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

Genovese, C; Schuster, ME; Gibson, EK; Gianolio, D; Posligua, V; Grau-Crespo, R; Cibin, G; Wells, PP; Garai, D; Solokha, V; Calderon, SK; Velasco-Vélez, JJ; Ampelli, C; Perathoner, S; Held, G; Centi, G; Arrigo, R

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.

Citation

Genovese, C., Schuster, M., Gibson, E., Gianolio, D., Posligua, V., Grau-Crespo, R., …Arrigo, R. (2018). Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon. Nature communications, 9, 935. https://doi.org/10.1038/s41467-018-03138-7

• Journal Article Type: Article
• Acceptance Date: Jan 23, 2018
• Online Publication Date: Mar 5, 2018
• Publication Date: Mar 5, 2018
• Deposit Date: Dec 4, 2018
• Publicly Available Date: Dec 4, 2018
• Journal: Nature Communications
• Print ISSN: 2041-1723
• Volume: 9
• Pages: 935
• DOI: https://doi.org/10.1038/s41467-018-03138-7
• Publisher URL: https://doi.org/10.1038/s41467-018-03138-7
• Related Public URLs: https://www.nature.com/ncomms/