Nontrivial Redox Behavior of Nanosized Cobalt: New Insights from Ambient Pressure X-ray Photoelectron and Absorption Spectroscopies

被引：90

作者：

Papaefthimiou, Vasiliki ^{[1
]}

Dintzer, Thierry ^{[1
]}

Dupuis, Veronique ^{[2
]}

Tamion, Alexandre ^{[2
]}

Tournus, Florent ^{[2
]}

Hillion, Arnaud ^{[2
]}

Teschner, Detre ^{[3
]}

Haevecker, Michael ^{[3
]}

Knop-Gericke, Axel ^{[3
]}

Schloegl, Robert ^{[3
]}

Zafeiratos, Spyridon ^{[1
]}

机构：

[1] Univ Strasbourg, CNRS, Lab LMSPC UMR7515, F-67087 Strasbourg 2, France

[2] Univ Lyon 1, CNRS, Lab PMCN UMR 5586, F-69622 Villeurbanne, France

[3] Max Planck Gesell, Fritz Haber Inst, D-14195 Berlin, Germany

来源：

ACS NANO | 2011年 / 5卷 / 03期

关键词：

cobalt; nanoparticles; wurtzite CoO; redox properties; XPS; APPES; NEXAFS; PARTICLE-SIZE; SURFACE; CATALYSTS; OXYGEN; NANOSTRUCTURES; NANOPARTICLES; OXIDATION; CARBON; PHASE; TEMPERATURE;

D O I：

10.1021/nn103392x

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reduction and oxidation of carbon-supported cobalt nanoparticles (3.50 +/- 0.22 nm) and a Co(0001) single crystal was investigated by ambient pressure X-ray photoelectron (APPES) and X-ray absorption (XAS) spectroseopies, applied in situ under 0.2 mbar hydrogen or oxygen atmospheres and at temperatures up to 620 K. It was found that cobalt nanoparticles are readily, oxidized to a distinct Co phase, which is significantly more stable to further oxidation or reduction compared to the thick oxide films formed on the Co(0001) crystal. The nontrivial size-dependence of redox behavior is followed by a difference in the electronic structure as Suggested by theoretical simulations of the Co L-edge absorption spectra. In particular, contrary to the stable rocksalt and spinel phases that exist in the bulk oxides cobalt nanoparticles contain a significant portion of metastable wurtzite-type CoO.

引用

页码：2182 / 2190

页数：9

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