Redox and Catalytic Properties of RhxCe1–xO2−δ Solid Solution Full article
| Journal |
The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455 |
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| Output data | Year: 2017, Volume: 121, Number: 48, Pages: 26925-26938 Pages count : 14 DOI: 10.1021/acs.jpcc.7b09983 | ||||||
| Tags | Catalyst activity; Catalytic oxidation; Reduction; Rhodium; Rhodium compounds; Solid solutions; Surface segregation; X ray photoelectron spectroscopy | ||||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | The Ministry of Education and Science of the Russian Federation | МК-6911.2016.3 |
| 2 | Federal Agency for Scientific Organizations | 0303-2016-0003 |
Abstract:
In this work, a detailed study of the redox properties of solid solution RhxCe1–xO2−δ in correlation with its catalytic activity in CO oxidation reaction was carried out. The ex situ X-ray photoelectron spectroscopy technique was applied to follow the charging states of the elements on the surface during the redox treatments at a temperature range of 25–450 °C. The results were compared with the data of temperature-programmed reduction by CO. The dissolution of rhodium in the ceria bulk considerably increased the mobility of CeO2 lattice oxygen, with redox transitions Ce4+ ↔ Ce3+ and Rh3+ ↔ Rhnδ+ observed already at low temperatures (below 150 °C). The reduced rhodium clusters (Rhnδ+) formed during the reduction treatment significantly improved the catalytic activity of the RhxCe1–xO2−δ solid solution. The small size of the rhodium clusters (Rhnδ+) and high defectiveness of the fluorite phase provided the reversibility of Rhnδ+/CeO2 ↔ RhxCe1–xO2−δ transitions upon redox treatment, resulting in the high reproducibility of the CO conversion curves in the temperature-programmed reaction CO + O2. The homogeneous solid solution was stable up to 800 °C. Above this temperature, the CeO2 volume was depleted of Rh3+ ions because of their partial segregation into the surface and/or subsurface layers with the formation of Rh2O3. For these inhomogeneous samples, the oxygen mobility was considerably lower, while the redox transitions, Ce4+ ↔ Ce3+ and Rh3+ ↔ Rhnδ+, required higher temperatures.
Cite:
Kibis L.S.
, Kardash T.Y.
, Derevyannikova E.A.
, Stonkus O.A.
, Slavinskaya E.M.
, Svetlichnyi V.A.
, Boronin A.I.
Redox and Catalytic Properties of RhxCe1–xO2−δ Solid Solution
The Journal of Physical Chemistry C. 2017. V.121. N48. P.26925-26938. DOI: 10.1021/acs.jpcc.7b09983 WOS Scopus РИНЦ ANCAN OpenAlex
Redox and Catalytic Properties of RhxCe1–xO2−δ Solid Solution
The Journal of Physical Chemistry C. 2017. V.121. N48. P.26925-26938. DOI: 10.1021/acs.jpcc.7b09983 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Oct 9, 2017 |
| Accepted: | Nov 8, 2017 |
| Published online: | Nov 21, 2017 |
| Published print: | Dec 7, 2017 |
Identifiers:
| Web of science: | WOS:000417671500038 |
| Scopus: | 2-s2.0-85038209237 |
| Elibrary: | 35479811 |
| Chemical Abstracts: | 2017:1782094 |
| Chemical Abstracts (print): | 168:10034 |
| OpenAlex: | W2767217799 |