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

Arrigo, R; Blume, R; Streibel, V; Genovese, C; Roldan, A; Schuster, ME; Ampelli, C; Perathoner, S; Vélez, JJV; Hävecker, M; Knop-Gericke, A; Schlögl, R; Centi, G

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 theo-retical modelling 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. Theo-retical modelling reveals that the ferrihydrite structure allows vicinal chemisorbed species in the appropriate geometrical arrangement for coupling. Based on our observations, we suggest a mechanism of three-carbon atoms product formation, which involves the intermediate formation of atomic carbon undergoing 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.

• Journal Article Type: Article
• Acceptance Date: Nov 22, 2021
• Online Publication Date: Dec 16, 2021
• Publication Date: Jan 7, 2022
• Deposit Date: Nov 24, 2021
• Publicly Available Date: Jan 6, 2022
• Journal: ACS Catalysis
• Electronic ISSN: 2155-5435
• Publisher: American Chemical Society
• Volume: 12
• Issue: 1
• Pages: 411-430
• DOI: https://doi.org/10.1021/acscatal.1c04296
• Publisher URL: https://doi.org/10.1021/acscatal.1c04296
• Related Public URLs: http://pubs.acs.org/page/accacs/about.html
• Additional Information: Funders : Engineering and Physical Sciences Research Council (EPSRC);EU Framework Programme for Research and Innovation HORIZON 2020; Projects : UKRI Interdisciplinary Centre for Circular Chemical Economy;The UK Catalysis Hub;Catalytic Science in the Harwell Research Centre;CALIPSOplus; Grant Number: EP/V011863/1; Grant Number: EP/K014706/1, EP/K014668/1, EP/K014854/1, EP/K014714/1; Grant Number: EP/I019693/1; Grant Number: 730872