Citation

Beibei Tang, Peiyi Wu*, and H. W. Siesler. In Situ Study of Diffusion and Interaction of Water and Mono- or Divalent Anions in a Positively Charged Membrane Using Two-Dimensional Correlation FT-IR/Attenuated Total Reflection Spectroscopy. J. Phys. Chem. B 2008, 112, 2880-2887.

Abstract

Two-dimensional (2D) correlation analysis based on time-resolved FT-IR/attenuated total reflection (ATR) spectroscopy has been used to study the diffusion behavior of water and mono- or divalent anions in the positively charged membranes of different charge density. In 2D FT-IR/ATR spectra, the splitting of the water δ(OH) bending band in the spectral range 1700−1500 cm-1 indicates that there are three different states of water in the positively charged membrane, that is, the water molecules forming strong or weak hydrogen bonds with hydrophilic groups of the membrane and water molecularly dispersed with weaker hydrogen bonds. The wavenumber difference of the δ(OH) band in the low- and high-charge-density membrane indicates that water molecules form much stronger hydrogen bonds with hydrophilic groups in the high-charge-density membrane. The sequential order of the three water bands intensity changes shows that, in the process of water diffusion into the high-charge-density membrane, the hydrogen-bonding interaction between hydrophilic groups of the membrane and water molecules takes place gradually due to the highly cross-linked network structure of the membrane; in the process of water diffusion into the low-charge-density membrane, the strong hydrogen-bonding interaction between hydrophilic groups of the membrane and water molecules takes place instantaneously and this type of water easily diffuses due to the weak interactions between the water molecules and the membrane polymer. Furthermore, the diffusion processes of the electrolyte solution such as NaAc and Na2SO4aqueous solutions in the positively charged membrane have also been examined.