Hybrid Alginate-Brushite Beads Easily Catalyze the Knoevenagel Condensation On-Water.

Abstract

An innovative hybrid organic–inorganic material composed of alginate–brushite xerogel beads was successfully applied for the catalysis of the Knoevenagel condensation. The catalyst was derived from phosphated alginate xerogel microspheres formed from the ionotropic gelling effect of phosphated alginate. To this end, alginate was phosphated by the addition of diammonium hydrogen phosphate in a 1% w/w alginate gel. The phosphated alginate was subsequently precipitated by chelation of Ca2+ cations, generating a phosphated alginate hydrogel microsphere, which was washed and dried, forming hybrid organic–inorganic xerogel beads as a crystalline phosphate-rich mineral fraction covered by alginate. X-ray diffraction analysis revealed that the crystalline inorganic matrix of the material was composed predominantly of brushite. SEM analysis revealed plate-like, ribbon-like, or needle-like morphologies in the hybrid alginate–brushite beads. The hybrid material was tested as a catalyst for Knoevenagel condensation, which was performed ″on-water″ under mild conditions with aromatic aldehydes and activated methylene compounds, giving high yields (up to 97%). The reaction rate and product yield increased together with the reaction temperature for all reagents. The recyclable solid catalyst was effective for three runs, revealing the potential of the innovative hybrid catalyst as an eco-friendly heterogeneous catalyst.