TY - JOUR

T1 - Steering carbon dioxide reduction toward C–C coupling using copper electrodes modified with porous molecular films

AU - Zhao, Siqi

AU - Christensen, Oliver

AU - Sun, Zhaozong

AU - Liang, Hongqing

AU - Bagger, Alexander

AU - Torbensen, Kristian

AU - Nazari, Pegah

AU - Lauritsen, Jeppe Vang

AU - Pedersen, Steen Uttrup

AU - Rossmeisl, Jan

AU - Daasbjerg, Kim

N1 - Funding Information: This research was supported by the Novo Nordisk Foundation CO2 Research Center (Grant no. NNF21SA0072700). S.Z. (CSC no.201906920080) acknowledges the China Scholarship Council. H.L. is grateful for a Humboldt Research Fellowship (Alexander von Humboldt Foundation). O.C., A.B., and J.R. acknowledge the Danish National Research Foundation Centers of Excellence, the Center for High Entropy Alloy Catalysis (Project DNRF149), and the Independent Research Fund Denmark (Grant no. 0217-00014B). Funding Information: This research was supported by the Novo Nordisk Foundation CO Research Center (Grant no. NNF21SA0072700). S.Z. (CSC no.201906920080) acknowledges the China Scholarship Council. H.L. is grateful for a Humboldt Research Fellowship (Alexander von Humboldt Foundation). O.C., A.B., and J.R. acknowledge the Danish National Research Foundation Centers of Excellence, the Center for High Entropy Alloy Catalysis (Project DNRF149), and the Independent Research Fund Denmark (Grant no. 0217-00014B). 2 Publisher Copyright: © 2023, The Author(s).

PY - 2023

Y1 - 2023

N2 - Copper offers unique capability as catalyst for multicarbon compounds production in the electrochemical carbon dioxide reduction reaction. In lieu of conventional catalysis alloying with other elements, copper can be modified with organic molecules to regulate product distribution. Here, we systematically study to which extent the carbon dioxide reduction is affected by film thickness and porosity. On a polycrystalline copper electrode, immobilization of porous bipyridine-based films of varying thicknesses is shown to result in almost an order of magnitude enhancement of the intrinsic current density pertaining to ethylene formation while multicarbon products selectivity increases from 9.7 to 61.9%. In contrast, the total current density remains mostly unaffected by the modification once it is normalized with respect to the electrochemical active surface area. Supported by a microkinetic model, we propose that porous and thick films increase both local carbon monoxide partial pressure and the carbon monoxide surface coverage by retaining in situ generated carbon monoxide. This reroutes the reaction pathway toward multicarbon products by enhancing carbon–carbon coupling. Our study highlights the significance of customizing the molecular film structure to improve the selectivity of copper catalysts for carbon dioxide reduction reaction.

AB - Copper offers unique capability as catalyst for multicarbon compounds production in the electrochemical carbon dioxide reduction reaction. In lieu of conventional catalysis alloying with other elements, copper can be modified with organic molecules to regulate product distribution. Here, we systematically study to which extent the carbon dioxide reduction is affected by film thickness and porosity. On a polycrystalline copper electrode, immobilization of porous bipyridine-based films of varying thicknesses is shown to result in almost an order of magnitude enhancement of the intrinsic current density pertaining to ethylene formation while multicarbon products selectivity increases from 9.7 to 61.9%. In contrast, the total current density remains mostly unaffected by the modification once it is normalized with respect to the electrochemical active surface area. Supported by a microkinetic model, we propose that porous and thick films increase both local carbon monoxide partial pressure and the carbon monoxide surface coverage by retaining in situ generated carbon monoxide. This reroutes the reaction pathway toward multicarbon products by enhancing carbon–carbon coupling. Our study highlights the significance of customizing the molecular film structure to improve the selectivity of copper catalysts for carbon dioxide reduction reaction.

U2 - 10.1038/s41467-023-36530-z

DO - 10.1038/s41467-023-36530-z

M3 - Journal article

C2 - 36792630

AN - SCOPUS:85148115010

VL - 14

JO - Nature Communications

JF - Nature Communications

SN - 2041-1723

IS - 1

M1 - 844

ER -