Kang, L;
Wang, B;
Bing, Q;
Zalibera, M;
Büchel, R;
Xu, R;
Wang, Q;
... Wang, FR; + view all
(2020)
Adsorption and activation of molecular oxygen over atomic copper(I/II) site on ceria.
Nature Communications
, 11
(1)
, Article 4008. 10.1038/s41467-020-17852-8.
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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.
| Type: | Article |
|---|---|
| Title: | Adsorption and activation of molecular oxygen over atomic copper(I/II) site on ceria |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1038/s41467-020-17852-8 |
| Publisher version: | https://doi.org/10.1038/s41467-020-17852-8 |
| Language: | English |
| Additional information: | This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Chemical Engineering UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > London Centre for Nanotechnology |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10107619 |
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