In situ quartz crystal microbalance monitoring of the adsorption of polyoxometalate on a polyampholyte polymer matrix

Raj, Gijo [UCL] Swalus, Colas [UCL] Delcroix, Marie [UCL] Devillers, Michel [UCL] Dupont-Gillain, Christine C. [UCL] Gaigneaux, Eric M. [UCL]

Hybridization of polyoxometalates (POMs) via an organic–inorganic association constitutes a new route to develop heterogeneous POM catalysts with tunable supramolecular architecture. As the structural stability of POMs is strongly influenced by the pH conditions, a quantitative understanding of the POMs-polymer association is important in practical applications. Herein, we use Quartz Crystal Microbalance (QCM) to systematically investigate the interactions of Keggin phosphotungstic acid POM with a polyampholyte polymer-coated QCM sensor as a function of pH. The mass of adsorbed POMs increases when pH decreases from 5.6 to 2, indicating that electrostatic forces play a major role in the formation of POM-polymer hybrids. This finding is complemented by AFM images that show an increase in the size of the hybrid entities from 5 to 12 nm as the pH decreases from 5.6 to 2. The POM adsorbed amount at a particular pH value reaches an equilibrium level with time. The hybrids further gain in adsorbed mass only when lowering the pH value of the POM solution. The hybrid structure formed above pH 2 shows resistance to leaching as indicated by the steady level of the adsorbed mass during a rinsing step with water. However, at pH 2, the rinsing step causes desorption of some weakly adsorbed POMs. It is shown that leached POMs can be re-adsorbed back into the polymer matrix during a second contact with a POM solution at pH 2. This adsorption–desorption cycles of POMs were successfully repeated. Our experiments shed light into the coexistence of tightly as well as loosely bound POMs in hybrid catalyst formed at pH 2. The loosely bound POMs can potentially act as homogeneous catalysts when desorbed. However, these leached POMs can be re-adsorbed back into the matrix, preserving the heterogeneous state of the catalyst. Our results show that QCM is a powerful technique to study in situ the dynamics of the adsorption of POMs on a polymer matrix under different pH conditions.