Selective Ammoximation of Ketones via In Situ H2O2Synthesis

Richard J. Lewis, Kenji Ueura, Xi Liu, Yukimasa Fukuta, Tian Qin, Thomas E. Davies, David J. Morgan, Alex Stenner, James Singleton, Jennifer K. Edwards, Simon J. Freakley, Christopher J. Kiely, Liwei Chen, Yasushi Yamamoto, Graham J. Hutchings

Research output: Contribution to journalArticlepeer-review

4 Citations (SciVal)

Abstract

The ammoximation of ketones to the corresponding oxime via the in situ production of H2O2 offers a viable alternative to the current means of industrial-scale production, in particular for the synthesis of cyclohexanone oxime, a key precursor to Nylon-6. Herein, we demonstrate that using a bifunctional catalyst, consisting of Pd-based bimetallic nanoparticles immobilized onto a TS-1 carrier, it is possible to bridge the considerable condition gap that exists between the two key distinct reaction pathways that constitute an in-situ approach (i.e., the direct synthesis of H2O2 and ketone ammoximation). The formation of PdAu nanoalloys is found to be crucial in achieving high reactivity and in promoting catalytic stability, with the optimal formulation significantly outperforming both alternative Pd-based materials and the monometallic Pd analogue.

Original languageEnglish
Pages (from-to)1934-1945
Number of pages12
JournalACS Catalysis
Volume13
Issue number3
Early online date19 Jan 2023
DOIs
Publication statusPublished - 3 Feb 2023

Bibliographical note

Funding Information:
We appreciate technical support from Mr. Hiroaki Matsumoto and Mr. Chaobin Zeng, Hitachi High-Technologies (Shanghai) Co. Ltd., for HR-STEM characterization. The authors would like to thank the CCI-Electron Microscopy Facility, which has been funded partly by the European Regional Development Fund through the Welsh Government, and The Wolfson Foundation. XPS data collection was performed at the EPSRC National Facility for XPS (“HarwellXPS”), operated by Cardiff University and UCL, under contract No. PR16195. Funding: The authors thank UBE Corporation for financial support and technical advise, R.J.L., A.S and G.J.H gratefully acknowledge Cardiff University and the Max Planck Centre for Fundamental Heterogeneous Catalysis (FUNCAT) for financial support. X.L. acknowledges financial support from National Key R&D Program of China (2021YFA1500300) and National Natural Science Foundation of China (21872163 and 22072090). S.J.F. acknowledges the award of a Prize Research Fellowship from the University of Bath.

Funding Information:
We appreciate technical support from Mr. Hiroaki Matsumoto and Mr. Chaobin Zeng, Hitachi High-Technologies (Shanghai) Co. Ltd., for HR-STEM characterization. The authors would like to thank the CCI-Electron Microscopy Facility, which has been funded partly by the European Regional Development Fund through the Welsh Government, and The Wolfson Foundation. XPS data collection was performed at the EPSRC National Facility for XPS ("HarwellXPS"), operated by Cardiff University and UCL, under contract No. PR16195. Funding: The authors thank UBE Corporation for financial support and technical advise, R.J.L., A.S and G.J.H gratefully acknowledge Cardiff University and the Max Planck Centre for Fundamental Heterogeneous Catalysis (FUNCAT) for financial support. X.L. acknowledges financial support from National Key R&D Program of China (2021YFA1500300) and National Natural Science Foundation of China (21872163 and 22072090). S.J.F. acknowledges the award of a Prize Research Fellowship from the University of Bath.

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.

Keywords

  • feedstock valorization
  • green chemistry
  • hydrogen peroxide
  • industrial catalysis
  • ketone ammoximation
  • palladium-gold

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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