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Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon

Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon
Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon
The carbon–carbon coupling via electrochemical reduction of carbon dioxide represents the biggest challenge for using this route as platform for chemicals synthesis. Here we show that nanostructured iron (III) oxyhydroxide on nitrogen-doped carbon enables high Faraday efficiency (97.4%) and selectivity to acetic acid (61%) at very-low potential (−0.5 V vs silver/silver chloride). Using a combination of electron microscopy, operando X-ray spectroscopy techniques and density functional theory simulations, we correlate the activity to acetic acid at this potential to the formation of nitrogen-coordinated iron (II) sites as single atoms or polyatomic species at the interface between iron oxyhydroxide and the nitrogen-doped carbon. The evolution of hydrogen is correlated to the formation of metallic iron and observed as dominant reaction path over iron oxyhydroxide on oxygen-doped carbon in the overall range of negative potential investigated, whereas over iron oxyhydroxide on nitrogen-doped carbon it becomes important only at more negative potentials.
1-12
Genovese, Chiara
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Schuster, Manfred
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Gibson, Emma K.
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Gianolio, Diego
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Posligua, Victor
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Grau-Crespo, Ricardo
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Cibin, Giannantonio
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Wells, Peter P.
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Garai, Debi
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Solokha, Vladyslav
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Krick Calderon, Sandra
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Velasco-Velez, Juan
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Ampelli, Claudio
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Perathoner, Siglinda
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Held, Georg
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Centi, Gabriele
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Arrigo, Rosa
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Genovese, Chiara
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Schuster, Manfred
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Gibson, Emma K.
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Gianolio, Diego
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Posligua, Victor
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Grau-Crespo, Ricardo
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Cibin, Giannantonio
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Wells, Peter P.
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Garai, Debi
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Solokha, Vladyslav
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Krick Calderon, Sandra
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Velasco-Velez, Juan
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Ampelli, Claudio
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Perathoner, Siglinda
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Held, Georg
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Centi, Gabriele
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Arrigo, Rosa
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Genovese, Chiara, Schuster, Manfred, Gibson, Emma K., Gianolio, Diego, Posligua, Victor, Grau-Crespo, Ricardo, Cibin, Giannantonio, Wells, Peter P., Garai, Debi, Solokha, Vladyslav, Krick Calderon, Sandra, Velasco-Velez, Juan, Ampelli, Claudio, Perathoner, Siglinda, Held, Georg, Centi, Gabriele and Arrigo, Rosa (2018) Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon. Nature Communications, 9 (1), 1-12. (doi:10.1038/s41467-018-03138-7).

Record type: Article

Abstract

The carbon–carbon coupling via electrochemical reduction of carbon dioxide represents the biggest challenge for using this route as platform for chemicals synthesis. Here we show that nanostructured iron (III) oxyhydroxide on nitrogen-doped carbon enables high Faraday efficiency (97.4%) and selectivity to acetic acid (61%) at very-low potential (−0.5 V vs silver/silver chloride). Using a combination of electron microscopy, operando X-ray spectroscopy techniques and density functional theory simulations, we correlate the activity to acetic acid at this potential to the formation of nitrogen-coordinated iron (II) sites as single atoms or polyatomic species at the interface between iron oxyhydroxide and the nitrogen-doped carbon. The evolution of hydrogen is correlated to the formation of metallic iron and observed as dominant reaction path over iron oxyhydroxide on oxygen-doped carbon in the overall range of negative potential investigated, whereas over iron oxyhydroxide on nitrogen-doped carbon it becomes important only at more negative potentials.

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Accepted/In Press date: 23 January 2018
e-pub ahead of print date: 5 March 2018

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Local EPrints ID: 418571
URI: https://eprints.soton.ac.uk/id/eprint/418571
PURE UUID: d141632d-94d0-4b21-a9e9-97fca4635adf
ORCID for Peter P. Wells: ORCID iD orcid.org/0000-0002-0859-9172

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Date deposited: 12 Mar 2018 17:30
Last modified: 14 Mar 2019 01:42

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Contributors

Author: Chiara Genovese
Author: Manfred Schuster
Author: Emma K. Gibson
Author: Diego Gianolio
Author: Victor Posligua
Author: Ricardo Grau-Crespo
Author: Giannantonio Cibin
Author: Peter P. Wells ORCID iD
Author: Debi Garai
Author: Vladyslav Solokha
Author: Sandra Krick Calderon
Author: Juan Velasco-Velez
Author: Claudio Ampelli
Author: Siglinda Perathoner
Author: Georg Held
Author: Gabriele Centi
Author: Rosa Arrigo

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