The University of Southampton
University of Southampton Institutional Repository

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
204c1a2f-07fa-4fa4-9c42-54113f89c620
Schuster, Manfred
80a2d548-3808-44ea-80d2-043e87b135cf
Gibson, Emma K.
f646c967-fe31-4497-b65f-2f29a888ffd3
Gianolio, Diego
5b316f7d-f314-4337-954e-8c0ce8e38223
Posligua, Victor
a823749e-0f3f-43a8-93a1-3180df57602c
Grau-Crespo, Ricardo
d3779631-8b1f-43e5-b38c-2c3bd2cfa5fa
Cibin, Giannantonio
61a833d3-097f-4817-bcd3-6b26cf42dbe5
Wells, Peter P.
bc4fdc2d-a490-41bf-86cc-400edecf2266
Garai, Debi
48313d7a-c788-4ad3-9b45-a21b864315bd
Solokha, Vladyslav
fab9086e-ae78-4571-b17e-e5c50dcdd9ab
Krick Calderon, Sandra
1f6a06ac-6480-479d-a40a-e4e2f6cde02b
Velasco-Velez, Juan
f83753d3-b8c5-4e1c-a39e-36cbbd6d95d8
Ampelli, Claudio
0b5ae47a-9335-4f7a-8cdd-3cff3d926955
Perathoner, Siglinda
097df468-1fb2-4747-96c5-4b44d9356a04
Held, Georg
ad070380-ba97-42db-9a0d-9e5d73b62cd0
Centi, Gabriele
b4127bb8-65fa-414e-9e88-047a88b06e94
Arrigo, Rosa
0998a17a-56f9-49c6-8a47-bdd9099c523a
Genovese, Chiara
204c1a2f-07fa-4fa4-9c42-54113f89c620
Schuster, Manfred
80a2d548-3808-44ea-80d2-043e87b135cf
Gibson, Emma K.
f646c967-fe31-4497-b65f-2f29a888ffd3
Gianolio, Diego
5b316f7d-f314-4337-954e-8c0ce8e38223
Posligua, Victor
a823749e-0f3f-43a8-93a1-3180df57602c
Grau-Crespo, Ricardo
d3779631-8b1f-43e5-b38c-2c3bd2cfa5fa
Cibin, Giannantonio
61a833d3-097f-4817-bcd3-6b26cf42dbe5
Wells, Peter P.
bc4fdc2d-a490-41bf-86cc-400edecf2266
Garai, Debi
48313d7a-c788-4ad3-9b45-a21b864315bd
Solokha, Vladyslav
fab9086e-ae78-4571-b17e-e5c50dcdd9ab
Krick Calderon, Sandra
1f6a06ac-6480-479d-a40a-e4e2f6cde02b
Velasco-Velez, Juan
f83753d3-b8c5-4e1c-a39e-36cbbd6d95d8
Ampelli, Claudio
0b5ae47a-9335-4f7a-8cdd-3cff3d926955
Perathoner, Siglinda
097df468-1fb2-4747-96c5-4b44d9356a04
Held, Georg
ad070380-ba97-42db-9a0d-9e5d73b62cd0
Centi, Gabriele
b4127bb8-65fa-414e-9e88-047a88b06e94
Arrigo, Rosa
0998a17a-56f9-49c6-8a47-bdd9099c523a

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, [935]. (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.

Text
s41467-018-03138-7 - Version of Record
Available under License Creative Commons Attribution.
Download (2MB)

More information

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

Identifiers

Local EPrints ID: 418571
URI: http://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

Catalogue record

Date deposited: 12 Mar 2018 17:30
Last modified: 16 Mar 2024 03:47

Export record

Altmetrics

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

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×