Electrocatalytic reduction of carbon dioxide to carbon monoxide and methane at an immobilized cobalt protoporphyrin.
The electrochemical conversion of carbon dioxide and water into useful products is a major challenge in facilitating a closed carbon cycle. Here we report a cobalt protoporphyrin immobilized on a pyrolytic graphite electrode that reduces carbon dioxide in an aqueous acidic solution at relatively low overpotential (0.5 V), with an efficiency and selectivity comparable to the best porphyrin-based electrocatalyst in the literature. While carbon monoxide is the main reduction product, we also observe methane as by-product. The results of our detailed pH-dependent studies are explained consistently by a mechanism in which carbon dioxide is activated by the cobalt protoporphyrin through the stabilization of a radical intermediate, which acts as Brønsted base. The basic character of this intermediate explains how the carbon dioxide reduction circumvents a concerted proton-electron transfer mechanism, in contrast to hydrogen evolution. Our results and their mechanistic interpretations suggest strategies for designing improved catalysts.
Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA Leiden, The Netherlands.
Jing
J
Shen
Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA Leiden, The Netherlands.
Ruud
R
Kortlever
PhotoCatalytic Synthesis Group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, PO Box 217, 7500 AE Enschede, The Netherlands.
Recep
R
Kas
Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA Leiden, The Netherlands.
Yuvraj Y
YY
Birdja
Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA Leiden, The Netherlands.
Oscar
O
Diaz-Morales
Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA Leiden, The Netherlands.
Youngkook
Y
Kwon
Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA Leiden, The Netherlands.
Isis
I
Ledezma-Yanez
Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA Leiden, The Netherlands.
Klaas Jan P
KJ
Schouten
PhotoCatalytic Synthesis Group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, PO Box 217, 7500 AE Enschede, The Netherlands.
Guido
G
Mul
Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA Leiden, The Netherlands.
Marc T M
MT
Koper