Effect of support oxygen storage capacity on the catalytic performance of Rh nanoparticles for CO2 reforming of methane

Ioannis V. Yentekakis; Grammatiki Goula; Maria Hatzisymeon; Ioanna Betsi-argyropoulou; Georgia Botzolaki; Kalliopi Kousi; Dimitris I. Kondarides; Martin J. Taylor; Christopher M.a. Parlett; Amin Osatiashtiani; Georgios Kyriakou; Juan Pedro Holgado; Richard M. Lambert

doi:10.1016/j.apcatb.2018.10.048

Effect of support oxygen storage capacity on the catalytic performance of Rh nanoparticles for CO2 reforming of methane

Ioannis V. Yentekakis, Grammatiki Goula, Maria Hatzisymeon, Ioanna Betsi-argyropoulou, Georgia Botzolaki, Kalliopi Kousi, Dimitris I. Kondarides, Martin J. Taylor, Christopher M.a. Parlett, Amin Osatiashtiani, Georgios Kyriakou, Juan Pedro Holgado, Richard M. Lambert

Research output: Contribution to journal › Article › peer-review

Abstract

The effects of the metal oxide support on the activity, selectivity, resistance to carbon deposition and high temperature oxidative aging on the Rh-catalyzed dry reforming of methane (DRM) were investigated. Three Rh catalysts supported on oxides characterized by very different oxygen storage capacities and labilities (γ-Al ₂O ₃, alumina-ceria-zirconia (ACZ) and ceria-zirconia (CZ)) were studied in the temperature interval 400–750 °C under both integral and differential reaction conditions. ACZ and CZ promoted CO ₂ conversion, yielding CO-enriched synthesis gas. Detailed characterization of these materials, including state of the art XPS measurements obtained via sample transfer between reaction cell and spectrometer chamber, provided clear insight into the factors that determine catalytic performance. The principal Rh species detected by post reaction XPS was Rh ⁰, its relative content decreasing in the order Rh/CZ(100%)>Rh/ACZ(72%)>Rh/γ-Al ₂O ₃(55%). The catalytic activity followed the same order, demonstrating unambiguously that Rh ⁰ is indeed the key active site. Moreover, the presence of CZ in the support served to maintain Rh in the metallic state and minimize carbon deposition under reaction conditions. Carbon deposition, low in all cases, increased in the order Rh/CZ < Rh/ACZ < Rh/γ-Al ₂O ₃ consistent with a bi-functional reaction mechanism whereby backspillover of labile lattice O ²⁻ contributes to carbon oxidation, stabilization of Rh ⁰ and modification of its surface chemistry; the resulting O vacancies in the support providing centers for dissociative adsorption of CO ₂. The lower apparent activation energy observed with CZ-containing samples suggests that CZ is a promising support component for use in low temperature DRM.

Original language	English
Pages (from-to)	490-501
Number of pages	12
Journal	Applied Catalysis B: Environmental
Volume	243
Early online date	28 Oct 2018
DOIs	https://doi.org/10.1016/j.apcatb.2018.10.048
Publication status	Published - 1 Apr 2019

Bibliographical note

© 2018, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/.

Funding: European Union and Greek national funds through the Operational Program "Competitiveness, Entrepreneurship and Innovation", under the call “RESEARCH-CREATE-INNOVATE” (project code: T1EΔK-00782), Royal Society and EPSRC (EP/M005186/2).

Keywords

Active sites
CO activation
Dry reforming of methane
Oxygen ions spillover
Oxygen storage capacity
Resistance to carbon deposition
Rhodium nanoparticles
Support effects
Synthesis gas

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10.1016/j.apcatb.2018.10.048

Effect of support oxygen storage capacity on the catalytic performance
© 2018, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/
Accepted author manuscript, 1.99 MBLicence: CC BY-NC-ND 3.0

Cite this

Yentekakis, I. V., Goula, G., Hatzisymeon, M., Betsi-argyropoulou, I., Botzolaki, G., Kousi, K., Kondarides, D. I., Taylor, M. J., Parlett, C. M. A., Osatiashtiani, A., Kyriakou, G., Holgado, J. P., & Lambert, R. M. (2019). Effect of support oxygen storage capacity on the catalytic performance of Rh nanoparticles for CO2 reforming of methane. Applied Catalysis B: Environmental, 243, 490-501. https://doi.org/10.1016/j.apcatb.2018.10.048

