Uncovering the reaction mechanism behind CoO as active phase for CO2 hydrogenation

Iris C.ten Have; Josepha J.G. Kromwijk; Matteo Monai; Davide Ferri; Ellen B. Sterk; Florian Meirer; Bert M. Weckhuysen

doi:10.1038/s41467-022-27981-x

Uncovering the reaction mechanism behind CoO as active phase for CO₂ hydrogenation

Iris C.ten Have, Josepha J.G. Kromwijk, Matteo Monai, Davide Ferri, Ellen B. Sterk, Florian Meirer^*, Bert M. Weckhuysen

^*Corresponding author for this work

Faculty of Science

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

Abstract

Transforming carbon dioxide into valuable chemicals and fuels, is a promising tool for environmental and industrial purposes. Here, we present catalysts comprising of cobalt (oxide) nanoparticles stabilized on various support oxides for hydrocarbon production from carbon dioxide. We demonstrate that the activity and selectivity can be tuned by selection of the support oxide and cobalt oxidation state. Modulated excitation (ME) diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveals that cobalt oxide catalysts follows the hydrogen-assisted pathway, whereas metallic cobalt catalysts mainly follows the direct dissociation pathway. Contrary to the commonly considered metallic active phase of cobalt-based catalysts, cobalt oxide on titania support is the most active catalyst in this study and produces 11% C₂₊ hydrocarbons. The C₂₊ selectivity increases to 39% (yielding 104 mmol h⁻¹ g_cat⁻¹ C₂₊ hydrocarbons) upon co-feeding CO and CO₂ at a ratio of 1:2 at 250 °C and 20 bar, thus outperforming the majority of typical cobalt-based catalysts.

Original language	English
Article number	324
Pages (from-to)	1-11
Journal	Nature Communications
Volume	13
Issue number	1
DOIs	https://doi.org/10.1038/s41467-022-27981-x
Publication status	Published - 14 Jan 2022

Bibliographical note

Funding Information:
This work was supported by the Netherlands Research Council (NWO) in the frame of a Technology Area (TA) grant of the Innovation Fund Chemistry, together with Shell, DSM Resolve and Leiden Probe Microscopy (grant no. 731016201). Ramon Oord (Utrecht University (UU)) is gratefully acknowledged for technical support regarding the catalytic testing set-up. Mark J. Meijerink (UU) and Nienke L. Visser (UU) are acknowledged for the TEM measurements. Jelle Kranenborg (UU) is thanked for help with the ME DRIFTS experiments. Maarten Nachtegaal (PSI) is thanked for providing access to the offline laboratory of the SuperXAS beamline for the ME DRIFTS experiments. Alexander P. van Bavel (Shell International BV) is thanked for fruitful discussions on the topic. Jaap N. Louwen is gratefully acknowledged for his input on and assistance with the DFT calculations.

Publisher Copyright:
© 2022, The Author(s).

Funding

This work was supported by the Netherlands Research Council (NWO) in the frame of a Technology Area (TA) grant of the Innovation Fund Chemistry, together with Shell, DSM Resolve and Leiden Probe Microscopy (grant no. 731016201). Ramon Oord (Utrecht University (UU)) is gratefully acknowledged for technical support regarding the catalytic testing set-up. Mark J. Meijerink (UU) and Nienke L. Visser (UU) are acknowledged for the TEM measurements. Jelle Kranenborg (UU) is thanked for help with the ME DRIFTS experiments. Maarten Nachtegaal (PSI) is thanked for providing access to the offline laboratory of the SuperXAS beamline for the ME DRIFTS experiments. Alexander P. van Bavel (Shell International BV) is thanked for fruitful discussions on the topic. Jaap N. Louwen is gratefully acknowledged for his input on and assistance with the DFT calculations.

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Cite this

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title = "Uncovering the reaction mechanism behind CoO as active phase for CO2 hydrogenation",

abstract = "Transforming carbon dioxide into valuable chemicals and fuels, is a promising tool for environmental and industrial purposes. Here, we present catalysts comprising of cobalt (oxide) nanoparticles stabilized on various support oxides for hydrocarbon production from carbon dioxide. We demonstrate that the activity and selectivity can be tuned by selection of the support oxide and cobalt oxidation state. Modulated excitation (ME) diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveals that cobalt oxide catalysts follows the hydrogen-assisted pathway, whereas metallic cobalt catalysts mainly follows the direct dissociation pathway. Contrary to the commonly considered metallic active phase of cobalt-based catalysts, cobalt oxide on titania support is the most active catalyst in this study and produces 11\% C2+ hydrocarbons. The C2+ selectivity increases to 39\% (yielding 104 mmol h−1 gcat−1 C2+ hydrocarbons) upon co-feeding CO and CO2 at a ratio of 1:2 at 250 °C and 20 bar, thus outperforming the majority of typical cobalt-based catalysts.",

