On the Nature of Field-Enhanced Water Dissociation in Bipolar Membranes

Bui, Justin C.; Corpus, Kaitlin Rae M.; Bell, Alexis T.; Weber, Adam Z.

doi:10.1021/acs.jpcc.1c08276

On the Nature of Field-Enhanced Water Dissociation in Bipolar Membranes

Journal Article · Tue Nov 09 00:00:00 EST 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c08276· OSTI ID:1897718

^[1]; ^[1]; ^[1]; ^[2]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Bipolar membranes (BPMs) possess the potential to optimize pH environments for electrochemical synthesis applications when employed in reverse bias. Unfortunately, the performance of BPMs in reverse bias has long been limited by the rate of water dissociation (WD) occurring at the interface of the BPM. Herein, we develop a continuum model of the BPM that agrees with experiment to understand and enhance WD catalyst performance by considering multiple kinetic pathways for WD in the BPM junction catalyst layer. Here, the model reveals that WD catalysts with a more highly alkaline or acidic pH at the point of zero charge (pH_PZC) exhibit accelerated WD kinetics because the more acidic or alkaline pH_PZC catalysts possess greater surface charge, enhancing the local electric field and rate of WD. The model is then employed to explore the sensitivity of the BPM performance to various BPM physical parameters. Finally, the model is used to simulate the operation of bimetallic WD catalysts, demonstrating that an optimal bimetallic catalyst has an acidic pH_PZC catalyst matched with the cation-exchange layer and an alkaline pH_PZC catalyst matched with the anion-exchange layer. The study provides insight into the operation of BPM WD catalysts and gives direction toward the development of next-generation WD catalysts for optimal BPM performance under water-splitting and related conditions.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: National Science Foundation (NSF); US Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0021266