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title = "Effect of support oxygen storage capacity on the catalytic performance of Rh nanoparticles for CO2 reforming of methane",

abstract = "The effects of the metal oxide support on the activity, selectivity, resistance to carbon deposition and high temperature oxidative aging on the Rh-catalyzed dry reforming of methane (DRM) were investigated. Three Rh catalysts supported on oxides characterized by very different oxygen storage capacities and labilities (γ-Al 2O 3, alumina-ceria-zirconia (ACZ) and ceria-zirconia (CZ)) were studied in the temperature interval 400–750 °C under both integral and differential reaction conditions. ACZ and CZ promoted CO 2 conversion, yielding CO-enriched synthesis gas. Detailed characterization of these materials, including state of the art XPS measurements obtained via sample transfer between reaction cell and spectrometer chamber, provided clear insight into the factors that determine catalytic performance. The principal Rh species detected by post reaction XPS was Rh 0, its relative content decreasing in the order Rh/CZ(100%)>Rh/ACZ(72%)>Rh/γ-Al 2O 3(55%). The catalytic activity followed the same order, demonstrating unambiguously that Rh 0 is indeed the key active site. Moreover, the presence of CZ in the support served to maintain Rh in the metallic state and minimize carbon deposition under reaction conditions. Carbon deposition, low in all cases, increased in the order Rh/CZ < Rh/ACZ < Rh/γ-Al 2O 3 consistent with a bi-functional reaction mechanism whereby backspillover of labile lattice O 2− contributes to carbon oxidation, stabilization of Rh 0 and modification of its surface chemistry; the resulting O vacancies in the support providing centers for dissociative adsorption of CO 2. The lower apparent activation energy observed with CZ-containing samples suggests that CZ is a promising support component for use in low temperature DRM. ",

keywords = "Active sites, CO activation, Dry reforming of methane, Oxygen ions spillover, Oxygen storage capacity, Resistance to carbon deposition, Rhodium nanoparticles, Support effects, Synthesis gas",

author = "Yentekakis, {Ioannis V.} and Grammatiki Goula and Maria Hatzisymeon and Ioanna Betsi-argyropoulou and Georgia Botzolaki and Kalliopi Kousi and Kondarides, {Dimitris I.} and Taylor, {Martin J.} and Parlett, {Christopher M.a.} and Amin Osatiashtiani and Georgios Kyriakou and Holgado, {Juan Pedro} and Lambert, {Richard M.}",

note = "{\textcopyright} 2018, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/. Funding: European Union and Greek national funds through the Operational Program {"}Competitiveness, Entrepreneurship and Innovation{"}, under the call “RESEARCH-CREATE-INNOVATE” (project code: T1EΔK-00782), Royal Society and EPSRC (EP/M005186/2).",

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doi = "10.1016/j.apcatb.2018.10.048",

language = "English",

volume = "243",

pages = "490--501",

journal = "Applied Catalysis B: Environmental",

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publisher = "Elsevier",

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Yentekakis, IV, Goula, G, Hatzisymeon, M, Betsi-argyropoulou, I, Botzolaki, G, Kousi, K, Kondarides, DI, Taylor, MJ, Parlett, CMA, Osatiashtiani, A, Kyriakou, G, Holgado, JP & Lambert, RM 2019, 'Effect of support oxygen storage capacity on the catalytic performance of Rh nanoparticles for CO2 reforming of methane', Applied Catalysis B: Environmental, vol. 243, pp. 490-501. https://doi.org/10.1016/j.apcatb.2018.10.048

TY - JOUR

T1 - Effect of support oxygen storage capacity on the catalytic performance of Rh nanoparticles for CO2 reforming of methane

AU - Yentekakis, Ioannis V.

AU - Goula, Grammatiki

AU - Hatzisymeon, Maria

AU - Betsi-argyropoulou, Ioanna

AU - Botzolaki, Georgia

AU - Kousi, Kalliopi

AU - Kondarides, Dimitris I.

AU - Taylor, Martin J.

AU - Parlett, Christopher M.a.

AU - Osatiashtiani, Amin

AU - Kyriakou, Georgios

AU - Holgado, Juan Pedro

AU - Lambert, Richard M.

N1 - © 2018, Elsevier. Licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/. Funding: European Union and Greek national funds through the Operational Program "Competitiveness, Entrepreneurship and Innovation", under the call “RESEARCH-CREATE-INNOVATE” (project code: T1EΔK-00782), Royal Society and EPSRC (EP/M005186/2).

