Controlled assembly of heterogeneous aggregates of clay, iron hydr(oxydes) and polysaccharide: Effects of preparation conditions

Abstract

The preparation of well-defined organo-mineral assemblies under controlled conditions is required to improve our understanding of the formation and surface reactivity of micrometric aggregates, ubiquitous in soils and continental aquatic media. We aim at investigating the building of organo-mineral assemblies with a specific focus on the assembly mode and its consequence on the final properties of the micrometric aggregates. In this work, the preparation and detailed characterization of clay-size aggregates composed of a clay mineral (illite), organic polymer (Dextran polysaccharide) and iron (hydr)oxide are reported, with a focus on the structural organization of the generated aggregates. A step-by-step strategy was developed, and three sets of clay-size composites were prepared with illite particles as a starting material. In two first steps, two distinct sets of two-component composites were obtained according to different procedures. Illite‑iron (hydr)oxide composites were obtained by alkaline hydrolysis of iron in the presence of illite particles, and illite-Dextran aggregates were obtained through the addition of Dextran polysaccharide to an illite suspension. In a third step, three-component micro-aggregates were obtained by subsequent addition of Dextran to suspensions containing the formed illite‑iron (hydr)oxide composite. The so-prepared 2- and 3- component aggregates were investigated by electrophoresis, electron microscopy, X-ray absorption and FTIR spectroscopies. For materials containing Dextran, electrophoretic mobility measurements evidenced variations of surface charge, combined with an increase of aggregate size highlighted by dynamic light scattering. Electron microscopy and EXAFS at iron K-edge evidenced the precipitation of nanoparticles of iron (hydr)oxide onto clay mineral surfaces. FTIR data in transmission and diffuse reflectance modes supported not only the adsorption of Dextran but also the preferential localization of Dextran at the external surfaces of the aggregates. All in all, data collected on the two- and three-component materials demonstrated that the presence of iron (hydr)oxide nanoparticles on the surface of illite strongly modified the organization of organic and mineral constituents.