A Host–Guest Strategy to Achieve Selective and Robust CO₂-to-CO Electrocatalysis in Aqueous Media
Abstract
Heterogeneous materials incorporating molecular catalysts hold strong promise for efficient electrocatalytic CO₂ reduction to value-added products. While activity and selectivity are traditionally tuned through ligand design, increasing attention is being paid to the second-coordination sphere, which modulates reactivity beyond the metal center. Inspired by enzymatic systems, this outer-sphere environment enhances catalysis through spatial confinement and noncovalent interactions. Here, we report a host–guest strategy to control CO₂ reduction using the [bpyMn(CO)₃MeCN]⁺ catalyst encapsulated in an anionic cage. When immobilized on an electrode surface, the assembly selectively produces CO. Mechanistic studies indicate that the cage promotes proton-coupled CO₂ binding while preventing catalyst deactivation. This demonstrates that supramolecular second-sphere engineering is a powerful strategy for enhancing electrocatalytic performance and provides a basis for future developments in molecular electrocatalysts.
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BibTeX
@article{suarezantuna2026hostguest,
title = {{A Host–Guest Strategy to Achieve Selective and Robust CO₂-to-CO Electrocatalysis in Aqueous Media}},
author = {Irene Suarez-Antuna and Guilherme Tripodi and György Szalóki and Carole Duboc and Noémie Lalaoui},
journal = {Journal of the American Chemical Society},
year = {2026},
month = sep,
doi = {10.1021/jacs.6c10366},
url = {https://hal.science/hal-05738616v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - A Host–Guest Strategy to Achieve Selective and Robust CO₂-to-CO Electrocatalysis in Aqueous Media
AU - Irene Suarez-Antuna
AU - Guilherme Tripodi
AU - György Szalóki
AU - Carole Duboc
AU - Noémie Lalaoui
PY - 2026
DA - 2026/09/03
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c10366
UR - https://hal.science/hal-05738616v1
AB - Heterogeneous materials incorporating molecular catalysts hold strong promise for efficient electrocatalytic CO₂ reduction to value-added products. While activity and selectivity are traditionally tuned through ligand design, increasing attention is being paid to the second-coordination sphere, which modulates reactivity beyond the metal center. Inspired by enzymatic systems, this outer-sphere environment enhances catalysis through spatial confinement and noncovalent interactions. Here, we report a host–guest strategy to control CO₂ reduction using the [bpyMn(CO)₃MeCN]⁺ catalyst encapsulated in an anionic cage. When immobilized on an electrode surface, the assembly selectively produces CO. Mechanistic studies indicate that the cage promotes proton-coupled CO₂ binding while preventing catalyst deactivation. This demonstrates that supramolecular second-sphere engineering is a powerful strategy for enhancing electrocatalytic performance and provides a basis for future developments in molecular electrocatalysts.
SN - 0002-7863
SN - 1520-5126
ER -