How the Hydrophobic Interface between a Perfluorosulfonic Acid Polymer and Water Vapor Controls Membrane Hydration

Soniat, Marielle; Houle, Frances A.

doi:10.1021/acsapm.1c01805

Title: How the Hydrophobic Interface between a Perfluorosulfonic Acid Polymer and Water Vapor Controls Membrane Hydration

Journal Article · Thu Apr 07 00:00:00 EDT 2022 · ACS Applied Polymer Materials

DOI:https://doi.org/10.1021/acsapm.1c01805· OSTI ID:1879823

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Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Stable hydration in perfluorinated polyelectrolyte membranes such as Nafion is essential to maintain good ion conductivity and manage permeation, especially in vapor-fed devices where water content depends on relative humidity in a gas stream. Extensive studies in the literature have shown that Nafion hydration in water vapor is controlled by its interfacial transport resistance. Nafion forms a fluorine-rich layer at the polymer-gas interface, and it has been proposed that this layer blocks water transport due to its hydrophobicity. To develop a molecular-level description of the physics underlying transport resistance in this system, we have performed a computational reaction-diffusion kinetics study of water evaporation from Nafion. Two distinct models are examined, one mimicking the blocking function proposed in the literature and the other assuming that there is no blocking, treating instead water evaporation as a dynamic balance between uptake from the gas and desorption from the polymer surface. Simulation results are compared to time-dependent infrared data over a range of 100-0% relative humidity from the literature. Only the dynamic model successfully reproduces experimental observations. This indicates that the physical nature of interfacial transport resistance is not slow diffusion across an interfacial layer; rather, it is due to the competition between dehydration and rehydration. The simulation data provide details on the accompanying water distributions throughout the membrane and on interfacial kinetics, showing that they are characterized by strong fluctuations.

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

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; SC0004993

OSTI ID:: 1879823

Journal Information:: ACS Applied Polymer Materials, Vol. 4, Issue 5; ISSN 2637-6105

