issue 1, p. 1-5
Anomalous ion transport in 2-nm hydrophilic nanochannels
journal, November 2010
- Duan, Chuanhua; Majumdar, Arun
- Nature Nanotechnology, Vol. 5, Issue 12
Functional Liquid-Crystalline Assemblies: Self-Organized Soft Materials
journal, January 2006
- Kato, Takashi; Mizoshita, Norihiro; Kishimoto, Kenji
- Angewandte Chemie International Edition, Vol. 45, Issue 1
Polymerized Lyotropic Liquid Crystal Assemblies for Membrane Applications
journal, March 2008
- Gin, Douglas L.; Bara, Jason E.; Noble, Richard D.
- Macromolecular Rapid Communications, Vol. 29, Issue 5
Water confined in self-assembled ionic surfactant nano-structures
journal, January 2015
- Hanot, Samuel; Lyonnard, Sandrine; Mossa, Stefano
- Soft Matter, Vol. 11, Issue 12
.alpha.-Alkylation of alkyl alkanesulfonates
journal, April 1970
- Truce, William E.; Vrencur, D. J.
- The Journal of Organic Chemistry, Vol. 35, Issue 4
Cross-Linked Normal Hexagonal and Bicontinuous Cubic Assemblies via Polymerizable Gemini Amphiphiles
journal, March 2003
- Pindzola, Brad A.; Jin, Jizhu; Gin, Douglas L.
- Journal of the American Chemical Society, Vol. 125, Issue 10
Unusually Stable Aqueous Lyotropic Gyroid Phases from Gemini Dicarboxylate Surfactants
journal, September 2011
- Sorenson, Gregory P.; Coppage, Keiva L.; Mahanthappa, Mahesh K.
- Journal of the American Chemical Society, Vol. 133, Issue 38
Gemini Surfactants
journal, June 2000
- Menger, Fredric M.; Keiper, Jason S.
- Angewandte Chemie International Edition, Vol. 39, Issue 11
Discovery of a tetracontinuous, aqueous lyotropic network phase with unusual 3D-hexagonal symmetry
journal, January 2014
- Sorenson, Gregory P.; Schmitt, Adam K.; Mahanthappa, Mahesh K.
- Soft Matter, Vol. 10, Issue 41
3D Continuous Water Nanosheet as a Gyroid Minimal Surface Formed by Bicontinuous Cubic Liquid-Crystalline Zwitterions
journal, July 2012
- Ichikawa, Takahiro; Kato, Takashi; Ohno, Hiroyuki
- Journal of the American Chemical Society, Vol. 134, Issue 28
Control of Crystalline Proton-Conducting Pathways by Water-Induced Transformations of Hydrogen-Bonding Networks in a Metal–Organic Framework
journal, May 2014
- Sadakiyo, Masaaki; Yamada, Teppei; Honda, Kyohei
- Journal of the American Chemical Society, Vol. 136, Issue 21
MOFs as proton conductors – challenges and opportunities
journal, January 2014
- Ramaswamy, Padmini; Wong, Norman E.; Shimizu, George K. H.
- Chem. Soc. Rev., Vol. 43, Issue 16
3D Anhydrous Proton-Transporting Nanochannels Formed by Self-Assembly of Liquid Crystals Composed of a Sulfobetaine and a Sulfonic Acid
journal, October 2013
- Soberats, Bartolome; Yoshio, Masafumi; Ichikawa, Takahiro
- Journal of the American Chemical Society, Vol. 135, Issue 41
Increased Water Retention in Polymer Electrolyte Membranes at Elevated Temperatures Assisted by Capillary Condensation
journal, November 2007
- Park, Moon Jeong; Downing, Kenneth H.; Jackson, Andrew
- Nano Letters, Vol. 7, Issue 11
Specific Ion Effects in Amphiphile Hydration and Interface Stabilization
journal, January 2014
- Scheu, Rüdiger; Chen, Yixing; de Aguiar, Hilton B.
