Energetics of Base–Acid Pairs for the Design of High-Temperature Fuel Cell Polymer Electrolytes
Abstract
The interaction energy of base–acid plays a key role in acid retention of phosphoric acid (PA)-doped polymer electrolytes under fuel cell operating conditions. Here, we investigate the energetics of proton-accepting and hydroxide-donating organic bases using density functional theory calculations. Because of their weak basicity, proton-accepting organic bases such as benzimidazole have relatively low interaction energy with the acid in the absence of water (15.3–28.0 kcal mol–1). Energetics of the proton-accepting base–PA complex increases by adding water, indicating that the interactions in the base–acid complex strengthen in the presence of water. On the other hand, hydroxide-donating organic bases, such as tetramethylammonium hydroxide, have high interaction energy with PA (~110 kcal mol–1), which remains high in the presence of water. The chemical shifts of 31P NMR support the energetics of the base–acid complexes. Overall, this study further discusses the benefit of incorporating hydroxide-donating organic bases into the polymeric structure over proton-accepting bases as a way to increase acid retention.
- Authors:
-
[1];
[2];
[2]
- Univ. of New Mexico, Albuquerque, NM (United States). Center for Micro-Engineered Materials (CMEM); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1711404
- Report Number(s):
- LA-UR-20-24283
Journal ID: ISSN 1520-6106
- Grant/Contract Number:
- 89233218CNA000001; AR0001003; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
- Additional Journal Information:
- Journal Volume: 124; Journal Issue: 35; Journal ID: ISSN 1520-6106
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Interaction energies; cations; acid and base chemistry; molecules; polymers
Citation Formats
Matanovic, Ivana, Lee, Albert S., and Kim, Yu Seung. Energetics of Base–Acid Pairs for the Design of High-Temperature Fuel Cell Polymer Electrolytes. United States: N. p., 2020.
Web. doi:10.1021/acs.jpcb.0c05672.
Matanovic, Ivana, Lee, Albert S., & Kim, Yu Seung. Energetics of Base–Acid Pairs for the Design of High-Temperature Fuel Cell Polymer Electrolytes. United States. https://doi.org/10.1021/acs.jpcb.0c05672
Matanovic, Ivana, Lee, Albert S., and Kim, Yu Seung. Tue .
"Energetics of Base–Acid Pairs for the Design of High-Temperature Fuel Cell Polymer Electrolytes". United States. https://doi.org/10.1021/acs.jpcb.0c05672. https://www.osti.gov/servlets/purl/1711404.
@article{osti_1711404,
title = {Energetics of Base–Acid Pairs for the Design of High-Temperature Fuel Cell Polymer Electrolytes},
author = {Matanovic, Ivana and Lee, Albert S. and Kim, Yu Seung},
abstractNote = {The interaction energy of base–acid plays a key role in acid retention of phosphoric acid (PA)-doped polymer electrolytes under fuel cell operating conditions. Here, we investigate the energetics of proton-accepting and hydroxide-donating organic bases using density functional theory calculations. Because of their weak basicity, proton-accepting organic bases such as benzimidazole have relatively low interaction energy with the acid in the absence of water (15.3–28.0 kcal mol–1). Energetics of the proton-accepting base–PA complex increases by adding water, indicating that the interactions in the base–acid complex strengthen in the presence of water. On the other hand, hydroxide-donating organic bases, such as tetramethylammonium hydroxide, have high interaction energy with PA (~110 kcal mol–1), which remains high in the presence of water. The chemical shifts of 31P NMR support the energetics of the base–acid complexes. Overall, this study further discusses the benefit of incorporating hydroxide-donating organic bases into the polymeric structure over proton-accepting bases as a way to increase acid retention.},
doi = {10.1021/acs.jpcb.0c05672},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 35,
volume = 124,
place = {United States},
year = {Tue Aug 04 00:00:00 EDT 2020},
month = {Tue Aug 04 00:00:00 EDT 2020}
}
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