Journal article
Adsorption and activation of molecular oxygen over atomic copper(I/II) site on ceria
- 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.
- Publication status:
- Published
- Peer review status:
- Peer reviewed
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(Preview, Version of record, 2.1MB, Terms of use)
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- Publisher copy:
- 10.1038/s41467-020-17852-8
Authors
- Publisher:
- Springer Nature
- Journal:
- Nature Communications More from this journal
- Volume:
- 11
- Issue:
- 1
- Article number:
- 4008
- Publication date:
- 2020-08-11
- Acceptance date:
- 2020-07-22
- DOI:
- EISSN:
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2041-1723
- Pmid:
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32782245
- Language:
-
English
- Keywords:
- Pubs id:
-
1125881
- Local pid:
-
pubs:1125881
- Deposit date:
-
2020-10-19
Terms of use
- Copyright holder:
- Kang et al.
- Copyright date:
- 2020
- Rights statement:
- ©2020 The Author(s).
- Notes:
- Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
- Licence:
- CC Attribution (CC BY)
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