OSTI ID:: 1897718

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 45 Vol. 125; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Electrochemical characterization of polymer ion‐exchange bipolar membranes Mafé, S.; Ramírez, P. Acta Polymerica, Vol. 48, Issue 7, p. 234-250 https://doi.org/10.1002/actp.1997.010480702	journal	July 1997
Bipolar Membrane-Assisted Solar Water Splitting in Optimal pH Luo, Jingshan; Vermaas, David A.; Bi, Dongqin Advanced Energy Materials, Vol. 6, Issue 13 https://doi.org/10.1002/aenm.201600100	journal	April 2016
Proton Transfer, Acid-Base Catalysis, and Enzymatic Hydrolysis. Part I: ELEMENTARY PROCESSES Eigen, M. Angewandte Chemie International Edition in English, Vol. 3, Issue 1 https://doi.org/10.1002/anie.196400011	journal	January 1964
Enhancing the Alkaline Hydrogen Evolution Reaction Activity through the Bifunctionality of Ni(OH) ₂ /Metal Catalysts Danilovic, N.; Subbaraman, Ram; Strmcnik, D. Angewandte Chemie International Edition, Vol. 51, Issue 50 https://doi.org/10.1002/anie.201204842	journal	November 2012
Use of Bipolar Membranes for Maintaining Steady-State pH Gradients in Membrane-Supported, Solar-Driven Water Splitting McDonald, Michael B.; Ardo, Shane; Lewis, Nathan S. ChemSusChem, Vol. 7, Issue 11 https://doi.org/10.1002/cssc.201402288	journal	September 2014
Assessing the Utility of Bipolar Membranes for use in Photoelectrochemical Water-Splitting Cells Vargas-Barbosa, Nella M.; Geise, Geoffrey M.; Hickner, Michael A. ChemSusChem, Vol. 7, Issue 11 https://doi.org/10.1002/cssc.201402535	journal	September 2014
Reduced Graphene Oxide Bipolar Membranes for Integrated Solar Water Splitting in Optimal pH McDonald, Michael B.; Bruce, Jared P.; McEleney, Kevin ChemSusChem, Vol. 8, Issue 16 https://doi.org/10.1002/cssc.201500538	journal	July 2015
Catalytic, Conductive Bipolar Membrane Interfaces through Layer-by-Layer Deposition for the Design of Membrane-Integrated Artificial Photosynthesis Systems McDonald, Michael B.; Freund, Michael S.; Hammond, Paula T. ChemSusChem, Vol. 10, Issue 22 https://doi.org/10.1002/cssc.201701397	journal	November 2017
Electric field-assisted proton transfer and water dissociation at the junction of a fixed-charge bipolar membrane Mafé, Salvador; Ramı́rez, Patricio; Alcaraz, Antonio Chemical Physics Letters, Vol. 294, Issue 4-5 https://doi.org/10.1016/S0009-2614(98)00877-X	journal	September 1998
Zeta-potential measurement using the Smoluchowski equation and the slope of the current–time relationship in electroosmotic flow Sze, Alice; Erickson, David; Ren, Liqing Journal of Colloid and Interface Science, Vol. 261, Issue 2 https://doi.org/10.1016/S0021-9797(03)00142-5	journal	May 2003
Enhance CO2-to-C2+ products yield through spatial management of CO transport in Cu/ZnO tandem electrodes Zhang, Tianyu; Li, Zhengyuan; Zhang, Jianfang Journal of Catalysis, Vol. 387 https://doi.org/10.1016/j.jcat.2020.05.002	journal	July 2020
Cu-Ag Tandem Catalysts for High-Rate CO2 Electrolysis toward Multicarbons Chen, Chubai; Li, Yifan; Yu, Sunmoon Joule, Vol. 4, Issue 8 https://doi.org/10.1016/j.joule.2020.07.009	journal	August 2020
Ion transport in phase-separated single ion conductors Peng, Jing; Zawodzinski, Thomas A. Journal of Membrane Science, Vol. 555 https://doi.org/10.1016/j.memsci.2018.03.029	journal	June 2018
A comprehensive mathematical model of water splitting in bipolar membranes: Impact of the spatial distribution of fixed charges and catalyst at bipolar junction Mareev, S. A.; Evdochenko, E.; Wessling, M. Journal of Membrane Science, Vol. 603 https://doi.org/10.1016/j.memsci.2020.118010	journal	May 2020
Bipolar membranes: A review on principles, latest developments, and applications Pärnamäe, R.; Mareev, S.; Nikonenko, V. Journal of Membrane Science, Vol. 617 https://doi.org/10.1016/j.memsci.2020.118538	journal	January 2021
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
Ion Diffusion Coefficients in Ion Exchange Membranes: Significance of Counterion Condensation Kamcev, Jovan; Paul, Donald R.; Manning, Gerald S. Macromolecules, Vol. 51, Issue 15 https://doi.org/10.1021/acs.macromol.8b00645	journal	July 2018
Reduced Ion Crossover in Bipolar Membrane Electrolysis via Increased Current Density, Molecular Size, and Valence Blommaert, Marijn A.; Verdonk, Joost A. H.; Blommaert, Hester C. B. ACS Applied Energy Materials, Vol. 3, Issue 6 https://doi.org/10.1021/acsaem.0c00687	journal	May 2020