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Elucidating Water Transport Mechanisms in Nafion Thin Films Davis, Eric M.; Stafford, Christopher M.; Page, Kirt A. ACS Macro Letters, Vol. 3, Issue 10 https://doi.org/10.1021/mz500515b	journal	September 2014
Group Vibrational Mode Assignments as a Broadly Applicable Tool for Characterizing Ionomer Membrane Structure as a Function of Degree of Hydration Loupe, Neili; Abu-Hakmeh, Khaldoon; Gao, Shuitao Chemistry of Materials, Vol. 32, Issue 5 https://doi.org/10.1021/acs.chemmater.9b04037	journal	February 2020
Ab initio study of cationic polymeric membranes in water and methanol Karpenko-Jereb, Larisa; Rynkowska, Edyta; Kujawski, Wojciech Ionics, Vol. 22, Issue 3 https://doi.org/10.1007/s11581-015-1551-7	journal	September 2015
Correlating Humidity-Dependent Ionically Conductive Surface Area with Transport Phenomena in Proton-Exchange Membranes He, Qinggang; Kusoglu, Ahmet; Lucas, Ivan T. The Journal of Physical Chemistry B, Vol. 115, Issue 40 https://doi.org/10.1021/jp206154y	journal	October 2011
Water-sorption and transport properties of Nafion 117 H Morris, David R.; Sun, Xiaodong Journal of Applied Polymer Science, Vol. 50, Issue 8 https://doi.org/10.1002/app.1993.070500816	journal	November 1993
Evidence for a crystallite-rich skin on perfluorosulfonate ionomer membranes Tang, Junkun; Yuan, Wangzhang; Zhang, Jidong RSC Advances, Vol. 3, Issue 23 https://doi.org/10.1039/c3ra40430g	journal	January 2013
Predictive simulation of non-steady-state transport of gases through rubbery polymer membranes Soniat, Marielle; Tesfaye, Meron; Brooks, Daniel Polymer, Vol. 134 https://doi.org/10.1016/j.polymer.2017.11.055	journal	January 2018
A vaporization-exchange model for water sorption and flux in Nafion Monroe, Charles W.; Romero, Tatiana; Mérida, Walter Journal of Membrane Science, Vol. 324, Issue 1-2 https://doi.org/10.1016/j.memsci.2008.05.080	journal	October 2008
Material requirements for membrane separators in a water-splitting photoelectrochemical cell Berger, Alan; Segalman, R. A.; Newman, J. Energy Environ. Sci., Vol. 7, Issue 4 https://doi.org/10.1039/c3ee43807d	journal	January 2014
Nanoscale Current Imaging of the Conducting Channels in Proton Exchange Membrane Fuel Cells Bussian, David A.; O'Dea, James R.; Metiu, Horia Nano Letters, Vol. 7, Issue 2 https://doi.org/10.1021/nl061170y	journal	February 2007
Dynamic Emergence of Nanostructure and Transport Properties in Perfluorinated Sulfonic Acid Ionomers Katzenberg, Adlai; Mukherjee, Debdyuti; Dudenas, Peter J. Macromolecules, Vol. 53, Issue 19 https://doi.org/10.1021/acs.macromol.0c01213	journal	September 2020
Insight into the Structure and Nanoscale Conductivity of Fluorinated Ionomer Membranes Hiesgen, Renate; Morawietz, Tobias; Handl, Michael Journal of The Electrochemical Society, Vol. 161, Issue 12 https://doi.org/10.1149/2.0701412jes	journal	January 2014
The Investigation of Water Diffusion into Teflon Copolymer Revealed by Fiber-optic Evanescent Wave Spectroscopy Raichlin, Yosef; Marx, Sharon; Katzir, Abraham The Journal of Physical Chemistry A, Vol. 111, Issue 28 https://doi.org/10.1021/jp071377v	journal	June 2007
Expressions for the Evaporation and Condensation Coefficients in the Hertz-Knudsen Relation Persad, Aaron H.; Ward, Charles A. Chemical Reviews, Vol. 116, Issue 14 https://doi.org/10.1021/acs.chemrev.5b00511	journal	June 2016
Diffusion of Water in Nafion Using Time-Resolved Fourier Transform Infrared−Attenuated Total Reflectance Spectroscopy Hallinan, Daniel T.; Elabd, Yossef A. The Journal of Physical Chemistry B, Vol. 113, Issue 13 https://doi.org/10.1021/jp811325v	journal	April 2009
Non-Fickian Diffusion of Water in Nafion Hallinan, Daniel T.; De Angelis, Maria Grazia; Giacinti Baschetti, Marco Macromolecules, Vol. 43, Issue 10 https://doi.org/10.1021/ma100047z	journal	May 2010
A purely kinetic description of the evaporation of water droplets Houle, Frances A.; Miles, Rachael E. H.; Pollak, Connor J. The Journal of Chemical Physics, Vol. 154, Issue 5 https://doi.org/10.1063/5.0037967	journal	February 2021
Water at Hydrophobic Surfaces: Weak Hydrogen Bonding and Strong Orientation Effects Scatena, L. F. Science, Vol. 292, Issue 5518 https://doi.org/10.1126/science.1059514	journal	May 2001
