Homogeneous Iron Porphyrin as a Molecular CO Shuttle Enables Electrochemical Multicarbon Product Formation from CO2.
- 1Division of Chemistry and Chemical Engineering, Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, California91125, United States.
Abstract
Homogeneous molecular catalysts for electrochemical CO2 reduction are generally limited to two-electron-reduced C1 products, primarily CO. Here we propose and demonstrate a fundamentally distinct role for molecular catalysts: as reversible CO shuttles that enhance the local CO activity at the electrical double layer. Using a water-soluble iron porphyrin as a CO shuttle, we observe the formation of isotopically verified C1-C4 hydrocarbons from CO2 in aqueous electrolyte. These products are not observed even in CO-saturated electrolyte in the absence of the iron porphyrin, indicating that the shuttle enhances local CO activity at the electrode surface beyond what bulk saturation can provide. Electrochemical and spectroscopic data support the formation of a stable FeII-CO species outside the compact layer, which releases CO upon further reduction at the electrode surface, consistent with an electrochemically gated shuttle mechanism. These findings suggest a potential design principle in which homogeneous catalysts function as molecular intermediate shuttles at the electrode surface and provide an alternative framework for interpreting beyond-CO products observed in heterogenized molecular catalyst systems.
Related
- Electrochemical Hydroformylation with a Homogeneous Rhodium Catalyst.
- Homogeneous Electrochemical Hydrogenation of 1-Octene with [( iPr PNP)CoCl] and Water
- Highly Charged Porphyrin Molecular Wires.
- Implementing modular design principles for molecular homogeneous catalyst discovery.
- Electrochemical Proton-Coupled Electron Transfer Free Energy Surfaces from Ab Initio Molecular Dynamics
BibTeX
@article{hwang2026homogeneous,
title = {{Homogeneous Iron Porphyrin as a Molecular CO Shuttle Enables Electrochemical Multicarbon Product Formation from CO2.}},
author = {Keon Ha Hwang and Stephen P DiLuzio and Kaitlin M Luedecke and Ryan G Hadt},
journal = {Journal of the American Chemical Society},
year = {2026},
month = sep,
doi = {10.1021/jacs.6c10179},
url = {https://europepmc.org/article/MED/42915548},
note = {CC BY},
}
RIS
TY - JOUR
TI - Homogeneous Iron Porphyrin as a Molecular CO Shuttle Enables Electrochemical Multicarbon Product Formation from CO2.
AU - Keon Ha Hwang
AU - Stephen P DiLuzio
AU - Kaitlin M Luedecke
AU - Ryan G Hadt
PY - 2026
DA - 2026/09/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c10179
UR - https://europepmc.org/article/MED/42915548
AB - Homogeneous molecular catalysts for electrochemical CO2 reduction are generally limited to two-electron-reduced C1 products, primarily CO. Here we propose and demonstrate a fundamentally distinct role for molecular catalysts: as reversible CO shuttles that enhance the local CO activity at the electrical double layer. Using a water-soluble iron porphyrin as a CO shuttle, we observe the formation of isotopically verified C1-C4 hydrocarbons from CO2 in aqueous electrolyte. These products are not observed even in CO-saturated electrolyte in the absence of the iron porphyrin, indicating that the shuttle enhances local CO activity at the electrode surface beyond what bulk saturation can provide. Electrochemical and spectroscopic data support the formation of a stable FeII-CO species outside the compact layer, which releases CO upon further reduction at the electrode surface, consistent with an electrochemically gated shuttle mechanism. These findings suggest a potential design principle in which homogeneous catalysts function as molecular intermediate shuttles at the electrode surface and provide an alternative framework for interpreting beyond-CO products observed in heterogenized molecular catalyst systems.
SN - 0002-7863
SN - 1520-5126
ER -