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

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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.

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Acknowledgments

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).

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Authors and Affiliations

  1. Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

    Qing Guo, Shiguang Mo, Pengxin Liu, Weidong Zheng, Ruixuan Qin, Chaofa Xu, Youyunqi Wu, Binghui Wu & Nanfeng Zheng

Authors
  1. Qing Guo
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  2. Shiguang Mo
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  3. Pengxin Liu
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  4. Weidong Zheng
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  5. Ruixuan Qin
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  6. Chaofa Xu
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  7. Youyunqi Wu
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  8. Binghui Wu
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  9. Nanfeng Zheng
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Correspondence to Binghui Wu or Nanfeng Zheng.

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Guo, Q., Mo, S., Liu, P. et al. Air-promoted selective hydrogenation of phenol to cyclohexanone at low temperature over Pd-based nanocatalysts. Sci. China Chem. 60, 1444–1449 (2017). https://doi.org/10.1007/s11426-017-9095-4

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  • DOI: https://doi.org/10.1007/s11426-017-9095-4

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