Metal-organic frameworks as kinetic modulators for branched selectivity in hydroformylation

Authors: Gerald Bauer1, Daniele Ongari2*, Davide Tiana3, Patrick Gäumann1, Thomas Rohrbach1, Gerard Pareras3, Mohamed Tarik4, Berend Smit2, Marco Ranocchiari1

  1. Laboratory for Catalysis and Sustainable Chemistry, Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland
  2. Laboratory of Molecular Simulation, EPFL Valais/Wallis, CH-1951 Sion, Switzerland
  3. School of Chemistry, University College Cork, College Rd, Cork, Ireland
  4. Laboratory for Bioenergy and Catalysis, Paul Scherrer Institute, CH-5232 Villigen PSI
  • Corresponding author email: daniele.ongari@epfl.ch

DOI10.24435/materialscloud:2020.0007/v1 (version v1, submitted on 16 January 2020)

How to cite this entry

Gerald Bauer, Daniele Ongari, Davide Tiana, Patrick Gäumann, Thomas Rohrbach, Gerard Pareras, Mohamed Tarik, Berend Smit, Marco Ranocchiari, Metal-organic frameworks as kinetic modulators for branched selectivity in hydroformylation, Materials Cloud Archive (2020), doi: 10.24435/materialscloud:2020.0007/v1.

Description

Finding heterogeneous catalysts that are superior to homogeneous ones for selective organic transformation is a major challenge in catalysis. Here we show how micropores in metal-organic frameworks (MOFs) push homogeneous catalytic reactions into kinetic regimes inaccessible under standard conditions. Such property allows branched selectivity up to 90% in the Co-catalysed hydroformylation of olefins without directing groups, not achievable with existing catalysts. This finding has a big potential in the production of aldehydes for the fine chemical industry. Monte Carlo and density functional theory simulations combined with kinetic models show that the micropores of MOFs with UMCM-1 and MOF-74 topologies increase the olefins density beyond neat conditions while partially preventing the adsorption of syngas leading to high branched selectivity. The easy experimental protocol and the chemical and structural flexibility of MOFs will attract the interest of the fine chemical industries towards the design of heterogeneous processes with exceptional selectivity.

Materials Cloud sections using this data

No Explore or Discover sections associated with this archive entry.

Files

File name Size Description
hydroformylation_archive_v1.zip
MD5MD5: 1eca0baf9ea8c4bd0b8b5ac25bcfd669
34.8 MiB Input/output files for the calculations.
README.txt
MD5MD5: 333c26291477149fd99ac93ed9aefe95
566 Bytes Description of the zip content.

License

Files and data are licensed under the terms of the following license: Creative Commons Attribution 4.0 International.

External references

Journal reference
Submitted

Keywords

MARVEL metal-organic frameworks MOF catalysis

Version history

16 January 2020 [This version]