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

Liqun Kang, Bolun Wang (), Qiming Bing, Michal Zalibera, Robert Büchel, Ruoyu Xu, Qiming Wang, Yiyun Liu, Diego Gianolio, Chiu C. Tang, Emma K. Gibson, Mohsen Danaie, Christopher Allen, Ke Wu, Sushila Marlow, Ling-dong Sun, Qian He, Shaoliang Guan, Anton Savitsky, Juan J. Velasco-Vélez, June Callison, Christopher W. M. Kay, Sotiris E. Pratsinis, Wolfgang Lubitz, Jing-yao Liu and Feng Ryan Wang ()
Additional contact information
Liqun Kang: University College London, Roberts Building, Torrington Place
Bolun Wang: University College London, Roberts Building, Torrington Place
Qiming Bing: Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University
Michal Zalibera: Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava, Faculty of Chemical and Food Technology, Radlinského 9
Robert Büchel: Particle Technology Laboratory, Institute of Process Engineering, Department of Mechanical and Process Engineering, ETH Zürich, 8092
Ruoyu Xu: University College London, Roberts Building, Torrington Place
Qiming Wang: University College London, Roberts Building, Torrington Place
Yiyun Liu: University College London, Roberts Building, Torrington Place
Diego Gianolio: Diamond Light Source Ltd., Harwell Science and Innovation Campus, Chilton
Chiu C. Tang: Diamond Light Source Ltd., Harwell Science and Innovation Campus, Chilton
Emma K. Gibson: School of Chemistry, University of Glasgow, Joseph Black Building. University Avenue
Mohsen Danaie: Electron Physical Science Imaging Center, Diamond Light Source Ltd.
Christopher Allen: Electron Physical Science Imaging Center, Diamond Light Source Ltd.
Ke Wu: College of Chemistry and Molecular Engineering, Peking University
Sushila Marlow: University College London, Roberts Building, Torrington Place
Ling-dong Sun: College of Chemistry and Molecular Engineering, Peking University
Qian He: National University of Singapore
Shaoliang Guan: Diamond Light Source Ltd., Harwell Science and Innovation Campus, Chilton
Anton Savitsky: Max-Planck-Institut Für Chemische Energiekonversion, Stiftstrasse 34-36
Juan J. Velasco-Vélez: Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6
June Callison: UK Catalysis Hub, Research Complex at Harwell (RCaH), Rutherford Appleton Laboratory
Christopher W. M. Kay: London Centre for Nanotechnology, University College London
Sotiris E. Pratsinis: Particle Technology Laboratory, Institute of Process Engineering, Department of Mechanical and Process Engineering, ETH Zürich, 8092
Wolfgang Lubitz: Max-Planck-Institut Für Chemische Energiekonversion, Stiftstrasse 34-36
Jing-yao Liu: Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University
Feng Ryan Wang: University College London, Roberts Building, Torrington Place

Nature Communications, 2020, vol. 11, issue 1, 1-11

Abstract: Abstract 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.

Date: 2020
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DOI: 10.1038/s41467-020-17852-8

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