TY - JOUR
T1 - Microhydration of Polymer Electrolyte Membranes
T2 - A Comparison of Hydrogen-Bonding Networks and Spectral Properties of Nafion and Bis[(perfluoroalkyl)sulfonyl] Imide
AU - Silva, Nadeesha J.
AU - Tunega, Daniel
AU - Korzeniewski, Carol
AU - Lischka, Hans
AU - Aquino, Adelia J.A.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/11/21
Y1 - 2019/11/21
N2 - The microhydration effects on two polymer electrolyte membrane materials, Nafion and bis[(perfluoroalkyl)sulfonyl] imide (PFSI), were investigated by analyzing optimized geometries and normal modes of vibration. The calculations were performed on periodic structural models with systematic increases of the number of water molecules around the polar head groups. A strong effect of microhydration on the structure of the polar head groups was observed due to a large red shift of the SO-H (Nafion) and N-H (PFSI) stretching modes of about 600-1000 cm-1. In addition, frequency calculations showed how H2O stretching vibrations contribute to the overall high frequency vibrational spectra. Both asymmetric and symmetric stretching modes of the SO2 group (νas(SO2) and νs(SO2)) were red-shifted indicating the S-O bond weakening upon microhydration. PFSI models showed spectral changes upon microhydration comparable to those observed for Nafion. However, distinct spectral features related to the differences in the polar head groups were observed. Lower N-H stretching frequency compared to the SO-H mode explained a stronger acid character of the PFSI polar headgroup and its earlier proton transfer ability (less water molecules needed for the proton release).
AB - The microhydration effects on two polymer electrolyte membrane materials, Nafion and bis[(perfluoroalkyl)sulfonyl] imide (PFSI), were investigated by analyzing optimized geometries and normal modes of vibration. The calculations were performed on periodic structural models with systematic increases of the number of water molecules around the polar head groups. A strong effect of microhydration on the structure of the polar head groups was observed due to a large red shift of the SO-H (Nafion) and N-H (PFSI) stretching modes of about 600-1000 cm-1. In addition, frequency calculations showed how H2O stretching vibrations contribute to the overall high frequency vibrational spectra. Both asymmetric and symmetric stretching modes of the SO2 group (νas(SO2) and νs(SO2)) were red-shifted indicating the S-O bond weakening upon microhydration. PFSI models showed spectral changes upon microhydration comparable to those observed for Nafion. However, distinct spectral features related to the differences in the polar head groups were observed. Lower N-H stretching frequency compared to the SO-H mode explained a stronger acid character of the PFSI polar headgroup and its earlier proton transfer ability (less water molecules needed for the proton release).
UR - http://www.scopus.com/inward/record.url?scp=85074913958&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcb.9b07815
DO - 10.1021/acs.jpcb.9b07815
M3 - Article
C2 - 31647234
AN - SCOPUS:85074913958
SN - 1520-6106
VL - 123
SP - 9899
EP - 9911
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 46
ER -