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)

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.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• 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: 2041-1723
• 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

Project Code	Award No	Project Name	Principal Investigator	Funder's Name	Funder Ref	Lead Dept
169321		Catalytic HDO : Queen's University of Belfast ref R1188CCE	Samuel Jackson	Engineering and Physical Sciences Research Council (EPSRC)	EP/K014706/1	Chemistry