FTIR spectroscopic study of the complex formation between H+and DMSO in Nafion.
Nafion membranes plasticized with dimethyl sulfoxide (DMSO) have been examined at room temperature using the vacuum ATR - FTIR spectroscopic technique in the range 50-4000cm-1. The amount of the plasticizer corresponds to the molecular ratio n=DMSO/H+=1.2, 2.3, 4.8, 7.0, 9.7 and 13.3. The medium intensity band with two maxima at 780 and 853cm-1have been assigned to the ν(SO) stretching vibrations of the H+(DMSO)2complex. The possible reason of ν(SO) splitting is symmetry decrease of hydrogen bond under the influence of the anion group SO3-electric field. Whereas the mutual association of free DMSO molecules in Nafion leads to appearance of weak band at 86cm-1assigned to the dipole-dipole interactions.
Institute of Problems of Chemical Physics of RAS, 142432, 1 Academician Semenov avenue, Chernogolovka, Moscow region, Russia. Electronic address: karelin@icp.ac.ru.
A I
AI
Karelin
Institute of Problems of Chemical Physics of RAS, 142432, 1 Academician Semenov avenue, Chernogolovka, Moscow region, Russia. Electronic address: kayumov@icp.ac.ru.
R R
RR
Kayumov
Institute of Problems of Chemical Physics of RAS, 142432, 1 Academician Semenov avenue, Chernogolovka, Moscow region, Russia. Electronic address: sanginov@icp.ac.ru.
E A
EA
Sanginov
Institute of Problems of Chemical Physics of RAS, 142432, 1 Academician Semenov avenue, Chernogolovka, Moscow region, Russia. Electronic address: dobr@icp.ac.ru.
Yu A
YA
Dobrovolsky
ATR - FTIR spectroscopy; Complexes H(+)(DMSO)(2) and H(+)(DMSO-d(6))(2); DMSO plasticization; Dipole-dipole interactions; Ion pair SO(3)(−)H(+)(DMSO)(2); Isotope substitution H(+)D(+); Nafion membrane; Protonic conductivity; Strong hydrogen bond OH(+)O; Symmetry decrease