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Title: Hydroxide Degradation Pathways for Imidazolium Cations. A DFT Study

Imidazolium cations are promising candidates as covalently tetherable cations for application in anion exchange membranes. They have generated specific interest in alkaline membrane fuel cell applications where ammonium-based cations have been the most commonly applied but have been found to be susceptible to hydroxide attack. In the search for high stability cations, a detailed understanding of the degradation pathways and reaction barriers is required. In this work, we investigate imidazolium and benzimidazolium cations in the presence of hydroxide using density functional theory calculations for their potential in alkaline membrane fuel cells. Moreover, the dominant degradation pathway for these cations is predicted to be the nucleophilic addition–elimination pathway at the C-2 atom position on the imidazolium ring. Steric interferences, introduced by substitutions at the C-2, C-4, and C-5 atom positions, were investigated and found to have a significant, positive impact on calculated degradation energy barriers. Benzimidazolium cations, with their larger conjugated systems, are predicted to degrade much faster than their imidazolium counterparts. Our results provide important insight into designing stable cations for anion exchange membranes. Some of the molecules studied have significantly increased degradation energy barriers suggesting that they could possess significantly improved (several orders of magnitude) durability compared to traditionalmore » cations and potentially enable new applications.« less
Authors:
 [1] ;  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
OSTI Identifier:
1136206
DOE Contract Number:
AC36-08GO28308
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. C; Journal Volume: 118; Journal Issue: 19, 15 May 2014
Publisher:
American Chemical Society
Research Org:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy; USDOE Office of Basic Energy Sciences, Division of Materials Science
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY Computational Sciences; Chemical and Material Sciences