In recent years it has been recognized that small metal nanoparticles hold the promise that their catalytic properties may be completely different from those of their bulk analogs or their monometallic complexes. Entirely new chem...
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Descripción del proyecto
In recent years it has been recognized that small metal nanoparticles hold the promise that their catalytic properties may be completely different from those of their bulk analogs or their monometallic complexes. Entirely new chemical conversions may be expected because of their shape and thermodynamic properties. So far, this promise has not led to important breakthroughs, as most findings can be categorized, mostly, as typical of homogeneous catalysis, or mimics of heterogeneous catalysts, especially hydrogenation. Nanoparticles need stabilizating reagents; polymers, dendrimers, ionic liquids, detergents, solid surfaces, and small ligands, have been discovered and used by trial and error. In this project we propose the use of concave, large organic molecules that will be developed and used to stabilize small nanoparticles by covering part of the vertices and apices, thereby controlling the size and the shape, leaving edges next to the molecular wings and uncovered surface available for interactions leading to catalysis. The controlling wings contain two or three strongly binding phosphines to prevent dissociation of the controlling agent and to modify, simultaneously the electronic properties of part of the metal atoms. The organic platforms have the advantage that additional groups can be connected to them which can serve as chiral modifiers, as recognition sites for larger molecules, as additional organic catalysts, or as ligands to hold a homogeneous co-catalyst. Three high-risk reactions will be investigated, (enantio)selective hydrogenation of aromatics, conversion of glycerol to high added value products and the selective conversion of syn gas by using devices derived from homogeneous and supramolecular catalysis.