NDLI: TPR and XPS study of cobalt–copper mixed oxide catalysts: evidence of a strong Co

Content Provider	Springer Nature Link
Author	Fierro, G. Lo Jaco, M. Inversi, M. Dragone, R. Porta, P.
Copyright Year	2000
Abstract	In this work the results of a TPR and XPS investigation of Co$_{x}$O$_{y}$–CuO mixed oxides in the range of composition Co : Cu=100:0–8:92 are reported and compared. The final catalysts were obtained by thermal decomposition in air and N$_{2}$ at 723 K for 24 h of single‐phase cobalt–copper hydroxycarbonates prepared by coprecipitation at constant pH. The Co : Cu=100 : 0 specimen calcined in air formed the Co$^{2+}$[Co$^{3}$]$_{2}$O$_{4}$ (Co$_{3}$O$_{4}$) spinel phase. The copper‐containing catalysts (Co : Cu=85 : 15–8 : 92) showed mainly two phases: (i) spinels, like Co$^{2+}$[Co$^{3+}$]$_{2}$O$_{4}$, Co 1-x 2+ Cu x 2+ [Co$^{3+}$]$_{2}$O$_{4}$ and (ii) pure CuO, the relative amount of each phase depending on the Co : Cu atomic ratio. The results of the XPS study are consistent with the bulk findings and revealed the presence of Co$^{2+}$, Co$^{3+}$ and Cu$^{2+}$ species at the catalyst surface. Moreover, the surface quantitative analysis evidenced a cobalt enrichment, in particular for the most diluted cobalt samples. The TPR study showed that the catalyst reduction is affected by a strong mutual influence between cobalt and copper. The reducibility of the mixed oxide catalysts was always promoted with respect to that of the pure Co$_{3}$O$_{4}$ and CuO phases and the reduction of cobalt was markedly enhanced by the presence of copper. Cobalt and copper were both reduced to metals regardless of the catalyst composition. On the other hand, the Co : Cu=100 : 0 specimen calcined in N$_{2}$ formed, as expected, CoO. The initial addition of copper resulted in the formation of the Cu$^{+}$Co$^{3+}$O$_{2}$ compound, besides CoO, up to a Co/Cu=1 atomic ratio at which the CuCoO$_{2}$ phase was the main component. A further addition of copper led to the formation of CuCoO$_{2}$ and CuO phases. The XPS results were in good agreement with these findings and the surface quantitative analysis revealed a less enrichment of cobalt with respect to the catalysts calcined in air. The TPR analysis confirmed that the reduction of the N$_{2}$‐calcined catalysts was also remarkably promoted by the presence of copper. Also in this case cobalt and copper metal were the final products of reduction.
Starting Page	39
Ending Page	48
Page Count	10
File Format	PDF
ISSN	10225528
Journal	Topics in Catalysis
Volume Number	10
Issue Number	1-2
e-ISSN	15729028
Language	English
Publisher	Kluwer Academic Publishers-Plenum Publishers
Publisher Date	2000-01-01
Publisher Place	New York
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Physical Chemistry Industrial Chemistry/Chemical Engineering Catalysis Characterization and Evaluation Materials Pharmacy
Content Type	Text
Resource Type	Article
Subject	Chemistry Catalysis

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