Subsurface oxide plays a critical role in CO ₂ activation by Cu(111) surfaces to form chemisorbed CO ₂ , the first step in reduction of CO ₂ Favaro, Marco; Xiao, Hai; Cheng, Tao Proceedings of the National Academy of Sciences https://doi.org/10.1073/pnas.1701405114	journal	June 2017
Ab initio and density functional theory (DFT) studies on triflic acid with water and protonated water clusters Prakash, M.; Subramanian, V. Journal of Molecular Modeling, Vol. 22, Issue 12 https://doi.org/10.1007/s00894-016-3158-y	journal	November 2016
ATR-FTIR Study of Water in Nafion Membrane Combined with Proton Conductivity Measurements during Hydration/Dehydration Cycle Kunimatsu, Keiji; Bae, Byungchan; Miyatake, Kenji The Journal of Physical Chemistry B, Vol. 115, Issue 15 https://doi.org/10.1021/jp112300c	journal	April 2011
Surface Structure of Nafion in Vapor and Liquid Bass, Maria; Berman, Amir; Singh, Amarjeet The Journal of Physical Chemistry B, Vol. 114, Issue 11 https://doi.org/10.1021/jp9113128	journal	March 2010
Water sorption, desorption and transport in Nafion membranes Majsztrik, Paul W.; Satterfield, M. Barclay; Bocarsly, Andrew B. Journal of Membrane Science, Vol. 301, Issue 1-2 https://doi.org/10.1016/j.memsci.2007.06.022	journal	September 2007
Molecular Dynamics Study of Structure and Transport of Water and Hydronium Ions at the Membrane/Vapor Interface of Nafion Selvan, Myvizhi Esai; Liu, Junwu; Keffer, David J. The Journal of Physical Chemistry C, Vol. 112, Issue 6 https://doi.org/10.1021/jp075611t	journal	February 2008
Non-Fickian Water Vapor Sorption Dynamics by Nafion Membranes Satterfield, M. Barclay; Benziger, J. B. The Journal of Physical Chemistry B, Vol. 112, Issue 12 https://doi.org/10.1021/jp7103243	journal	March 2008
Comprehensive Picture of Water Dynamics in Nafion Membranes at Different Levels of Hydration Hammer, Regine; Schönhoff, Monika; Hansen, Michael Ryan The Journal of Physical Chemistry B, Vol. 123, Issue 39 https://doi.org/10.1021/acs.jpcb.9b05093	journal	September 2019
Swelling and Diffusion during Methanol Sorption into Hydrated Nafion Soniat, Marielle; Houle, Frances A. The Journal of Physical Chemistry B, Vol. 122, Issue 34 https://doi.org/10.1021/acs.jpcb.8b03169	journal	August 2018
New Insights into Perfluorinated Sulfonic-Acid Ionomers Kusoglu, Ahmet; Weber, Adam Z. Chemical Reviews, Vol. 117, Issue 3 https://doi.org/10.1021/acs.chemrev.6b00159	journal	January 2017
Mechanistic Understanding of CO ₂ Reduction Reaction (CO2RR) Toward Multicarbon Products by Heterogeneous Copper-Based Catalysts Todorova, Tanya K.; Schreiber, Moritz W.; Fontecave, Marc ACS Catalysis, Vol. 10, Issue 3 https://doi.org/10.1021/acscatal.9b04746	journal	December 2019
Multiscale Modeling of Chemical Kinetics via the Master Equation MacNamara, Shev; Burrage, Kevin; Sidje, Roger B. Multiscale Modeling & Simulation, Vol. 6, Issue 4 https://doi.org/10.1137/060678154	journal	January 2008
Water transport and condensation in fluoropolymer films Hansen, Charles M. Progress in Organic Coatings, Vol. 42, Issue 3-4 https://doi.org/10.1016/s0300-9440(01)00168-0	journal	September 2001
Molecular Dynamics Simulations of Water Permeation across Nafion Membrane Interfaces Daly, Kevin B.; Benziger, Jay B.; Panagiotopoulos, Athanassios Z. The Journal of Physical Chemistry B, Vol. 118, Issue 29 https://doi.org/10.1021/jp5024718	journal	July 2014
Penetration of Water Vapor through Perfluorinated Polyether Films on Concentrated Sulfuric Acid Porter, Jeremy J.; Klassen, Jane K.; Nathanson, Gilbert M. Langmuir, Vol. 12, Issue 22 https://doi.org/10.1021/la960460z	journal	January 1996
Hydrated Arrays of Acidic Surface Groups as Model Systems for Interfacial Structure and Mechanisms in PEMs Roudgar, A.; Narasimachary, S. P.; Eikerling, M. The Journal of Physical Chemistry B, Vol. 110, Issue 41 https://doi.org/10.1021/jp063189v	journal	September 2006
Understanding Water Uptake and Transport in Nafion Using X-ray Microtomography Hwang, Gi Suk; Parkinson, Dilworth Y.; Kusoglu, Ahmet ACS Macro Letters, Vol. 2, Issue 4 https://doi.org/10.1021/mz300651a	journal	March 2013
Surface Morphology of Nafion at Hydrated and Dehydrated Conditions O’Dea, James R.; Economou, Nicholas J.; Buratto, Steven K. Macromolecules, Vol. 46, Issue 6 https://doi.org/10.1021/ma302399e	journal	March 2013
Adsorption properties of water vapor on sulfonated perfluoropolymer membranes Takata, H.; Mizuno, N.; Nishikawa, M. International Journal of Hydrogen Energy, Vol. 32, Issue 3 https://doi.org/10.1016/j.ijhydene.2006.09.041	journal	March 2007
