Reduction characteristics of copper oxide in cerium and zirconium oxide systems

被引:400
作者
Kundakovic, L [1 ]
Flytzani-Stephanopoulos, M [1 ]
机构
[1] Tufts Univ, Dept Chem Engn, Medford, MA 02155 USA
关键词
cerium oxide; reducibility; copper oxide; zirconium oxide; temperature-programmed-reduction; catalytic methane oxidation;
D O I
10.1016/S0926-860X(98)00056-8
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The reduction of CuO dispersed on fluorite-type oxide catalysts, namely La-doped CeO(2) and Y-doped ZrO(2) was studied in this work. On both supports distinct copper species were identified as a function of copper content by temperature-programmed reduction (TPR) by H(2) and CH(4), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and scanning transmission electron microscopy/energy dispersive X-ray (STEM/EDX) analyses. At low copper loading (<15 at%), the copper phase is present as small clusters, which are reduced at lower temperature than bulk CuO. At higher Cu loading (>15 at%), in addition to clusters, larger CuO particles are present which are reduced at higher temperature close to the reduction temperature of bulk CuO. At copper loading lower than ca. 5 at%, copper is present as highly dispersed clusters or isolated Cu ions, which interact strongly with the fluorite-type oxide, thus requiring higher reduction temperature. However, the latter is still below the bulk CuO reduction temperature. Copper is more stabilized when dispersed in Ce(La)O(2) than in Zr(Y)O(2) matrix, so that reduction of copper oxide species requires lower temperatures on the Zr(Y)O(2)-based catalysts. The reducibility of the doped ceria is enhanced by the presence of copper in both H(2)- and CH(4)-TPR. On the other hand no such interaction is present in CuZr(Y)O(2) system. The activity of various copper species for methane oxidation is discussed. (C) 1998 Elsevier Science B.V. All rights reserved.
引用
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页码:13 / 29
页数:17
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