Effect of Metal Dopant on the Performance of Ni@CeMeO<sub>2</sub> Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane
Biogas upgrading by a catalytic process has been studied in order to obtain syngas using renewable source of methane. This work evaluates the influence of metal dopant (Gd, Sm, and Zr) on the CeO<sub>2</sub> structure for the dry reforming of methane over Ni nanoparticle embedded catalys...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-11-01
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| Series: | Methane |
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| Online Access: | https://www.mdpi.com/2674-0389/1/4/23 |
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| author | André L. A. Marinho Raimundo C. Rabelo-Neto Florence Epron Fabio S. Toniolo Fabio B. Noronha Nicolas Bion |
| author_facet | André L. A. Marinho Raimundo C. Rabelo-Neto Florence Epron Fabio S. Toniolo Fabio B. Noronha Nicolas Bion |
| author_sort | André L. A. Marinho |
| collection | DOAJ |
| description | Biogas upgrading by a catalytic process has been studied in order to obtain syngas using renewable source of methane. This work evaluates the influence of metal dopant (Gd, Sm, and Zr) on the CeO<sub>2</sub> structure for the dry reforming of methane over Ni nanoparticle embedded catalysts. The doping with Zr improved the thermal stability of the catalyst, leading to the formation of small Ni nanoparticles, while Ni metal sintering was observed for Ni@CeO<sub>2</sub>, Ni@CeGdO<sub>2</sub>, and Ni@SmO<sub>2</sub>, according to in situ XRD under reduction conditions. The ceria reducibility was affected by the dopant nature, for which the addition of Zr caused distortions in the ceria lattice, promoting the diffusion of oxygen bulk to surface. The doping with Gd and Sm created oxygen vacancies by charge compensation, and the saturation of oxygen vacancies in the fresh samples decreased the degree of Ce reduction, according to TPR results. The larger Ni particles and poor redox behavior for Ni@CeGdO<sub>2</sub> and Ni@CeSmO<sub>2</sub> were responsible for the high carbon formation on these catalysts during the DRM reaction. The Ni@CeZrO<sub>2</sub> catalyst did not present coke formation because of smaller Ni crystallite size and higher ceria reducibility. Therefore, the control of Ni particle size and the high oxygen mobility in the Ni@CeZrO<sub>2</sub> catalyst inhibits carbon deposition and enhances the mechanism of carbon removal, promoting the catalyst stability. |
| first_indexed | 2024-03-11T09:34:55Z |
| format | Article |
| id | doaj.art-f6be1d3f1e4c4151b9d78626d1de0c5e |
| institution | Directory Open Access Journal |
| issn | 2674-0389 |
| language | English |
| last_indexed | 2024-03-11T09:34:55Z |
| publishDate | 2022-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Methane |
| spelling | doaj.art-f6be1d3f1e4c4151b9d78626d1de0c5e2023-11-16T17:24:54ZengMDPI AGMethane2674-03892022-11-011430031910.3390/methane1040023Effect of Metal Dopant on the Performance of Ni@CeMeO<sub>2</sub> Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of MethaneAndré L. A. Marinho0Raimundo C. Rabelo-Neto1Florence Epron2Fabio S. Toniolo3Fabio B. Noronha4Nicolas Bion5Chemical Engineering Program of COPPE/UFRJ, Federal University of Rio de Janeiro, P.O. Box 68502, Rio de Janeiro 21941-972, RJ, BrazilNational Institute of Technology, Catalysis Division, Rio de Janeiro 20081-312, RJ, BrazilInstitut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), CNRS, University of Poitiers, 86073 Poitiers, FranceChemical Engineering Program of COPPE/UFRJ, Federal University of Rio de Janeiro, P.O. Box 68502, Rio de Janeiro 21941-972, RJ, BrazilNational Institute of Technology, Catalysis Division, Rio de Janeiro 20081-312, RJ, BrazilInstitut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), CNRS, University of Poitiers, 86073 Poitiers, FranceBiogas upgrading by a catalytic process has been studied in order to obtain syngas using renewable source of methane. This work evaluates the influence of metal dopant (Gd, Sm, and Zr) on the CeO<sub>2</sub> structure for the dry reforming of methane over Ni nanoparticle embedded catalysts. The doping with Zr improved the thermal stability of the catalyst, leading to the formation of small Ni nanoparticles, while Ni metal sintering was observed for Ni@CeO<sub>2</sub>, Ni@CeGdO<sub>2</sub>, and Ni@SmO<sub>2</sub>, according to in situ XRD under reduction conditions. The ceria reducibility was affected by the dopant nature, for which the addition of Zr caused distortions in the ceria lattice, promoting the diffusion of oxygen bulk to surface. The doping with Gd and Sm created oxygen vacancies by charge compensation, and the saturation of oxygen vacancies in the fresh samples decreased the degree of Ce reduction, according to TPR results. The larger Ni particles and poor redox behavior for Ni@CeGdO<sub>2</sub> and Ni@CeSmO<sub>2</sub> were responsible for the high carbon formation on these catalysts during the DRM reaction. The Ni@CeZrO<sub>2</sub> catalyst did not present coke formation because of smaller Ni crystallite size and higher ceria reducibility. Therefore, the control of Ni particle size and the high oxygen mobility in the Ni@CeZrO<sub>2</sub> catalyst inhibits carbon deposition and enhances the mechanism of carbon removal, promoting the catalyst stability.https://www.mdpi.com/2674-0389/1/4/23Ni-embeddedceriaceria-zirconiaGd-doped ceriaSm-doped ceriaoxygen storage capacity |
| spellingShingle | André L. A. Marinho Raimundo C. Rabelo-Neto Florence Epron Fabio S. Toniolo Fabio B. Noronha Nicolas Bion Effect of Metal Dopant on the Performance of Ni@CeMeO<sub>2</sub> Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane Methane Ni-embedded ceria ceria-zirconia Gd-doped ceria Sm-doped ceria oxygen storage capacity |
| title | Effect of Metal Dopant on the Performance of Ni@CeMeO<sub>2</sub> Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane |
| title_full | Effect of Metal Dopant on the Performance of Ni@CeMeO<sub>2</sub> Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane |
| title_fullStr | Effect of Metal Dopant on the Performance of Ni@CeMeO<sub>2</sub> Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane |
| title_full_unstemmed | Effect of Metal Dopant on the Performance of Ni@CeMeO<sub>2</sub> Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane |
| title_short | Effect of Metal Dopant on the Performance of Ni@CeMeO<sub>2</sub> Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane |
| title_sort | effect of metal dopant on the performance of ni cemeo sub 2 sub embedded catalysts me gd sm and zr for dry reforming of methane |
| topic | Ni-embedded ceria ceria-zirconia Gd-doped ceria Sm-doped ceria oxygen storage capacity |
| url | https://www.mdpi.com/2674-0389/1/4/23 |
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