Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance upgrade on Thursday 4th of May 2017 from 8.00am to 9.00am (BST).

During this time our websites will be offline temporarily. If you have any questions please use the feedback button on this page. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 21, 2016
Previous Article Next Article

Solvent inhibition in the liquid-phase catalytic oxidation of 1,4-butanediol: understanding the catalyst behaviour from NMR relaxation time measurements

Author affiliations

Abstract

Catalytic reaction studies and nuclear magnetic resonance (NMR) relaxation time measurements have been compared to study the influence of competitive adsorption of reactant and solvent on catalytic conversion. The reaction chosen is the aerobic catalytic oxidation of 1,4-butanediol in methanol over different supported-metal catalysts. From the NMR T1/T2 ratio, where T1 is the longitudinal and T2 the transverse spin relaxation time, the relative affinity of reactant and solvent for different catalytic surfaces is determined. The catalysts with the lowest activity show a preferential surface affinity for the solvent compared to the reactant. Conversely, the catalyst with the highest activity shows a preferential surface affinity for the reactant compared to the solvent. Significantly, Ru/SiO2, which is totally inactive for the oxidation of 1,4-butanediol, exhibited a lower T1/T2 ratio (surface affinity) for 1,4-butanediol (reactant) than for a “weakly-interacting” alkane, indicating a very poor surface affinity for the diol functionality. The results provide direct evidence of the importance of the adsorbate–adsorbent interactions on catalyst activity in liquid-phase oxidations and indicate that the competitive adsorption of the solvent plays an important role in these reactions. This work demonstrates that NMR relaxation time analysis is a powerful method for comparing adsorption of liquids in porous catalysts, providing valuable information on the affinity of different chemical species for a catalyst surface. Moreover, the results demonstrate that NMR relaxation time measurements can be used not only to guide selection of solvent for use with a specific catalyst, but also selection of the catalyst itself. The results suggest that this method may be used to predict catalyst behaviour, enabling improved design and optimisation of heterogeneous catalytic processes.

Graphical abstract: Solvent inhibition in the liquid-phase catalytic oxidation of 1,4-butanediol: understanding the catalyst behaviour from NMR relaxation time measurements

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 07 Jul 2016, accepted on 29 Sep 2016 and first published on 30 Sep 2016


Article type: Paper
DOI: 10.1039/C6CY01458E
Citation: Catal. Sci. Technol., 2016,6, 7896-7901
  • Open access: Creative Commons BY license
  •   Request permissions

    Solvent inhibition in the liquid-phase catalytic oxidation of 1,4-butanediol: understanding the catalyst behaviour from NMR relaxation time measurements

    C. D'Agostino, M. R. Feaviour, G. L. Brett, J. Mitchell, A. P. E. York, G. J. Hutchings, M. D. Mantle and L. F. Gladden, Catal. Sci. Technol., 2016, 6, 7896
    DOI: 10.1039/C6CY01458E

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author