Discrete simulation methods in combustion kinetics Bunker, Don L.; Garrett, Bruce; Kleindienst, Tadeusz Combustion and Flame, Vol. 23, Issue 3 https://doi.org/10.1016/0010-2180(74)90120-5	journal	December 1974
Molecular Mechanism of Water Evaporation Nagata, Yuki; Usui, Kota; Bonn, Mischa Physical Review Letters, Vol. 115, Issue 23 https://doi.org/10.1103/physrevlett.115.236102	journal	November 2015
Mechanism of Ionization, Hydration, and Intermolecular H-Bonding in Proton Conducting Nanostructured Ionomers Dalla Bernardina, Simona; Brubach, Jean-Blaise; Berrod, Quentin The Journal of Physical Chemistry C, Vol. 118, Issue 44 https://doi.org/10.1021/jp5074818	journal	October 2014
Comparison of Approaches for Measuring the Mass Accommodation Coefficient for the Condensation of Water and Sensitivities to Uncertainties in Thermophysical Properties Miles, Rachael E. H.; Reid, Jonathan P.; Riipinen, Ilona The Journal of Physical Chemistry A, Vol. 116, Issue 44 https://doi.org/10.1021/jp3083858	journal	October 2012
Erratum to “Water transport and condensation in fluoropolymer films” [Prog. Org. Coat. 142 (2001) 167–178] Hansen, Charles M.; Just, Lisbeth Progress in Organic Coatings, Vol. 44, Issue 3 https://doi.org/10.1016/s0300-9440(02)00005-x	journal	June 2002
Water Permeation through Nafion Membranes: The Role of Water Activity Majsztrik, Paul; Bocarsly, Andrew; Benziger, Jay The Journal of Physical Chemistry B, Vol. 112, Issue 51 https://doi.org/10.1021/jp804197x	journal	November 2008
Activation energies of water vaporization from the bulk and from laponite, montmorillonite, and chitosan powders Prado, J. Rachel; Vyazovkin, Sergey Thermochimica Acta https://doi.org/10.1016/j.tca.2011.06.005	journal	June 2011
Gas-Diffusion Electrodes for Carbon Dioxide Reduction: A New Paradigm Higgins, Drew; Hahn, Christopher; Xiang, Chengxiang ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b02035	journal	December 2018
Characterisation of Fuel Cell Membranes as a Function of Drying by Means of Contact Angle Measurements Brack, H. -P.; Slaski, M.; Gubler, L. Fuel Cells, Vol. 4, Issue 3 https://doi.org/10.1002/fuce.200400018	journal	August 2004
Toward predictive permeabilities: Experimental measurements and multiscale simulation of methanol transport in Nafion Soniat, Marielle; Dischinger, Sarah M.; Weng, Lien‐Chun Journal of Polymer Science, Vol. 59, Issue 7 https://doi.org/10.1002/pol.20200771	journal	February 2021
Humidity-Dependent Structure of Surface Water on Perfluorosulfonated Ionomer Thin Film Studied by Sum Frequency Generation Spectroscopy Noguchi, Hidenori; Taneda, Kento; Minowa, Hiroshi The Journal of Physical Chemistry C, Vol. 114, Issue 9 https://doi.org/10.1021/jp907194k	journal	February 2010
Permeation of CO ₂ and N ₂ through glassy poly(dimethyl phenylene) oxide under steady‐ and presteady‐state conditions Soniat, Marielle; Tesfaye, Meron; Mafi, Amirhossein Journal of Polymer Science, Vol. 58, Issue 9 https://doi.org/10.1002/pol.20200053	journal	February 2020
Interfacial Water Transport Effects in Proton-Exchange Membranes Kientiz, Brian; Yamada, Haruhiko; Nonoyama, Nobuaki Journal of Fuel Cell Science and Technology, Vol. 8, Issue 1 https://doi.org/10.1115/1.4002398	journal	November 2010
Collisions of protic and aprotic gases with a perfluorinated liquid Saecker, Mary E.; Nathanson, Gilbert M. The Journal of Chemical Physics, Vol. 100, Issue 5 https://doi.org/10.1063/1.466333	journal	March 1994
A general method for numerically simulating the stochastic time evolution of coupled chemical reactions Gillespie, Daniel T. Journal of Computational Physics, Vol. 22, Issue 4 https://doi.org/10.1016/0021-9991(76)90041-3	journal	December 1976
Dramatic differences in carbon dioxide adsorption and initial steps of reduction between silver and copper Ye, Yifan; Yang, Hao; Qian, Jin Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09846-y	journal	April 2019
Simple kinetic models from Arrhenius to the computer Bunker, Don L. Accounts of Chemical Research, Vol. 7, Issue 6 https://doi.org/10.1021/ar50078a005	journal	June 1974

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Title: How the Hydrophobic Interface between a Perfluorosulfonic Acid Polymer and Water Vapor Controls Membrane Hydration

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