Open AccessDefect engineering by synchrotron radiation X‐rays in CeO 2 nanocrystals
Author(s) -
Wu Tai-Sing,
Syu Leng-You,
Weng Shih-Chang,
Jeng Horng-Tay,
Chang Shih-Lin,
Soo Yun-Liang
Publication year - 2018
Publication title -
journal of synchrotron radiation
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.172
H-Index - 99
ISSN - 1600-5775
DOI - 10.1107/s1600577518008184
Subject(s) - synchrotron radiation , nanocrystal , materials science , valence (chemistry) , synchrotron , photon , radiation damage , irradiation , chemistry , nanotechnology , optics , nuclear physics , physics , organic chemistry
This work reports an unconventional defect engineering approach using synchrotron‐radiation‐based X‐rays on ceria nanocrystal catalysts of particle sizes 4.4–10.6 nm. The generation of a large number of oxygen‐vacancy defects (OVDs), and therefore an effective reduction of cations, has been found in CeO 2 catalytic materials bombarded by high‐intensity synchrotron X‐ray beams of beam size 1.5 mm × 0.5 mm, photon energies of 5.5–7.8 keV and photon fluxes up to 1.53 × 10 12 photons s −1 . The experimentally observed cation reduction was theoretically explained by a first‐principles formation‐energy calculation for oxygen vacancy defects. The results clearly indicate that OVD formation is mainly a result of X‐ray‐excited core holes that give rise to valence holes through electron down conversion in the material. Thermal annealing and subvalent Y‐doping were also employed to modulate the efficiency of oxygen escape, providing extra control on the X‐ray‐induced OVD generating process. Both the core‐hole‐dominated bond breaking and oxygen escape mechanisms play pivotal roles for efficient OVD formation. This X‐ray irradiation approach, as an alternative defect engineering method, can be applied to a wide variety of nanostructured materials for physical‐property modification.