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

Kang, L. et al. (2020) Adsorption and activation of molecular oxygen over atomic copper(I/II) site on ceria. Nature Communications, 11, 4008. (doi: 10.1038/s41467-020-17852-8) (PMID:32782245) (PMCID:PMC7419315)

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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.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Gibson, Dr Emma
Authors: Kang, L., Wang, B., Bing, Q., Zalibera, M., Büchel, R., Xu, R., Wang, Q., Liu, Y., Gianolio, D., Tang, C. C., Gibson, E. K., Danaie, M., Allen, C., Wu, K., Marlow, S., Sun, L.-d., He, Q., Guan, S., Savitsky, A., Velasco-Vélez, J. J., Callison, J., Kay, C. W.M., Pratsinis, S. E., Lubitz, W., Liu, J.-y., and Wang, F. R.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Nature Communications
Publisher:Nature Research
ISSN (Online):2041-1723
Copyright Holders:Copyright © 2020 The Authors
First Published:First published in Nature Communications 11: 4008
Publisher Policy:Reproduced under a Creative Commons License

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
169321Catalytic HDO : Queen's University of Belfast ref R1188CCESamuel JacksonEngineering and Physical Sciences Research Council (EPSRC)EP/K014706/1Chemistry