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Isokinetic behavior in the gas phase hydrogenation of nitroarenes over Au/TiO2: application of the selective energy transfer model

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Abstract

The gas phase selective hydrogenation of a series of nitroarenes (nitrobenzene, p-chloronitrobenzene, p-bromonitrobenzene, p-nitroaniline, p-nitrotoluene, p-nitrophenol and p-nitroanisole) has been examined over Au/TiO2 (0.3 % w/w Au, mean Au particle size = 3.9 nm). Compensation behavior is demonstrated with an associated isokinetic temperature (T iso) of 558 ± 32 K. We account for this response in terms of the selective energy transfer (SET) model where the occurrence of resonance between catalyst and reactant vibrations generates the activated complex. An analysis of the stepwise variation of the activation energies has identified a critical vibrational frequency of 853 cm−1, which is close (±2 cm−1) to the reference value for nitro-group (in-plane symmetric O–N–O bending and stretching) vibrations. Application of SET suggests activation of weakly adsorbed nitroarene (at the support or metal/support interface) by excitation of the nitro-group via IR radiation from a strongly adsorbed surface nitroarene component. The excited nitroarene is then attacked by reactive hydrogen supplied by the Au sites to generate the respective aromatic amine with 100 % selectivity. Agreement of the SET predicted T iso with the experimental value requires the incorporation of a term due to C–N torsional entropy resulting from distortion of the O–N–O plane.

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Acknowledgments

We note the contribution of Dr. F. Cárdenas-Lizana and X. Wang to this work. EPSRC support for free access to the TEM/SEM facility at the University of St Andrews is also acknowledged.

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  1. Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, Scotland, UK

    Mark A. Keane

  2. Chemical Engineering II, University of Lund, P O Box 124, 221 00, Lund, Sweden

    Ragnar Larsson

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  1. Mark A. Keane
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Correspondence to Mark A. Keane.

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Keane, M.A., Larsson, R. Isokinetic behavior in the gas phase hydrogenation of nitroarenes over Au/TiO2: application of the selective energy transfer model. Reac Kinet Mech Cat 106, 267–288 (2012). https://doi.org/10.1007/s11144-012-0440-6

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