Tuning covalence for phosphorus-mediated C-C coupling in carbon monoxide electroreduction to multicarbon oxygenates
12 affiliations
- 1Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Sorbonne Université, CNRS, 4 place Jussieu, Paris, France, F-75005
- 2Collège de France
- 3Sorbonne Université, CNRS, Laboratoire de Chimie des Processus Biologiques
- 4Dpto. de Química Inorgánica I, Facultad de Ciencias Químicas
- 5Universidad Complutense
- 6ENSL, CNRS, Laboratoire de Chimie UMR, 46 allée d'Italie, Lyon, France, 69342
- 7Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), UMR CNRS 7285
- 8Université de Poitiers, CNRS
- 9Laboratoire de Réactivité de Surface (LRS), Sorbonne Université, CNRS, 4 place Jussieu, Paris, France, F-75005
- 10FCMat, Sorbonne Université, CNRS, 4 Place Jussieu, Paris, France, 75005
- 11SOLEIL synchrotron
- 12European Synchrotron Radiation Facility (ESRF
Abstract
Electrochemical carbon monoxide reduction (COR) is a promising route for sustainable production of multicarbon chemicals from CO2, as it bypasses the large carbon losses of direct CO2 electroreduction. In most electrocatalysts currently explored to tune COR selectivity towards highadded value multicarbon oxygenated molecules, like acetate and ethanol, copper is the catalytic site of C-C bond formation. Herein, we show that by designing nanoparticles of a strongly covalent copper compound, CuSi2P3, we retain isolated copper atoms during COR and trigger the intervention of phosphorus atoms as C-C coupling sites, without directly involving copper atoms. This profound change in COR mechanism results in a high selectivity towards C2 molecules (80 % Faradaic efficiency), especially oxygenates (73%), at a current density of -150 mA cm-2. This work reveals the importance of tailoring, via the crystal structure, the local environment of metal atoms, to achieve original selectivity in COR with new families of electrocatalysts.
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BibTeX
@misc{ghoridi2026tuning,
title = {{Tuning covalence for phosphorus-mediated C-C coupling in carbon monoxide electroreduction to multicarbon oxygenates}},
author = {Anissa Ghoridi and Carlos V. M. Inocêncio and Hong Phong Duong and Ngoc-Huan Tran and Zubair Ahmed and Isabel Gómez-Recio and Maria Luisa Ruiz-Gonzàlez and Stephan Steinmann and Preeti Verma and Claudia Morais and Nadia Guignard and Antoine Miche and Sandra Casale and Christel Gervais and Cristina Coelho Diogo and Isabelle Génois and Andrea Zitolo and Christoph Sahle and Alessandro Longo and José Maria González-Calbet and Marc Fontecave and David Portehault},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15007881/v2},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007881/v2},
note = {CC BY},
}
RIS
TY - UNPB
TI - Tuning covalence for phosphorus-mediated C-C coupling in carbon monoxide electroreduction to multicarbon oxygenates
AU - Anissa Ghoridi
AU - Carlos V. M. Inocêncio
AU - Hong Phong Duong
AU - Ngoc-Huan Tran
AU - Zubair Ahmed
AU - Isabel Gómez-Recio
AU - Maria Luisa Ruiz-Gonzàlez
AU - Stephan Steinmann
AU - Preeti Verma
AU - Claudia Morais
AU - Nadia Guignard
AU - Antoine Miche
AU - Sandra Casale
AU - Christel Gervais
AU - Cristina Coelho Diogo
AU - Isabelle Génois
AU - Andrea Zitolo
AU - Christoph Sahle
AU - Alessandro Longo
AU - José Maria González-Calbet
AU - Marc Fontecave
AU - David Portehault
PY - 2026
DA - 2026/10/22
PB - ChemRxiv
DO - 10.26434/chemrxiv.15007881/v2
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007881/v2
AB - Electrochemical carbon monoxide reduction (COR) is a promising route for sustainable production of multicarbon chemicals from CO2, as it bypasses the large carbon losses of direct CO2 electroreduction. In most electrocatalysts currently explored to tune COR selectivity towards highadded value multicarbon oxygenated molecules, like acetate and ethanol, copper is the catalytic site of C-C bond formation. Herein, we show that by designing nanoparticles of a strongly covalent copper compound, CuSi2P3, we retain isolated copper atoms during COR and trigger the intervention of phosphorus atoms as C-C coupling sites, without directly involving copper atoms. This profound change in COR mechanism results in a high selectivity towards C2 molecules (80 % Faradaic efficiency), especially oxygenates (73%), at a current density of -150 mA cm-2. This work reveals the importance of tailoring, via the crystal structure, the local environment of metal atoms, to achieve original selectivity in COR with new families of electrocatalysts.
ER -