Understanding Multi-Ion Transport Mechanisms in Bipolar Membranes Bui, Justin C.; Digdaya, Ibadillah; Xiang, Chengxiang ACS Applied Materials & Interfaces, Vol. 12, Issue 47 https://doi.org/10.1021/acsami.0c12686	journal	November 2020
High-Performance Bipolar Membrane Development for Improved Water Dissociation Chen, Yingying; Wrubel, Jacob A.; Klein, W. Ellis ACS Applied Polymer Materials, Vol. 2, Issue 11 https://doi.org/10.1021/acsapm.0c00653	journal	August 2020
Thin Cation-Exchange Layers Enable High-Current-Density Bipolar Membrane Electrolyzers via Improved Water Transport Oener, Sebastian Z.; Twight, Liam P.; Lindquist, Grace A. ACS Energy Letters https://doi.org/10.1021/acsenergylett.0c02078	journal	November 2020
Insights and Challenges for Applying Bipolar Membranes in Advanced Electrochemical Energy Systems Blommaert, Marijn A.; Aili, David; Tufa, Ramato Ashu ACS Energy Letters, Vol. 6, Issue 7 https://doi.org/10.1021/acsenergylett.1c00618	journal	June 2021
Ionic Processes in Water Electrolysis: The Role of Ion-Selective Membranes Oener, S. Z.; Ardo, S.; Boettcher, S. W. ACS Energy Letters, Vol. 2, Issue 11 https://doi.org/10.1021/acsenergylett.7b00764	journal	October 2017
CO ₂ Electroreduction from Carbonate Electrolyte Li, Yuguang C.; Lee, Geonhui; Yuan, Tiange ACS Energy Letters, Vol. 4, Issue 6 https://doi.org/10.1021/acsenergylett.9b00975	journal	May 2019
Graphene Oxide as a Water Dissociation Catalyst in the Bipolar Membrane Interfacial Layer McDonald, Michael B.; Freund, Michael S. ACS Applied Materials & Interfaces, Vol. 6, Issue 16 https://doi.org/10.1021/am503242v	journal	July 2014
Recombination of hydrogen ion (H+) and hydroxide in pure liquid water Natzle, Wesley C.; Moore, C. Bradley The Journal of Physical Chemistry, Vol. 89, Issue 12 https://doi.org/10.1021/j100258a035	journal	June 1985
Irreversible Processes in Electrolytes. Diffusion, Conductance and Viscous Flow in Arbitrary Mixtures of Strong Electrolytes Onsager, Lars; Fuoss, R. M. The Journal of Physical Chemistry, Vol. 36, Issue 11 https://doi.org/10.1021/j150341a001	journal	November 1932
Dielectric Constant for the Dioxane—Water System from 20 to 35° Critchfield, Frank E.; Gibson, John A.; Hall, James L. Journal of the American Chemical Society, Vol. 75, Issue 8 https://doi.org/10.1021/ja01104a506	journal	April 1953
Ion and Water Transport Characteristics of Perfluorosulfonated Ionomer Membranes with H ⁺ and Alkali Metal Cations Okada, Tatsuhiro; Satou, Hiroyuki; Okuno, Mitsuhiro The Journal of Physical Chemistry B, Vol. 106, Issue 6 https://doi.org/10.1021/jp013195l	journal	February 2002
Characterization and Surface-Reactivity of Nanocrystalline Anatase in Aqueous Solutions Ridley, Moira K.; Hackley, Vincent A.; Machesky, Michael L. Langmuir, Vol. 22, Issue 26 https://doi.org/10.1021/la061774h	journal	December 2006
Strong electric field effects on proton transfer between membrane-bound amines and water Simons, R. Nature, Vol. 280, Issue 5725 https://doi.org/10.1038/280824a0	journal	August 1979
Onsager’s Wien effect on a lattice Kaiser, V.; Bramwell, S. T.; Holdsworth, P. C. W. Nature Materials, Vol. 12, Issue 11 https://doi.org/10.1038/nmat3729	journal	August 2013
A direct coupled electrochemical system for capture and conversion of CO2 from oceanwater Digdaya, Ibadillah A.; Sullivan, Ian; Lin, Meng Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-18232-y	journal	September 2020
Ion diode logics for pH control Gabrielsson, Erik O.; Tybrandt, Klas; Berggren, Magnus Lab on a Chip, Vol. 12, Issue 14 https://doi.org/10.1039/c2lc40093f	journal	January 2012
Modeling and simulation of the water gradient within a Nafion membrane Ozmaian, Masoumeh; Naghdabadi, Reza Physical Chemistry Chemical Physics, Vol. 16, Issue 7 https://doi.org/10.1039/c3cp54015d	journal	January 2014
Surface acidity of quartz: understanding the crystallographic control Liu, Xiandong; Cheng, Jun; Lu, Xiancai Phys. Chem. Chem. Phys., Vol. 16, Issue 48 https://doi.org/10.1039/c4cp02955k	journal	January 2014
Partitioning of mobile ions between ion exchange polymers and aqueous salt solutions: importance of counter-ion condensation Kamcev, Jovan; Galizia, Michele; Benedetti, Francesco M. Physical Chemistry Chemical Physics, Vol. 18, Issue 8 https://doi.org/10.1039/c5cp06747b	journal	January 2016
High performance electrospun bipolar membrane with a 3D junction Shen, Chunhui; Wycisk, Ryszard; Pintauro, Peter N. Energy & Environmental Science, Vol. 10, Issue 6 https://doi.org/10.1039/c7ee00345e	journal	January 2017
