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

^*Corresponding author for this work

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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-Al₂O₃, 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 CO₂ 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 Rh⁰, its relative content decreasing in the order Rh/CZ(100%)>Rh/ACZ(72%)>Rh/γ-Al₂O₃(55%). The catalytic activity followed the same order, demonstrating unambiguously that Rh⁰ 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-Al₂O₃ consistent with a bi-functional reaction mechanism whereby backspillover of labile lattice O²⁻ contributes to carbon oxidation, stabilization of Rh⁰ and modification of its surface chemistry; the resulting O vacancies in the support providing centers for dissociative adsorption of CO₂. 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

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

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1016/j.apcatb.2018.10.048

Effect of support oxygen storage capacityAccepted author manuscript, 1.93 MBLicence: CC BY-NC-ND

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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

@article{2a421dd4c717493188308e2de28bf5af,

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-Al2O3, 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 CO2 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 Rh0, its relative content decreasing in the order Rh/CZ(100%)>Rh/ACZ(72%)>Rh/γ-Al2O3(55%). The catalytic activity followed the same order, demonstrating unambiguously that Rh0 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-Al2O3 consistent with a bi-functional reaction mechanism whereby backspillover of labile lattice O2− contributes to carbon oxidation, stabilization of Rh0 and modification of its surface chemistry; the resulting O vacancies in the support providing centers for dissociative adsorption of CO2. 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.}",

year = "2019",

month = apr,

day = "1",

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

language = "English",

volume = "243",

pages = "490--501",

journal = "Applied Catalysis B: Environmental",

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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.

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-Al2O3, 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 CO2 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 Rh0, its relative content decreasing in the order Rh/CZ(100%)>Rh/ACZ(72%)>Rh/γ-Al2O3(55%). The catalytic activity followed the same order, demonstrating unambiguously that Rh0 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-Al2O3 consistent with a bi-functional reaction mechanism whereby backspillover of labile lattice O2− contributes to carbon oxidation, stabilization of Rh0 and modification of its surface chemistry; the resulting O vacancies in the support providing centers for dissociative adsorption of CO2. 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-Al2O3, 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 CO2 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 Rh0, its relative content decreasing in the order Rh/CZ(100%)>Rh/ACZ(72%)>Rh/γ-Al2O3(55%). The catalytic activity followed the same order, demonstrating unambiguously that Rh0 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-Al2O3 consistent with a bi-functional reaction mechanism whereby backspillover of labile lattice O2− contributes to carbon oxidation, stabilization of Rh0 and modification of its surface chemistry; the resulting O vacancies in the support providing centers for dissociative adsorption of CO2. 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

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U2 - 10.1016/j.apcatb.2018.10.048

DO - 10.1016/j.apcatb.2018.10.048

M3 - Article

AN - SCOPUS:85056180242

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

Keywords

UN SDGs

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UoMaH: The University of Manchester at Harwell

Cite this

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

Abstract

Keywords

UN SDGs

Access to Document

Other files and links

Fingerprint

Projects

UoMaH: The University of Manchester at Harwell

Cite this

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