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Article

Effect of Metal Dopant on the Performance of Ni@CeMeO2 Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane

by
André L. A. Marinho
1,2,3,
Raimundo C. Rabelo-Neto
2,
Florence Epron
3,
Fabio S. Toniolo
1,
Fabio B. Noronha
2,4,* and
Nicolas Bion
3,*
1
Chemical Engineering Program of COPPE/UFRJ, Federal University of Rio de Janeiro, P.O. Box 68502, Rio de Janeiro 21941-972, RJ, Brazil
2
National Institute of Technology, Catalysis Division, Rio de Janeiro 20081-312, RJ, Brazil
3
Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), CNRS, University of Poitiers, 86073 Poitiers, France
4
University of Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181—UCCS—Unité de Catalyse et Chimie du Solide, 59000 Lille, France
*
Authors to whom correspondence should be addressed.
Methane 2022, 1(4), 300-319; https://doi.org/10.3390/methane1040023
Submission received: 18 August 2022 / Revised: 2 November 2022 / Accepted: 18 November 2022 / Published: 28 November 2022
(This article belongs to the Special Issue Methane Dry Reforming)
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Abstract

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 CeO2 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@CeO2, Ni@CeGdO2, and Ni@SmO2, 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@CeGdO2 and Ni@CeSmO2 were responsible for the high carbon formation on these catalysts during the DRM reaction. The Ni@CeZrO2 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@CeZrO2 catalyst inhibits carbon deposition and enhances the mechanism of carbon removal, promoting the catalyst stability.
Keywords: Ni-embedded; ceria; ceria-zirconia; Gd-doped ceria; Sm-doped ceria; oxygen storage capacity; oxygen isotopic exchange; methane dry reforming; biogas Ni-embedded; ceria; ceria-zirconia; Gd-doped ceria; Sm-doped ceria; oxygen storage capacity; oxygen isotopic exchange; methane dry reforming; biogas
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MDPI and ACS Style

Marinho, A.L.A.; Rabelo-Neto, R.C.; Epron, F.; Toniolo, F.S.; Noronha, F.B.; Bion, N. Effect of Metal Dopant on the Performance of Ni@CeMeO2 Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane. Methane 2022, 1, 300-319. https://doi.org/10.3390/methane1040023

AMA Style

Marinho ALA, Rabelo-Neto RC, Epron F, Toniolo FS, Noronha FB, Bion N. Effect of Metal Dopant on the Performance of Ni@CeMeO2 Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane. Methane. 2022; 1(4):300-319. https://doi.org/10.3390/methane1040023

Chicago/Turabian Style

Marinho, André L. A., Raimundo C. Rabelo-Neto, Florence Epron, Fabio S. Toniolo, Fabio B. Noronha, and Nicolas Bion. 2022. "Effect of Metal Dopant on the Performance of Ni@CeMeO2 Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane" Methane 1, no. 4: 300-319. https://doi.org/10.3390/methane1040023

APA Style

Marinho, A. L. A., Rabelo-Neto, R. C., Epron, F., Toniolo, F. S., Noronha, F. B., & Bion, N. (2022). Effect of Metal Dopant on the Performance of Ni@CeMeO2 Embedded Catalysts (Me = Gd, Sm and Zr) for Dry Reforming of Methane. Methane, 1(4), 300-319. https://doi.org/10.3390/methane1040023

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