Maria Jose Valero Romero

Maria Jose Valero

Van der Maasweg 9, 2629 HZ Delft
Room: E2.280
Tel: *31 (0)15-2784371

Design and development of heterogeneous catalysts for hydroformylation of olefins 

Hydroformylation was first discovered by the German industrial chemist Otto Roelen in 1938 during the course of his studies on the oxygenated side products of cobalt-catalyzed Fischer-Tropsch reactions [1]. The hydroformylation reaction is catalyzed by transition metal complexes, such as Co and Rh, and involves the cis addition of hydrogen and carbon monoxide to olefins, yielding linear and branched aldehydes as primary products in an efficient manner (Scheme). 



General hydroformylation scheme

It is currently known as one of the most widely used industrial homogeneous catalytic processes for the synthesis of aldehydes or alcohols (approximately, 9 million metric tons per annum) and its relevance is well documented by the number of books and review articles on the subject [2]. In this sense, immense effort has been invested in the development of selective syntheses of linear aldehydes, which are desired products for bulk applications; for example, butyraldehyde is the starting material for the production of phthalates. On the other hand, the synthesis of branched aldehydes is of interest for the synthesis of pharmaceuticals and fine chemicals because of the potential formation of a stereogenic center.

The state of the art homogeneous reaction widely employs Rh-based complexes (often bearing triphenylphosphine ligands) as catalysts to convert a feed of olefin(s), H2, and CO. In spite of various advantages of homogeneous catalytic systems, separation (of products from the catalyst) is a limitation of a high concern, especially when it comes to precious metals (e.g., Rh). One of the main strategies to achieve these goals is based on the heterogenization of homogeneous catalysts via immobilization on solid supports [3]. Such heterogenization of the catalyst not only eases its separation/reutilization, but also brings about the potential to enhance its performance by means of confinement effects, introduced by solid porous materials.

The main objective of this project is to develop efficient heterogeneous catalysts for the hydroformylation of olefins based on metal organic frameworks (MOFs) and to explore the advantages that MOFs may offer as carriers for hydroformylation functions.

  1. O. Roelen, DE Patent 849548, 1938/52; US2327066943. 
  2. B. Cornils, W. Herrmann,  Applied Homogeneous Catalysis with Organometallic Compounds, Wiley-VCH, Weinheim, Germany, 2nd ed., 2002, p. 31; R. Franke, D. Selent, A. Börner. Chem. Rev. 2012, 112, 5675−5732; J. Pospech, Iv. Fleischer, R. Franke, S. Buchholz, M. Beller. Angew. Chem. lnt. Ed. 2013, 52, 2852- 2872.
  3. Â.C.B. Neves, M.J.F. Calvete,  T.M.V.D. Pinho E Melo, M. M. Pereira. Eur. J. Org. Chem. 2012,  6309-6320.


This research receives funding from Shell Global Solutions.