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

DOI: 10.1038/s41467-020-17852-8

Authors: Liqun Kang (University College London (UCL)) , Bolun Wang (University College London (UCL)) , Qiming Bing (Jilin University) , Michal Zalibera (Slovak University of Technology in Bratislava) , Robert Büchel (ETH Zürich) , Ruoyu Xu (University College London (UCL)) , Qiming Wang (University College London (UCL)) , Yiyun Liu (University College London) , Diego Gianolio (Diamond Light Source) , Chiu C. Tang (Diamond Light Source) , Emma K. Gibson (University of Glasgow) , Mohsen Danaie (Diamond Light Source; University of Oxford) , Christopher Allen (Diamond Light Source; University of Oxford) , Ke Wu (Peking University) , Sushila Marlow (University College London (UCL)) , Ling-Dong Sun (Peking University) , Qian He (National University of Singapore) , Shaoliang Guan (Diamond Light Source; HarwellXPS—The EPSRC National Facility for Photoelectron Spectroscopy, Research Complex at Harwell (RCaH)) , Anton Savitsky (Max-Planck-Institut Für Chemische Energiekonversion; Technical University of Dortmund) , Juan J. Velasco-Vélez (Fritz-Haber-Institut der Max-Planck-Gesellschaft) , June Callison (UK Catalysis Hub, Research Complex at Harwell (RCaH)) , Christopher W. M. Kay (University College London; University of Saarland) , Sotiris E. Pratsinis (ETH Zürich) , Wolfgang Lubitz (Max-Planck-Institut Für Chemische Energiekonversion) , Jing-Yao Liu (Jilin University) , Feng Ryan Wang (University College London)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Nature Communications , VOL 11

State: Published (Approved)
Published: August 2020
Diamond Proposal Number(s): 15151 , 15763 , 16966 , 17377 , 19072 , 19246 , 20939 , 17559 , 24285 , 19318 , 19850

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.

Journal Keywords: Heterogeneous catalysis; Reaction kinetics and dynamics

Subject Areas: Chemistry, Engineering

Diamond Offline Facilities: Electron Physical Sciences Imaging Centre (ePSIC)
Instruments: B18-Core EXAFS , E01-JEM ARM 200CF , E02-JEM ARM 300CF , I11-High Resolution Powder Diffraction , I20-Scanning-X-ray spectroscopy (XAS/XES)

Other Facilities: BESSY II; SPring-8

Added On: 11/08/2020 22:56

Documents:
s41467-020-17852-8.pdf

Discipline Tags:

Physical Chemistry Catalysis Chemistry Chemical Engineering Engineering & Technology

Technical Tags:

Diffraction Microscopy Spectroscopy X-ray Powder Diffraction Electron Microscopy (EM) Transmission Electron Microscopy (TEM) X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS) High Energy Resolution Fluorescence Detected XAS (HERFD-XAS) X-ray Absorption Near Edge Structure (XANES)