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

Kang, Liqun, Wang, Bolun, Bing, Qiming, Zalibera, Michal, Büchel, Robert, Xu, Ruoyu, Wang, Qiming, Liu, Yiyun, Gianolio, Diego, Tang, Chiu C., Gibson, Emma K., Danaie, Mohsen, Allen, Christopher, Wu, Ke, Marlow, Sushila, Sun, Ling-dong, He, Qian, Guan, Shaoliang, Savitsky, Anton, Velasco-Vélez, Juan J., Callison, June, Kay, Christopher W. M., Pratsinis, Sotiris E., Lubitz, Wolfgang, Liu, Jing-yao and Wang, Feng Ryan 2020. Adsorption and activation of molecular oxygen over atomic copper(I/II) site on ceria. Nature Communications 11 , 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.

Item Type: Article
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Publisher: Nature Research
ISSN: 2041-1723
Date of First Compliant Deposit: 21 May 2021
Date of Acceptance: 22 July 2020
Last Modified: 28 May 2021 08:19
URI: http://orca.cardiff.ac.uk/id/eprint/141500

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