author = "Have, \{Iris C.ten\} and Kromwijk, \{Josepha J.G.\} and Matteo Monai and Davide Ferri and Sterk, \{Ellen B.\} and Florian Meirer and Weckhuysen, \{Bert M.\}",

note = "Funding Information: This work was supported by the Netherlands Research Council (NWO) in the frame of a Technology Area (TA) grant of the Innovation Fund Chemistry, together with Shell, DSM Resolve and Leiden Probe Microscopy (grant no. 731016201). Ramon Oord (Utrecht University (UU)) is gratefully acknowledged for technical support regarding the catalytic testing set-up. Mark J. Meijerink (UU) and Nienke L. Visser (UU) are acknowledged for the TEM measurements. Jelle Kranenborg (UU) is thanked for help with the ME DRIFTS experiments. Maarten Nachtegaal (PSI) is thanked for providing access to the offline laboratory of the SuperXAS beamline for the ME DRIFTS experiments. Alexander P. van Bavel (Shell International BV) is thanked for fruitful discussions on the topic. Jaap N. Louwen is gratefully acknowledged for his input on and assistance with the DFT calculations. Publisher Copyright: {\textcopyright} 2022, The Author(s).",

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AU - Have, Iris C.ten

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AU - Monai, Matteo

AU - Ferri, Davide

AU - Sterk, Ellen B.

AU - Meirer, Florian

AU - Weckhuysen, Bert M.

N1 - Funding Information: This work was supported by the Netherlands Research Council (NWO) in the frame of a Technology Area (TA) grant of the Innovation Fund Chemistry, together with Shell, DSM Resolve and Leiden Probe Microscopy (grant no. 731016201). Ramon Oord (Utrecht University (UU)) is gratefully acknowledged for technical support regarding the catalytic testing set-up. Mark J. Meijerink (UU) and Nienke L. Visser (UU) are acknowledged for the TEM measurements. Jelle Kranenborg (UU) is thanked for help with the ME DRIFTS experiments. Maarten Nachtegaal (PSI) is thanked for providing access to the offline laboratory of the SuperXAS beamline for the ME DRIFTS experiments. Alexander P. van Bavel (Shell International BV) is thanked for fruitful discussions on the topic. Jaap N. Louwen is gratefully acknowledged for his input on and assistance with the DFT calculations. Publisher Copyright: © 2022, The Author(s).

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N2 - Transforming carbon dioxide into valuable chemicals and fuels, is a promising tool for environmental and industrial purposes. Here, we present catalysts comprising of cobalt (oxide) nanoparticles stabilized on various support oxides for hydrocarbon production from carbon dioxide. We demonstrate that the activity and selectivity can be tuned by selection of the support oxide and cobalt oxidation state. Modulated excitation (ME) diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveals that cobalt oxide catalysts follows the hydrogen-assisted pathway, whereas metallic cobalt catalysts mainly follows the direct dissociation pathway. Contrary to the commonly considered metallic active phase of cobalt-based catalysts, cobalt oxide on titania support is the most active catalyst in this study and produces 11% C2+ hydrocarbons. The C2+ selectivity increases to 39% (yielding 104 mmol h−1 gcat−1 C2+ hydrocarbons) upon co-feeding CO and CO2 at a ratio of 1:2 at 250 °C and 20 bar, thus outperforming the majority of typical cobalt-based catalysts.

AB - Transforming carbon dioxide into valuable chemicals and fuels, is a promising tool for environmental and industrial purposes. Here, we present catalysts comprising of cobalt (oxide) nanoparticles stabilized on various support oxides for hydrocarbon production from carbon dioxide. We demonstrate that the activity and selectivity can be tuned by selection of the support oxide and cobalt oxidation state. Modulated excitation (ME) diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveals that cobalt oxide catalysts follows the hydrogen-assisted pathway, whereas metallic cobalt catalysts mainly follows the direct dissociation pathway. Contrary to the commonly considered metallic active phase of cobalt-based catalysts, cobalt oxide on titania support is the most active catalyst in this study and produces 11% C2+ hydrocarbons. The C2+ selectivity increases to 39% (yielding 104 mmol h−1 gcat−1 C2+ hydrocarbons) upon co-feeding CO and CO2 at a ratio of 1:2 at 250 °C and 20 bar, thus outperforming the majority of typical cobalt-based catalysts.

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