We present a simple and generalizable synthetic route toward phase-pure, monodisperse transition-metal-substituted ceria nanoparticles (M0.1Ce0.9O2-x, M = Mn, Fe, Co, Ni, Cu). The solution-based pyrolysis of a series of heterobimetallic Schiff base complexes ensures a rigorous control of the size, morphology and composition of 3 nm M0.1Ce0.9O2-x crystallites for CO oxidation catalysis and other applications. X-ray absorption spectroscopy confirms the dispersion of aliovalent (M3+ and M2+) transition metal ions into the ceria matrix without the formation of any bulk transition metal oxide phases, while steady-state CO oxidation catalysis reveals an order of magnitude increase in catalytic activity with copper substitution. Density functional calculations of model slabs of these compounds confirm the stabilization of M3+ and M2+ in the lattice of CeO2. These results highlight the role of the host CeO2 lattice in stabilizing high oxidation states of aliovalent transition metal dopants that ordinarily would be intractable, such as Cu3+, as well as demonstrating a rational approach to catalyst design. The current work demonstrates, for the first time, a generalizable approach for the preparation of transition-metal-substituted CeO2 for a broad range of transition metals with unparalleled synthetic control and illustrates that Cu3+ is implicated in the mechanism for CO oxidation on CuO-CeO2 catalysts.

Elias, J., Risch, M., Giordano, L., Mansour, A., Shao Horn, Y. (2014). Structure, bonding, and catalytic activity of monodisperse, transition-metal-substituted CeO2 nanoparticles. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136(49), 17193-17200 [10.1021/ja509214d].

Structure, bonding, and catalytic activity of monodisperse, transition-metal-substituted CeO2 nanoparticles

GIORDANO, LIVIA;
2014

Abstract

We present a simple and generalizable synthetic route toward phase-pure, monodisperse transition-metal-substituted ceria nanoparticles (M0.1Ce0.9O2-x, M = Mn, Fe, Co, Ni, Cu). The solution-based pyrolysis of a series of heterobimetallic Schiff base complexes ensures a rigorous control of the size, morphology and composition of 3 nm M0.1Ce0.9O2-x crystallites for CO oxidation catalysis and other applications. X-ray absorption spectroscopy confirms the dispersion of aliovalent (M3+ and M2+) transition metal ions into the ceria matrix without the formation of any bulk transition metal oxide phases, while steady-state CO oxidation catalysis reveals an order of magnitude increase in catalytic activity with copper substitution. Density functional calculations of model slabs of these compounds confirm the stabilization of M3+ and M2+ in the lattice of CeO2. These results highlight the role of the host CeO2 lattice in stabilizing high oxidation states of aliovalent transition metal dopants that ordinarily would be intractable, such as Cu3+, as well as demonstrating a rational approach to catalyst design. The current work demonstrates, for the first time, a generalizable approach for the preparation of transition-metal-substituted CeO2 for a broad range of transition metals with unparalleled synthetic control and illustrates that Cu3+ is implicated in the mechanism for CO oxidation on CuO-CeO2 catalysts.
Articolo in rivista - Articolo scientifico
Chemistry (all); Catalysis; Biochemistry; Colloid and Surface Chemistry
English
2014
136
49
17193
17200
none
Elias, J., Risch, M., Giordano, L., Mansour, A., Shao Horn, Y. (2014). Structure, bonding, and catalytic activity of monodisperse, transition-metal-substituted CeO2 nanoparticles. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136(49), 17193-17200 [10.1021/ja509214d].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/90720
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