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

DOI: 10.1038/s41467-018-03138-7 DOI Help

Authors: Chiara Genovese (University of Messina) , Manfred E. Schuster (Johnson Matthey Technology Centre) , Emma K. Gibson (UK Catalysis Hub; UCL) , Diego Gianolio (Diamond Light Source) , Victor Posligua (University of Reading) , Ricardo Grau-Crespo (University of Reading) , Giannantonio Cibin (Diamond Light Source) , Peter Wells (Diamond Light Source; University of Southampton) , Debi Garai (Diamond Light Source) , Vladyslav Solokha (Diamond Light Source) , Sandra Krick Calderon (FAU Erlangen-Nürnberg) , Juan J. Velasco-Velez (Max-Planck Institut für Chemische Energiekonversion) , Claudio Ampelli (University of Messina) , Siglinda Perathoner (University of Messina) , Georg Held (Diamond Light Source; University of Reading) , Gabriele Centi (University of Messina) , Rosa Arrigo (Diamond Light Source; University of Reading)
Co-authored by industrial partner: Yes

Type: Journal Paper
Journal: Nature Communications , VOL 9

State: Published (Approved)
Published: March 2018
Diamond Proposal Number(s): 17031 , 10306

Open Access Open Access

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.

Journal Keywords: Catalytic mechanisms; Electrocatalysis

Subject Areas: Chemistry

Diamond Offline Facilities: Electron Physical Sciences Imaging Center (ePSIC)
Instruments: B18-Core EXAFS , E01-JEM ARM 200CF

Added On: 12/03/2018 09:52


Discipline Tags:

Physical Chemistry Catalysis Chemistry

Technical Tags:

Microscopy Spectroscopy Electron Microscopy (EM) X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS) X-ray Absorption Near Edge Structure (XANES) Scanning Transmission Electron Microscopy (STEM)