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Metal–support cooperation in Al(PO3)3-supported platinum nanoparticles for the selective hydrogenolysis of phenols to arenes

Nature Catalysis volume 4, pages 312–321 (2021)Cite this article

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Abstract

The hydrogenolysis of phenols to yield arenes is of importance to the production of fine chemicals, as well as biorefinery application; however, the conversion of phenols through cleavage of their strong C(sp2)–OH bonds remains a highly challenging task in synthetic chemistry. Here we report the use of Al(PO3)3-supported platinum nanoparticles for the selective hydrogenolysis of a broad range of phenols (including sterically highly demanding phenols and lignin model compounds) to afford arenes under relatively low temperatures (<150 °C) and ambient pressure (Ar/H2 = 9/1, 1 atm). This heterogeneous catalyst is expected to find a broad application in fine chemical synthesis and biorefinery.

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Fig. 1: Methods for hydrodeoxygenation of phenols to arenes.
Fig. 2: Characterization of the catalysts.
Fig. 3: Hydrogenolysis of various lignin model compounds.
Fig. 4: Leaching test and catalyst reuse experiment.
Fig. 5: Possible reaction pathways.
Fig. 6: Control experiments for mechanistic studies.

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Data availability

The data supporting the findings of this study are available within this article and its Supplementary Information file or from the authors on reasonable request.

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Acknowledgements

This work was supported by JSPS KAKENHI JP18H05259, JP19K15357, JP20H04803 and JP17H06443. We are grateful to N. Chatani (Osaka University) for helpful discussions. We would like to thank K. Yamaguchi (U. Tokyo) for generous sharing of analytical instruments. A part of this work was conducted at the Advanced Characterisation Nanotechnology Platform of the University of Tokyo, supported by the Nanotechnology Platform of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.

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Authors and Affiliations

  1. Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, Tokyo, Japan

    Xiongjie Jin, Rio Tsukimura & Kyoko Nozaki

  2. Department of Applied Chemistry for Environment, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Tokyo, Japan

    Takeshi Aihara, Hiroki Miura & Tetsuya Shishido

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  1. Xiongjie Jin
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Contributions

X.J. and K.N. designed the studies and conceived the main idea. R.T. and X.J. executed all of the experimental work except for the FTIR measurements using the probe molecules. T.A., H.M. and T.S. carried out the FTIR experiments using pyridine or p-cresol as the probe molecule. All authors discussed the results and wrote the paper.

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Correspondence to Xiongjie Jin or Kyoko Nozaki.

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Peer review information Nature Catalysis thanks Changhai Liang, Igor Slowing and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Tables 1 and 2, Figs. 1–15, GC chromatograms, GC–MS or NMR spectra of the crude reaction mixtures and references.

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Jin, X., Tsukimura, R., Aihara, T. et al. Metal–support cooperation in Al(PO3)3-supported platinum nanoparticles for the selective hydrogenolysis of phenols to arenes. Nat Catal 4, 312–321 (2021). https://doi.org/10.1038/s41929-021-00598-x

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