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Dynamics at polarized carbon dioxide-iron oxyhydroxide interfaces unveil the origin of multicarbon product formation

Arrigo, Rosa, Blume, Raoul, Streibel, Verena, Genovese, Chiara, Roldan, Alberto, Schuster, Manfred E., Ampelli, Claudio, Perathoner, Siglinda, Velasco Vélez, Juan J., Hävecker, Michael, Knop-Gericke, Axel, Schlögl, Robert and Centi, Gabriele 2022. Dynamics at polarized carbon dioxide-iron oxyhydroxide interfaces unveil the origin of multicarbon product formation. ACS Catalysis 12 , pp. 411-430. 10.1021/acscatal.1c04296

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Abstract

Surface-sensitive ambient pressure X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy combined with an electrocatalytic reactivity study, multilength-scale electron microscopy, and theoretical modeling provide insights into the gas-phase selective reduction of carbon dioxide to isopropanol on a nitrogen-doped carbon-supported iron oxyhydroxide electrocatalyst. Dissolved atomic carbon forms at relevant potentials for carbon dioxide reduction from the reduction of carbon monoxide chemisorbed on the surface of the ferrihydrite-like phase. Theoretical modeling reveals that the ferrihydrite structure allows vicinal chemisorbed carbon monoxide in the appropriate geometrical arrangement for coupling. Based on our observations, we suggest a mechanism of three-carbon-atom product formation, which involves the intermediate formation of atomic carbon that undergoes hydrogenation in the presence of hydrogen cations upon cathodic polarization. This mechanism is effective only in the case of thin ferrihydrite-like nanostructures coordinated at the edge planes of the graphitic support, where nitrogen edge sites stabilize these species and lower the overpotential for the reaction. Larger ferrihydrite-like nanoparticles are ineffective for electron transport.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Publisher: American Chemical Society
ISSN: 2155-5435
Funders: EPSRC
Date of First Compliant Deposit: 22 December 2021
Date of Acceptance: 22 November 2021
Last Modified: 04 Oct 2022 14:16
URI: https://orca.cardiff.ac.uk/id/eprint/146283

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