- Journal of the American Chemical Society, Vol. 136, Issue 5
Structure and polymorphism of bipolar isopranyl ether lipids from archaebacteria
journal, March 1985
- Gulik, Annette; Luzzati, Vittorio; De Rosa, Mario
- Journal of Molecular Biology, Vol. 182, Issue 1
Limits of Proton Conductivity
journal, August 2012
- Kreuer, Klaus-Dieter; Wohlfarth, Andreas
- Angewandte Chemie International Edition, Vol. 51, Issue 42
Proton Solvation and Transport in Hydrated Nafion
journal, May 2011
- Feng, Shulu; Voth, Gregory A.
- The Journal of Physical Chemistry B, Vol. 115, Issue 19
Wide Control of Proton Conductivity in Porous Coordination Polymers
journal, February 2011
- Shigematsu, Akihito; Yamada, Teppei; Kitagawa, Hiroshi
- Journal of the American Chemical Society, Vol. 133, Issue 7
Water Uptake by and Transport Through Nafion® 117 Membranes
journal, January 1993
- Zawodzinski, Thomas A.
- Journal of The Electrochemical Society, Vol. 140, Issue 4
Equilibrium acidities in dimethyl sulfoxide solution
journal, December 1988
- Bordwell, Frederick G.
- Accounts of Chemical Research, Vol. 21, Issue 12
Formation and mobility of protonic charge carriers in methyl sulfonic acid–water mixtures: A model for sulfonic acid based ionomers at low degree of hydration
journal, April 2010
- Telfah, A.; Majer, G.; Kreuer, K. D.
- Solid State Ionics, Vol. 181, Issue 11-12
Proton Mobilities in Water and in Different Stereoisomers of Covalently Linked Gramicidin A Channels
journal, April 2000
- Cukierman, Samuel
- Biophysical Journal, Vol. 78, Issue 4
Modeling Electrical Conductivity in Concentrated and Mixed-Solvent Electrolyte Solutions
journal, December 2004
- Wang, Peiming; Anderko, Andrzej; Young, Robert D.
- Industrial & Engineering Chemistry Research, Vol. 43, Issue 25
Application of Conductivity Measurement of Nitric Acid Concentration to Plant Control
journal, September 1933
- Coster, H. Marvin
- Industrial & Engineering Chemistry, Vol. 25, Issue 9
Properties of Trifluoromethanesulfonic Acid Monohydrate Pertinent to Its Use as a Fuel Cell Electrolyte
journal, December 1978
- Sarada, T.; Granata, R. D.; Foley, R. T.
- Journal of The Electrochemical Society, Vol. 125, Issue 12
A Fundamental Study of the Transport Properties of Aqueous Superacid Solutions
journal, July 2010
- Suarez, Sophia N.; Jayakody, Jay R. P.; Greenbaum, Steve G.
- The Journal of Physical Chemistry B, Vol. 114, Issue 27
Proton Conduction Properties of Sulfonicacid Type Polymer Gel Electrolytes
journal, January 2009
- Saito, Yuria; Umecky, Tatsuya; Omukai, Hiromasa
- The Journal of Physical Chemistry C, Vol. 113, Issue 7
Controlling Water Content and Proton Conductivity through Copolymer Morphology
journal, December 2013
- Narimani, Rasoul; Yang, Ami C. C.; Tsang, Emily M. W.
- Macromolecules, Vol. 46, Issue 24
Water Uptake and Proton Conductivity in Porous Block Copolymer Electrolyte Membranes
journal, August 2015
- Chen, X. Chelsea; Kortright, Jeffrey B.; Balsara, Nitash P.
- Macromolecules, Vol. 48, Issue 16
Main-chain, statistically sulfonated proton exchange membranes: the relationships of acid concentration and proton mobility to water content and their effect upon proton conductivity
journal, January 2007
- Peckham, Timothy J.; Schmeisser, Jennifer; Rodgers, Marianne
- Journal of Materials Chemistry, Vol. 17, Issue 30
Large protonated water clusters H+(H2O)n (1.ltoreq. n >60): the production and reactivity of clathrate-like structures under thermal conditions
journal, August 1989
- Yang, Xiaolin; Castleman, A. W.
