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Adsorption and activation of molecular oxygen over atomic copper(I/II) site on ceria.

  • Kang L Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London, WC1E 7JE, UK.
  • Wang B Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London, WC1E 7JE, UK. bolun.wang@ucl.ac.uk.
  • Bing Q Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, Jilin, 130023, P. R. China.
  • Zalibera M Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava, Faculty of Chemical and Food Technology, Radlinského 9, 81237, Bratislava, Slovak Republic.
  • Büchel R Particle Technology Laboratory, Institute of Process Engineering, Department of Mechanical and Process Engineering, ETH Zürich, 8092, Zürich, Switzerland.
  • Xu R Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London, WC1E 7JE, UK.
  • Wang Q Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London, WC1E 7JE, UK.
  • Liu Y Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London, WC1E 7JE, UK.
  • Gianolio D Diamond Light Source Ltd., Harwell Science and Innovation Campus, Chilton, Didcot, OX11 0DE, UK.
  • Tang CC Diamond Light Source Ltd., Harwell Science and Innovation Campus, Chilton, Didcot, OX11 0DE, UK.
  • Gibson EK School of Chemistry, University of Glasgow, Joseph Black Building. University Avenue, Glasgow, G12 8QQ, UK.
  • Danaie M Electron Physical Science Imaging Center, Diamond Light Source Ltd., Didcot, OX11 0DE, UK.
  • Allen C Electron Physical Science Imaging Center, Diamond Light Source Ltd., Didcot, OX11 0DE, UK.
  • Wu K College of Chemistry and Molecular Engineering, Peking University, Beijing, P. R. China.
  • Marlow S Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London, WC1E 7JE, UK.
  • Sun LD College of Chemistry and Molecular Engineering, Peking University, Beijing, P. R. China.
  • He Q Department of Materials Science and Engineering, National University of Singapore, Singapore, 117575, Singapore.
  • Guan S Diamond Light Source Ltd., Harwell Science and Innovation Campus, Chilton, Didcot, OX11 0DE, UK.
  • Savitsky A Max-Planck-Institut Für Chemische Energiekonversion, Stiftstrasse 34-36, D-45470, Mülheim an der Ruhr, Germany.
  • Velasco-Vélez JJ Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195, Berlin, Germany.
  • Callison J UK Catalysis Hub, Research Complex at Harwell (RCaH), Rutherford Appleton Laboratory, Harwell, OX11 0FA, UK.
  • Kay CWM London Centre for Nanotechnology, University College London, 17-19 Gordon Street, London, WC1H 0AH, UK.
  • Pratsinis SE Particle Technology Laboratory, Institute of Process Engineering, Department of Mechanical and Process Engineering, ETH Zürich, 8092, Zürich, Switzerland.
  • Lubitz W Max-Planck-Institut Für Chemische Energiekonversion, Stiftstrasse 34-36, D-45470, Mülheim an der Ruhr, Germany.
  • Liu JY Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, Jilin, 130023, P. R. China.
  • Wang FR Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London, WC1E 7JE, UK. ryan.wang@ucl.ac.uk.
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  • 2020-08-13
Published in:
  • Nature communications. - 2020
General Biochemistry, Genetics and Molecular Biology
General Physics and Astronomy
General Chemistry
English Supported atomic metal sites have discrete molecular orbitals. Precise control over the energies of these sites is key to achieving novel reaction pathways with superior selectivity. Here, we achieve selective oxygen (O2) activation by utilising a framework of cerium (Ce) cations to reduce the energy of 3d orbitals of isolated copper (Cu) sites. Operando X-ray absorption spectroscopy, electron paramagnetic resonance and density-functional theory simulations are used to demonstrate that a [Cu(I)O2]3- site selectively adsorbs molecular O2, forming a rarely reported electrophilic η2-O2 species at 298 K. Assisted by neighbouring Ce(III) cations, η2-O2 is finally reduced to two O2-, that create two Cu-O-Ce oxo-bridges at 453 K. The isolated Cu(I)/(II) sites are ten times more active in CO oxidation than CuO clusters, showing a turnover frequency of 0.028 ± 0.003 s-1 at 373 K and 0.01 bar PCO. The unique electronic structure of [Cu(I)O2]3- site suggests its potential in selective oxidation.
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  • English
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gold
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https://sonar.ch/global/documents/185622
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