Selective Hydrogenation of α,β-Unsaturated Aldehydes and Ketones using Novel Manganese Oxide and Platinum Supported on Manganese Oxide Octahedral Molecular Sieves as Catalysts

Authors

  • Dr. Haresh G. Manyar,

    1. CenTACat, School of Chemistry and Chemical Engineering, Queen's University, David Keir Building, Stranmillis Road, Belfast BT9 5AG (UK), Fax: (+44) 28-9097-4687
    Search for more papers by this author
  • Bo Yang,

    1. CenTACat, School of Chemistry and Chemical Engineering, Queen's University, David Keir Building, Stranmillis Road, Belfast BT9 5AG (UK), Fax: (+44) 28-9097-4687
    Search for more papers by this author
  • Dr. Helen Daly,

    1. CenTACat, School of Chemistry and Chemical Engineering, Queen's University, David Keir Building, Stranmillis Road, Belfast BT9 5AG (UK), Fax: (+44) 28-9097-4687
    Search for more papers by this author
  • Dr. Helen Moor,

    1. CenTACat, School of Chemistry and Chemical Engineering, Queen's University, David Keir Building, Stranmillis Road, Belfast BT9 5AG (UK), Fax: (+44) 28-9097-4687
    Search for more papers by this author
  • Stephen McMonagle,

    1. CenTACat, School of Chemistry and Chemical Engineering, Queen's University, David Keir Building, Stranmillis Road, Belfast BT9 5AG (UK), Fax: (+44) 28-9097-4687
    Search for more papers by this author
  • Yu Tao,

    1. CenTACat, School of Chemistry and Chemical Engineering, Queen's University, David Keir Building, Stranmillis Road, Belfast BT9 5AG (UK), Fax: (+44) 28-9097-4687
    Search for more papers by this author
  • Prof. Ganapati D. Yadav,

    1. Department of Chemical Engineering, Institute of Chemical Technology, Matunga, Mumbai, 400 019 (India)
    Search for more papers by this author
  • Dr. Alexandre Goguet,

    1. CenTACat, School of Chemistry and Chemical Engineering, Queen's University, David Keir Building, Stranmillis Road, Belfast BT9 5AG (UK), Fax: (+44) 28-9097-4687
    Search for more papers by this author
  • Prof.  P. Hu,

    1. CenTACat, School of Chemistry and Chemical Engineering, Queen's University, David Keir Building, Stranmillis Road, Belfast BT9 5AG (UK), Fax: (+44) 28-9097-4687
    Search for more papers by this author
  • Prof. Christopher Hardacre

    Corresponding author
    1. CenTACat, School of Chemistry and Chemical Engineering, Queen's University, David Keir Building, Stranmillis Road, Belfast BT9 5AG (UK), Fax: (+44) 28-9097-4687
    • CenTACat, School of Chemistry and Chemical Engineering, Queen's University, David Keir Building, Stranmillis Road, Belfast BT9 5AG (UK), Fax: (+44) 28-9097-4687
    Search for more papers by this author

Abstract

The selective hydrogenation of α,β-unsaturated aldehydes and ketones has been studied using ketoisophorone and cinnamaldehyde as model substrates using manganese oxide octahedral molecular sieve (OMS-2) based catalysts. For the first time, OMS-2 has been shown to be an efficient and selective hydrogenation catalyst. High selectivities for either the C[DOUBLE BOND]C or C[DOUBLE BOND]O double bond at ≈100 % conversion were achieved by using OMS-2 and platinum supported on OMS-2 catalysts. Density functional theory (DFT) calculations showed that the dissociation of H2 on OMS-2 was water assisted and occurred on the surface Mn of OMS-2(0 0 1) that had been modified by an adsorbed H2O molecule. The theoretically calculated activation barrier was in good agreement with the experimentally determined value for the hydrogenation reactions, indicating that H2 dissociation on OMS-2 is likely to be the rate-determining step. A significant increase in the rate of reaction was observed in the presence of Pt as a result of the enhancement of H2 dissociative adsorption and subsequent reaction on the Pt or spillover of the hydrogen to the OMS-2 support. The relative adsorption strengths of ketoisophorone and cinnamaldehyde on the OMS-2 support compared with the Pt were found to determine the product selectivity.

Ancillary