Organic transformations on metal nanoparticles: controlling activity, stability, and recyclability by support and solvent interactions.

The different mechanisms by which the support and the solvent can influence the catalytic properties of a metal nanoparticle (NP) are reviewed. The use of a support not only significantly facilitates the recycling of NPs but also has many additional advantages varying from enhanced stabilization of the NP dispersion to the alteration of the electronic properties of the metal, shape selectivity effects, and even active participation in the reaction mechanism. The correct choice of solvent, on the other hand, can drastically influence properties such as the morphology of the particles and, in the case of alloys, determine the composition of the NPs. Judicious solvent selection also enhances recyclability and stability, and in some cases, the solvent plays a cocatalytic role. Despite the many beneficial effects of combining metal NPs with the correct support or solvent, many processes are not well understood. Further research should be conducted on elucidating the general mechanisms behind the support-NP or solvent-NP interactions.

Transition-metal-free catalysts for the sustainable epoxidation of alkenes: from discovery to optimisation by means of high throughput experimentation.

Transition-metal-free oxides were studied as heterogeneous catalysts for the sustainable epoxidation of alkenes with aqueous H2O2 by means of high throughput experimentation (HTE) techniques. A full-factorial HTE approach was applied in the various stages of the development of the catalysts: the synthesis of the materials, their screening as heterogeneous catalysts in liquid-phase epoxidation and the optimisation of the reaction conditions. Initially, the chemical composition of transition-metal-free oxides was screened, leading to the discovery of gallium oxide as a novel, active and selective epoxidation catalyst. On the basis of these results, the research line was continued with the study of structured porous aluminosilicates, gallosilicates and silica-gallia composites. In general, the gallium-based materials showed the best catalytic performances. This family of materials represents a promising class of heterogeneous catalysts for the sustainable epoxidation of alkenes and offers a valid alternative to the transition-metal heterogeneous catalysts commonly used in epoxidation. High throughput experimentation played an important role in promoting the development of these catalytic systems.