Structural investigation of combustion synthesized Cu/CeO2 catalysts by EXAFS and other physical techniques: Formation of a Ce1-xCuxO2-δ solid solution

Parthasarathi Bera, K. R. Priolkar, P. R. Sarode, M. S. Hegde, S. Emura, Ryotaro Kumashiro, N. P. Lalla

    Research output: Contribution to journalArticlepeer-review

    244 Citations (Scopus)

    Abstract

    The structure and chemical environment of Cu in Cu/CeO2 catalysts synthesized by the solution combustion method have been investigated by x-ray diffraction (XRD), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR) spectroscopy, x-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and extended x-ray fine structure (EXAFS) spectroscopy. High-resolution XRD studies of 3 and 5 atom % Cu/CeO2 do not show CuO lines in their respective patterns. The structure could be refined for the composition Ce1-xCuxO2-δ (x = 0.03 and 0.05; δ ∼ 0.13 and 0.16) in the fluorite structure with 5-8% oxide ion vacancy. High-resolution TEM did not show CuO particles in 5 atom % CU/CeO2. EPR as well as XPS studies confirm the presence of Cu2+ species in the CeO2 matrix. Redox potentials of Cu species in the CeO2 matrix are lower than those in CuO. EXAFS investigations of these catalysts show an average coordination number of 3 around the Cu2+ ion in the first shell at a distance of 1.96 Å, indicating the O2- ion vacancy around the Cu2+ ion. The Cu-O bond length also decreases compared to that in CuO. The second and third shell around the Cu2+ ion in the catalysts are attributed to -Cu2+-O2--Cu2+- at 2.92 Å and -Cu2+-O2--Ce4+- at the distance of 3.15 Å, respectively. The present results provide direct evidence for the formation of a Ce1-xCuxO2-δ type of solid solution phase having -□- Cu2+-O-Ce4+- kind of linkages.

    Original languageEnglish
    Pages (from-to)3591-3601
    Number of pages11
    JournalChemistry of Materials
    Volume14
    Issue number8
    DOIs
    Publication statusPublished - 2002 Aug 1

    ASJC Scopus subject areas

    • Chemistry(all)
    • Chemical Engineering(all)
    • Materials Chemistry

    Fingerprint Dive into the research topics of 'Structural investigation of combustion synthesized Cu/CeO<sub>2</sub> catalysts by EXAFS and other physical techniques: Formation of a Ce<sub>1-x</sub>Cu<sub>x</sub>O<sub>2-δ</sub> solid solution'. Together they form a unique fingerprint.

    Cite this