- Journal of the American Chemical Society, Vol. 111, Issue 17
Proton transfer from 1‐naphthol to water: Small clusters to the bulk
journal, July 1989
- Knochenmuss, Richard; Leutwyler, Samuel
- The Journal of Chemical Physics, Vol. 91, Issue 2
Calculation of the aqueous solvation free energy of the proton
journal, September 1998
- Tawa, G. J.; Topol, I. A.; Burt, S. K.
- The Journal of Chemical Physics, Vol. 109, Issue 12
Proton transport mechanism in concentrated aqueous solutions and solid hydrates of acids☆
journal, May 1991
- Dippel, T.; Kreuer, K.
- Solid State Ionics, Vol. 46, Issue 1-2
Water-mediated transport in ion-containing polymers
journal, October 2011
- Hickner, Michael A.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 50, Issue 1
Proton Conduction Mechanisms at Low Degrees of Hydration in Sulfonic Acid–Based Polymer Electrolyte Membranes
journal, August 2003
- Paddison, S. J.
- Annual Review of Materials Research, Vol. 33, Issue 1
Proton Transfer 200 Years after von Grotthuss: Insights from Ab Initio Simulations
journal, September 2006
- Marx, Dominik
- ChemPhysChem, Vol. 7, Issue 9
Effect of Water on the Low Temperature Conductivity of Polymer Electrolytes
journal, March 2006
- Siu, Ana; Schmeisser, Jennifer; Holdcroft, Steven
- The Journal of Physical Chemistry B, Vol. 110, Issue 12
Heterogeneous Catalysis with Cross-Linked Lyotropic Liquid Crystal Assemblies: Organic Analogues to Zeolites and Mesoporous Sieves
journal, October 1999
- Miller, Seth A.; Kim, Esther; Gray, David H.
- Angewandte Chemie International Edition, Vol. 38, Issue 20
How and Why Nanoparticle’s Curvature Regulates the Apparent p K a of the Coating Ligands
journal, February 2011
- Wang, Dawei; Nap, Rikkert J.; Lagzi, István
- Journal of the American Chemical Society, Vol. 133, Issue 7
Water Dynamics in Gyroid Phases of Self-Assembled Gemini Surfactants
journal, February 2016
- Roy, Santanu; Skoff, David; Perroni, Dominic V.
- Journal of the American Chemical Society, Vol. 138, Issue 8
An investigation of proton conduction in select PEM’s and reaction layer interfaces-designed for elevated temperature operation
journal, July 2003
- Ma, Chengsong; Zhang, Lei; Mukerjee, Sanjeev
- Journal of Membrane Science, Vol. 219, Issue 1-2
Poly(arylene ether) Block Copolymer Membranes: Synthesis, Properties and Durability
journal, September 2009
- Bae, Byungchan; Miyatake, Kenji; Watanabe, Masahiro
- ECS Transactions, Vol. 25, Issue 1
Aromatic Ionomers with Highly Acidic Sulfonate Groups: Acidity, Hydration, and Proton Conductivity
journal, November 2011
- Chang, Ying; Brunello, Giuseppe F.; Fuller, Jeffrey
- Macromolecules, Vol. 44, Issue 21
Proton Conductivity of Acid-Functionalized Zeolite Beta, MCM-41, and MCM-48: Effect of Acid Strength
journal, August 2008
- McKeen, John C.; Yan, Yushan S.; Davis, Mark E.
- Chemistry of Materials, Vol. 20, Issue 16
Dynamics of Water in Gemini Surfactant-Based Lyotropic Liquid Crystals
journal, October 2016
- McDaniel, Jesse G.; Mantha, Sriteja; Yethiraj, Arun
- The Journal of Physical Chemistry B, Vol. 120, Issue 41
Works referencing / citing this record:
Nanoporous Polymers Based on Liquid Crystals
journal, January 2018
- Lugger, Jody; Mulder, Dirk; Sijbesma, Rint
- Materials, Vol. 11, Issue 1