Colas Swalus

Supramolecular Organization in Organic–Inorganic Heterogeneous Hybrid Catalysts Formed from Polyoxometalate and Poly(ampholyte) Polymer

Hybridization of polyoxometalates (POMs) via the formation of an organic-inorganic association constitutes a new route to develop a heterogeneous POM catalyst with tunable functionality imparted through supramolecular assembly. Herein, we report on strategies to obtain tunable well-defined supramolecular architectures of an organic-inorganic heterogeneous hybrid catalyst formed by the association of a hydrophobically substituted polyampholyte copolymer (poly N, N-diallyl-N-hexylamine-alt-maleic acid) and phosphotungstic acid (H3PW12O40) POMs. The self-assembling property of the initial polyampholyte copolymer matrix is modulated by controlling the pH of the hybridization solution. When deposited on a mica surface, isolated, long and extended polymer chains are formed under basic conditions (pH 7.9), while globular or coiled structures are formed under acidic conditions (pH 2). The supramolecular assembly of the POM-polymer hybrid is found to be directed by the type and quantities of charges present on the polyampholyte copolymer, which themselves depend on the pH conditions. The hypothesis is that the Keggin type [PW12O40](3-) anions, which have a size of ~1 nm, electrostatically bind to the positive charge sites of the polymer backbone. The hybrid material stabilized at pH 5.3 consists of POM-decorated polymer chains. Statistical analysis of distances between pairs of POM entities show narrow density distributions, suggesting that POM entities are attached to the polymer chains with a high level of order. Conversely, under acidic conditions (pH 2), the hybrid shows the formation of a core-shell type of structure. The strategies reported here, to tune the supramolecular assembly of organic-inorganic hybrid materials, are highly valuable for the design and a more rational utilization of POM heterogeneous catalysts in several chemical transformations.

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

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.

Controlling the dispersion of supported polyoxometalate heterogeneous catalysts: impact of hybridization and the role of hydrophilicity-hydrophobicity balance and supramolecularity.

Summary The hybridization of polyoxometalates (POMs) through an organic–inorganic association offers several processing advantages in the design of heterogeneous catalysts. A clear understanding of the organization of these hybrid materials on solid surfaces is necessary to optimise their properties. Herein, we report for the first time the organization of Keggin phosphotungstic [PW12O40]3− and Wells–Dawson (WD) phosphomolybdic [P2Mo18O62]6− anions deposited on mica (hydrophilic), and highly oriented pyrolytic graphite (HOPG) (hydrophobic) surfaces. Next, the supramolecular organization of the organic–inorganic hybrid materials formed from the association of POM anions and dimethyldioctadecylammonium bromide (DODA) is investigated as a function of the hydrophilic or hydrophobic nature of the surfaces. The height of the Keggin-POM anions, measured with tapping mode (TM-AFM) is always in good agreement with the molecular dimension of symmetric Keggin-POM anions (ca. 1 nm). However, the asymmetric WD-POM anions form monolayer assemblies on the surfaces with the orientation of their long molecular axis (ca. 1.6 nm) depending on the hydrophilic or hydrophobic properties of the substrate. Namely, the long axis is parallel on mica, and perpendicular on HOPG. When hybridized with DODA, the organization of the hybrid material is dictated by the interaction of the alkyl side chains of DODA with the substrate surface. On HOPG, the DODA–POM hybrid forms small domains of epitaxially arranged straight nanorod structures with their orientation parallel to each other. Conversely, randomly distributed nanospheres are formed when the hybrid material is deposited on freshly cleaved mica. Finally, a UV–ozone treatment of the hybrid material allows one to obtain highly dispersed isolated POM entities on both hydrophilic and hydrophobic surfaces. The hybridization strategy to prevent the clustering of POMs on various supports would enable to develop highly dispersed POM-based heterogeneous catalysts with enhanced functionalities.