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SCIENCE CHINA Chemistry, Volume 60, Issue 11: 1444-1449(2017) https://doi.org/10.1007/s11426-017-9095-4

Air-promoted selective hydrogenation of phenol to cyclohexanone at low temperature over Pd-based nanocatalysts

More info
  • ReceivedMar 31, 2017
  • AcceptedJun 12, 2017
  • PublishedAug 11, 2017

Abstract

Attaining high activity with high selectivity at low temperature is challenging in the selective hydrogenation of phenol to cyclohexanone due to its high activation energy (Ea, 55–70 kJ/mol). Here we report a simple and efficient strategy for phenol hydrogenation catalyzed by Pd in aqueous phase at 30 °C by introducing air to promote the catalysis. With the assistance of air, >99% conversion and >99% selectivity were achieved over Pd(111)/Al2O3 with an overall turnover frequency (TOF) of 621 h−1, ~80 times greater than that of the state-of-art Pd catalyst at 30 °C. Mechanism studies revealed that phenol was activated to generate phenoxyl radicals. The radicals were yielded from the reaction between phenol and hydroxyl radicals in the presence of hydrogen, oxygen and protic solvent on Pd. The phenoxyl pathway resulted in a low apparent Ea (8.2 kJ/mol) and thus high activity. More importantly, this strategy of activating substrate by air can be adapted to other Pd based catalysts, offering a new thinking for the rational design of cyclohexanone production in industry.


Funded by

MOST of China(2015CB93230)

National Natural Science Foundation of China(21420102001,21333008)


Acknowledgment

This work was supported by the Ministry of Science and Technology of China (2017YFA0207302, 2015CB93230) and the National Natural Science Foundation of China (21420102001, 21333008).


Interest statement

The authors declare that they have no conflict of interest.


Supplement

The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


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  • Figure 1

    (a) Comparison of initial reaction rates of phenol hydrogenation catalyzed by commercial Pd catalyst (Pd NP/C) and home-made Pd NP/Al2O3 in the presence of 0.2 MPa H2 or 0.1 MPa H2+0.1 MPa air; (b) HR-TEM image of as-prepared Pd(111)/Al2O3; (c) time profiles of the conversion and selectivity of phenol hydrogenation to cyclohexanone catalyzed by Pd(111)/Al2O3 at 30 °C; (d) apparent Ea of phenol hydrogenation catalyzed by Pd(111)/Al2O3 (color online).

  • Figure 2

    (a) Conversion of phenol to cyclohexanone catalyzed by Pd(111)/Al2O3 as a function of oxygen amount (within 38-mL gas space); (b) the existence of hydroxyl radicals was testified by fluorescence spectroscopy using TA as a spin trapping agent. Pd(111)/Al2O3 was used as catalyst throughout reactions (color online).

  • Figure 3

    Experimental and simulated ESR spectra of DMPO adducts obtained in water solution (a) after introducing air and then (b) adding phenol into the reaction system; (c) mechanism of phenoxyl radical isomerism to ketocyclohexadienyl radicals (·Ph) (color online).

  • Figure 4

    Proposed mechanism of phenol hydrogenation by introducing air over Pd-based nanocatalysts (color online).

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