PY - 2019/4/1

Y1 - 2019/4/1

N2 - The effects of the metal oxide support on the activity, selectivity, resistance to carbon deposition and high temperature oxidative aging on the Rh-catalyzed dry reforming of methane (DRM) were investigated. Three Rh catalysts supported on oxides characterized by very different oxygen storage capacities and labilities (γ-Al 2O 3, alumina-ceria-zirconia (ACZ) and ceria-zirconia (CZ)) were studied in the temperature interval 400–750 °C under both integral and differential reaction conditions. ACZ and CZ promoted CO 2 conversion, yielding CO-enriched synthesis gas. Detailed characterization of these materials, including state of the art XPS measurements obtained via sample transfer between reaction cell and spectrometer chamber, provided clear insight into the factors that determine catalytic performance. The principal Rh species detected by post reaction XPS was Rh 0, its relative content decreasing in the order Rh/CZ(100%)>Rh/ACZ(72%)>Rh/γ-Al 2O 3(55%). The catalytic activity followed the same order, demonstrating unambiguously that Rh 0 is indeed the key active site. Moreover, the presence of CZ in the support served to maintain Rh in the metallic state and minimize carbon deposition under reaction conditions. Carbon deposition, low in all cases, increased in the order Rh/CZ < Rh/ACZ < Rh/γ-Al 2O 3 consistent with a bi-functional reaction mechanism whereby backspillover of labile lattice O 2− contributes to carbon oxidation, stabilization of Rh 0 and modification of its surface chemistry; the resulting O vacancies in the support providing centers for dissociative adsorption of CO 2. The lower apparent activation energy observed with CZ-containing samples suggests that CZ is a promising support component for use in low temperature DRM.

AB - The effects of the metal oxide support on the activity, selectivity, resistance to carbon deposition and high temperature oxidative aging on the Rh-catalyzed dry reforming of methane (DRM) were investigated. Three Rh catalysts supported on oxides characterized by very different oxygen storage capacities and labilities (γ-Al 2O 3, alumina-ceria-zirconia (ACZ) and ceria-zirconia (CZ)) were studied in the temperature interval 400–750 °C under both integral and differential reaction conditions. ACZ and CZ promoted CO 2 conversion, yielding CO-enriched synthesis gas. Detailed characterization of these materials, including state of the art XPS measurements obtained via sample transfer between reaction cell and spectrometer chamber, provided clear insight into the factors that determine catalytic performance. The principal Rh species detected by post reaction XPS was Rh 0, its relative content decreasing in the order Rh/CZ(100%)>Rh/ACZ(72%)>Rh/γ-Al 2O 3(55%). The catalytic activity followed the same order, demonstrating unambiguously that Rh 0 is indeed the key active site. Moreover, the presence of CZ in the support served to maintain Rh in the metallic state and minimize carbon deposition under reaction conditions. Carbon deposition, low in all cases, increased in the order Rh/CZ < Rh/ACZ < Rh/γ-Al 2O 3 consistent with a bi-functional reaction mechanism whereby backspillover of labile lattice O 2− contributes to carbon oxidation, stabilization of Rh 0 and modification of its surface chemistry; the resulting O vacancies in the support providing centers for dissociative adsorption of CO 2. The lower apparent activation energy observed with CZ-containing samples suggests that CZ is a promising support component for use in low temperature DRM.

KW - Active sites

KW - CO activation

KW - Dry reforming of methane

KW - Oxygen ions spillover

KW - Oxygen storage capacity

KW - Resistance to carbon deposition

KW - Rhodium nanoparticles

KW - Support effects

KW - Synthesis gas

UR - https://linkinghub.elsevier.com/retrieve/pii/S092633731831004X

UR - https://doi.org/10.17036/researchdata.aston.ac.uk.00000391

UR - http://www.scopus.com/inward/record.url?scp=85056180242&partnerID=8YFLogxK

U2 - 10.1016/j.apcatb.2018.10.048

DO - 10.1016/j.apcatb.2018.10.048

M3 - Article

SN - 0926-3373

VL - 243

SP - 490

EP - 501

JO - Applied Catalysis B: Environmental

JF - Applied Catalysis B: Environmental

ER -

Effect of support oxygen storage capacity on the catalytic performance of Rh nanoparticles for CO2 reforming of methane

Abstract

Bibliographical note

Keywords

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