Analysis
of the Hydration Process and Rotational Dynamics
of Water in a Nafion Membrane Studied by <sup>1</sup>H NMR Spectroscopy
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Abstract
<sup>1</sup>H NMR spectroscopy is employed to reveal the hydration
process of a Nafion membrane by measuring both the chemical shift
and the spin–lattice relaxation time. In a former study, the
hydration process was suggested to comprise two steps: the molecular
adsorption of water on the sulfonic acid groups and wetting with liquid
water. The present study has revealed the first step can further be
divided into two steps. By introducing a new experimental technique,
the quantitatively reliable NMR measurements of protons (<sup>1</sup>H) of water involved in the polymer membrane are realized. In addition,
a new analytical procedure is developed using a reciprocal concentration
on a saturation–adsorption model, and the hydration is clearly
revealed to have three individual steps. Both the chemical shift and
the relaxation time plots against the reciprocal concentration exhibit
three linear parts with apparently different slopes. Of great interest
is that the initial hydration is divided into two stages: the first
hydration is a very strong adsorption of water probably on the hydroxyl
group of the sulfonic acid group, and the second one is a relatively
weak adsorption on another site of the sulfonic acid group. The third
hydration is readily assigned to excess bulk (liquid-like) water as
expected. These adsorption processes are readily correlated with the
rotational motion of water by converting the spin–lattice relaxation
time to the rotational correlation time