Metal nanoparticles have been deeply studied in the last few decades due to their attractive physical and chemical properties, finding a wide range of applications in several fields. Among them, well-defined nano-structures can combine the main advantages of heterogeneous and homogeneous catalysts. Especially, catalyzed multi-step processes for the production of added-value chemicals represent straightforward synthetic methodologies, including tandem and sequential reactions that avoid the purification of intermediate compounds. In particular, palladium- and copper-based nanocatalysts are often applied, becoming a current strategy in the sustainable synthesis of fine chemicals. The rational tailoring of nanosized materials involving both those immobilized on solid supports and liquid phases and their applications in organic synthesis are herein reviewed.

The combination of first‐row transition compounds or nanoparticles with silica‐based supports offers a great possibility for catalyst design. In particular, iron, cobalt and nickel‐based materials rise in attention due to their availability, low cost and interesting reactivity, enabling transformations that are not possible with noble metals. Different support strategies exist where mesoporous silica‐based supports are of particular interest due to their morphology and stability. Their high surface area, tunable pore size and volume and both, thermal and chemical stability, are of great interest in terms of catalyst adsorption and reactants diffusion. The state of the art on the catalyzed transformations to attain fine chemicals is nowadays explored from a sustainable point of view. However, up to now, it is difficult to predict or understand the key features in silica supported first‐row transition metals‐based catalyst, despite the fact that there are widely applied. The rational tailoring of nanosized materials immobilized on silica‐based supports and their application in catalysis requires to be reviewed.

Thiolate-capped RhNPs in imidazolium-based ionic liquids were synthesized from [Rh(μ-SR)(COD)]₂dimmers under H₂pressure without external addition of ligand stabilizers, preserving thiolate integrity on the nanoparticle surface. This nanoparticulated systems showed a remarkable selectivity that led to their application in theone potreductiveN-alkylation to produce amines.

RhNPs supported on mesoporous silica functionalized with nicotinamide groups provided active hydrogenation catalysts for several functional groups, wherein the shape and size of the RhNPs are maintained after catalysis.