The hydroformylation of olefins is one of the most important homogeneously catalyzed processes in industry to produce bulk chemicals. Despite the high catalytic activities and selectivity’s using rhodium-based homogeneous hydroformylation catalysts, catalyst recovery and recycling from the reaction mixture remain a challenging topic on a process level. Therefore, technical solutions involving alternate approaches with heterogeneous catalysts for the conversion of olefins into aldehydes have been considered and research activities have addressed the synthesis and development of heterogeneous rhodium-based hydroformylation catalysts. Different strategies were pursued by different groups of authors, such as the deposition of molecular rhodium complexes, metallic rhodium nanoparticles and single-atom catalysts on a solid support as well as rhodium complexes present in supported liquids. An overview of the recent developments made in the area of the heterogenization of homogeneous rhodium catalysts and their application in the hydroformylation of short-chain olefins is given. A special focus is laid on the mechanistic understanding of the heterogeneously catalyzed reactions at a molecular level in order to provide a guide for the future design of rhodium-based heterogeneous hydroformylation catalysts.

Bio-nanohybrid materials based on the combination of biomolecules and inorganic supports are interesting by their versatile applications in regenerative medicine, drug delivery, bio-engineering and catalysis. In that context, understanding of organic/inorganic interactions offers an important key to design new and more complex bio-systems with modified interactions. In this thesis, amino acids and synthesised poly-amino acids were immobilised in hydrotalcite-like materials under green, controllable and efficient protocols. Additionally, these nanohybrid materials were used as heterogenized catalysts exhibiting high catalytic activity and selectivity in comparison with their counterpart components. All result data showed that the location and nature of the immobilization had an important role in the final chemical properties; moreover, this novel bio-nanohybrid material exhibited excellent synergistic behaviour which was unique for each material and could be modified according with the reaction requirements. All novel bio-nanohybrid materials were easily synthesised, recovered and, in some cases, reused without appreciable deactivation. / Materiales bio-nanohíbridos compuestos por la combinación de biomoléculas y soportes inorgánicos son interesantes por sus versátiles aplicaciones en medicina regenerativa, transporte de medicamentos, bio-ingeniería y catálisis. En este contexto, el entendimiento de las interacciones orgánico/inorgánicas ofrece importante información para el diseño de nuevos y más complejos bio-sistemas con interacciones modificadas. En esta tesis, amino ácidos y poli-amino ácidos sintéticos fueron inmovilizados en materiales tipo hidrotalcita a través de eficientes y controlables protocolos amigables con el medioambiente. Adicionalmente, estos materiales fueron usados como catalizadores heterogeneizados mostrando alta actividad y selectividad en comparación con sus componentes de partida. En este sentido, la localización y naturaleza de la interacción tuvo un importante rol en las propiedades catalíticas finales; además, estos novedosos materiales mostraron un excelente comportamiento sinérgico el cual fue único y pudo ser modificado de acuerdo a las necesidades en reacción. Todos los materiales bio-nanohíbirdos fueron sintetizados y recuperados con facilidad del medio de reacción y en algunos casos fueron reutilizados sin desactivación apreciable.