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Ce=O Terminated CeO 2
Author(s) -
Grinter David C.,
Allan Michael,
Yang Hyun Jin,
Salcedo Agustín,
Murgida Gustavo E.,
Shaw BobbieJean,
Pang Chi L.,
Idriss Hicham,
GandugliaPirovano M. Verónica,
Thornton Geoff
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202101771
Subject(s) - lanthanide , density functional theory , crystallography , vacancy defect , scanning tunneling microscope , electron energy loss spectroscopy , oxide , chemistry , oxygen , surface reconstruction , low energy electron diffraction , spectroscopy , materials science , electron diffraction , diffraction , nanotechnology , computational chemistry , surface (topology) , physics , geometry , ion , transmission electron microscopy , organic chemistry , quantum mechanics , optics , mathematics
Multiply bonded lanthanide oxo groups are rare in coordination compounds and have not previously been reported for a surface termination of a lanthanide oxide. Here we report the observation of a Ce=O terminated ceria surface in a CeO 2 (111)‐( 3 × 3 )R30° reconstruction of ≈3 nm thick ceria islands prepared on Pt(111). This is evidenced by scanning tunnelling microscopy (STM), low energy electron diffraction (LEED) and high‐resolution electron energy loss spectroscopy (HREELS) measurements in conjunction with density functional theory (DFT) calculations. A Ce=O stretching frequency of 775 cm −1 is observed in HREELS, compared with 766 cm −1 calculated by DFT. The calculations also predict that the Ce=O bond is weak, with an oxygen vacancy formation energy of 0.85 eV. This could play an important role in the facile removal of lattice oxygen from CeO 2 , accompanied by the reduction of Ce IV to Ce III , which is a key attribute of ceria‐based systems in connection with their unique catalytic properties.