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 O^2-, that create tw

SUBMITTER: Kang L 

PROVIDER: S-EPMC7419315 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature