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Design and Preparation of MnO2/CeO2–MnO2 Double-Shelled Binary Oxide Hollow Spheres and Their Application in CO Oxidation

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School of Materials Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333403, China
State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China
Cite this: ACS Appl. Mater. Interfaces 2016, 8, 13, 8670–8677
Publication Date (Web):March 21, 2016
Copyright © 2016 American Chemical Society
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Herein, we designed an extremely facile method to prepare well-defined MnO2@CeO2–MnO2 ball-in-ball binary oxide hollow spheres by employing carbon spheres (CSs) as sacrificial templates. The synthesis process involves a novel self-assembled approach to prepare core–shell [email protected]2 precursor, which would directly react with KMnO4 aqueous solution to form yolk–shell [email protected]2/CeO2–MnO2 precursor in the following step. Well-dispersed Ce–Mn binary oxide with double-shelled hollow sphere structure could be achieved after annealing the precursor in air. The evolution process and formation mechanism of this novel structure were thoroughly studied in this paper. Especially the as-prepared double-shell MnO2/CeO2–MnO2 hollow spheres exhibited enhanced catalytic activity for CO oxidation compared with the pure MnO2 hollow spheres and pure CeO2 hollow spheres. We believe the high surface area, hierarchical porous structures, and strong synergistic interaction between CeO2 and MnO2 contribute to the excellent catalytic activity. Most importantly, this method could be extended to prepare other transition metal oxides. As an example, triple-shelled Co–Mn composite hollow spheres assembled by ultrathin nanoplates were successfully prepared.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b00002.

  • SEM and TEM images of carbon spheres; images of CeO2 precursor particles and Ce–Mn composite particles and corresponding EDS spectra; magnified SEM images of core–shell [email protected]2 precursor; yolk–shell [email protected]2/CeO2–MnO2; double-shell hollow structure MnO2/CeO2–MnO2 spheres; HR-TEM images of [email protected]2 precursor and double-shell hollow structure MnO2/CeO2–MnO2 spheres; STEM images and its cross-sectional compositional line profiles of the MnO2/CeO2–MnO2 composite hollow sphere; magnified XRD patterns of pure CeO2 and MnO2/CeO2–MnO2 composite hollow spheres; N2 adsorption–desorption isotherms of CeO2 hollow spheres, MnO2 hollow spheres, and MnO2/CeO2–MnO2 composite hollow spheres (PDF)

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