The balance of electric field and interfacial catalysis in promoting water dissociation in bipolar membranes Yan, Zhifei; Zhu, Liang; Li, Yuguang C. Energy & Environmental Science, Vol. 11, Issue 8 https://doi.org/10.1039/c8ee01192c	journal	January 2018
Ion transport mechanisms in bipolar membranes for (photo)electrochemical water splitting Vermaas, David A.; Wiegman, Sandra; Nagaki, Tetsuro Sustainable Energy & Fuels, Vol. 2, Issue 9 https://doi.org/10.1039/c8se00118a	journal	January 2018
Towards membrane-electrode assembly systems for CO ₂ reduction: a modeling study Weng, Lien-Chun; Bell, Alexis T.; Weber, Adam Z. Energy & Environmental Science, Vol. 12, Issue 6 https://doi.org/10.1039/c9ee00909d	journal	January 2019
Modeling the electrochemical behavior and interfacial junction profiles of bipolar membranes at solar flux relevant operating current densities Lin, Meng; Digdaya, Ibadillah A.; Xiang, Chengxiang Sustainable Energy & Fuels, Vol. 5, Issue 7 https://doi.org/10.1039/d1se00201e	journal	January 2021
Deviations from Ohm's Law in Weak Electrolytes Onsager, Lars The Journal of Chemical Physics, Vol. 2, Issue 9 https://doi.org/10.1063/1.1749541	journal	September 1934
Current‐voltage curves of bipolar membranes Ramírez, P.; Rapp, H. J.; Reichle, S. Journal of Applied Physics, Vol. 72, Issue 1 https://doi.org/10.1063/1.352124	journal	July 1992
Selective reduction of CO to acetaldehyde with CuAg electrocatalysts Wang, Lei; Higgins, Drew C.; Ji, Yongfei Proceedings of the National Academy of Sciences, Vol. 117, Issue 23 https://doi.org/10.1073/pnas.1821683117	journal	January 2020
Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces Subbaraman, R.; Tripkovic, D.; Strmcnik, D. Science, Vol. 334, Issue 6060 https://doi.org/10.1126/science.1211934	journal	December 2011
Accelerating water dissociation in bipolar membranes and for electrocatalysis Oener, Sebastian Z.; Foster, Marc J.; Boettcher, Shannon W. Science, Vol. 369, Issue 6507 https://doi.org/10.1126/science.aaz1487	journal	July 2020
A Dusty Fluid Model for Predicting Hydroxyl Anion Conductivity in Alkaline Anion Exchange Membranes Grew, Kyle N.; Chiu, Wilson K. S. Journal of The Electrochemical Society, Vol. 157, Issue 3 https://doi.org/10.1149/1.3273200	journal	January 2010
Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part I. Thermodynamic Model and Validation Crothers, Andrew R.; Darling, Robert M.; Kusoglu, Ahmet Journal of The Electrochemical Society, Vol. 167, Issue 1 https://doi.org/10.1149/1945-7111/ab6723	journal	January 2020
Theory of Multicomponent Phenomena in Cation-Exchange Membranes: Part II. Transport Model and Validation Crothers, Andrew R.; Darling, Robert M.; Kusoglu, Ahmet Journal of The Electrochemical Society, Vol. 167, Issue 1 https://doi.org/10.1149/1945-7111/ab6724	journal	January 2020
Modeling Water Electrolysis in Bipolar Membranes Wrubel, Jacob A.; Chen, Yingying; Ma, Zhiwen Journal of The Electrochemical Society, Vol. 167, Issue 11 https://doi.org/10.1149/1945-7111/ab9ccb	journal	July 2020
Effects of Temperature and Carbon Dioxide on Anion Exchange Membrane Conductivity Grew, Kyle N.; Ren, Xiaoming; Chu, Deryn Electrochemical and Solid-State Letters, Vol. 14, Issue 12 https://doi.org/10.1149/2.011112esl	journal	January 2011
Understanding Transport at the Acid-Alkaline Interface of Bipolar Membranes Grew, Kyle N.; McClure, Joshua P.; Chu, Deryn Journal of The Electrochemical Society, Vol. 163, Issue 14 https://doi.org/10.1149/2.0941614jes	journal	January 2016
Design Principles of Bipolar Electrochemical Co-Electrolysis Cells for Efficient Reduction of Carbon Dioxide from Gas Phase at Low Temperature Pătru, Alexandra; Binninger, Tobias; Pribyl, Bernhard Journal of The Electrochemical Society, Vol. 166, Issue 2 https://doi.org/10.1149/2.1221816jes	journal	January 2019

Similar Records

Measuring pH Changes Inside a Bipolar Membrane Junction

Journal Article · Sun Feb 08 19:00:00 EST 2026 · ACS Energy Letters · OSTI ID:3020738

Materials descriptors for advanced water dissociation catalysts in bipolar membranes

Journal Article · Sun Jun 30 20:00:00 EDT 2024 · Nature Materials · OSTI ID:2569640

Bipolar Membranes for Ion Management in (Photo)Electrochemical Energy Conversion

Journal Article · Mon Oct 25 20:00:00 EDT 2021 · Accounts of Materials Research · OSTI ID:3011121

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysts
electric fields
electrodes
interfaces
pH

On the Nature of Field-Enhanced Water Dissociation in Bipolar Membranes

Citation Formats

References (54)

Similar Records

Related Subjects