Electrochemical Hydroformylation with a Homogeneous Rhodium Catalyst.
- 1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California91125, United States.
Abstract
Electrochemical hydroformylation is an attractive pathway to synthesize aldehydes at ambient conditions using electrons sourced from renewable energy as a reductant instead of hydrogen gas sourced from energy-intensive steam methane reforming. However, previously reported electrochemical hydroformylation systems have shown limited rates and selectivities using heterogeneous catalysts, motivating continued development. In this work, we report a homogeneously catalyzed system that achieved a maximum partial current density of 1.1 ± 0.1 mA cm-2 and a Faradaic efficiency of 29 ± 1% toward the conversion of styrene to 2-phenylpropanal at 5 bar CO and 25 °C. Infrared and UV-visible spectroscopies suggested that the initial Rh2Cl2(CO)4 precatalyst undergoes pressure-dependent speciation to Rh(I)-CO species in the presence of CO. Kinetic experiments revealed a complex mechanism in which the rate-determining step likely shifts between electron transfer, substrate coordination, and Rh-H bond cleavage in different substrate concentration and overpotential regimes. Looking forward, the insight from this work informs future strategies to improve the rate and selectivity of electrochemical hydroformylation and other electrochemical C-C bond formation reactions.
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BibTeX
@article{cosner2026electrochemical,
title = {{Electrochemical Hydroformylation with a Homogeneous Rhodium Catalyst.}},
author = {Emma L Cosner and Spencer P Delgado-Kukuczka and Haochen Zhang and Abigail L Blenko and Evan V Miu and Karthish Manthiram},
journal = {Journal of the American Chemical Society},
year = {2026},
month = oct,
doi = {10.1021/jacs.6c15582},
url = {https://europepmc.org/article/MED/42913590},
note = {CC BY},
}
RIS
TY - JOUR
TI - Electrochemical Hydroformylation with a Homogeneous Rhodium Catalyst.
AU - Emma L Cosner
AU - Spencer P Delgado-Kukuczka
AU - Haochen Zhang
AU - Abigail L Blenko
AU - Evan V Miu
AU - Karthish Manthiram
PY - 2026
DA - 2026/10/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c15582
UR - https://europepmc.org/article/MED/42913590
AB - Electrochemical hydroformylation is an attractive pathway to synthesize aldehydes at ambient conditions using electrons sourced from renewable energy as a reductant instead of hydrogen gas sourced from energy-intensive steam methane reforming. However, previously reported electrochemical hydroformylation systems have shown limited rates and selectivities using heterogeneous catalysts, motivating continued development. In this work, we report a homogeneously catalyzed system that achieved a maximum partial current density of 1.1 ± 0.1 mA cm-2 and a Faradaic efficiency of 29 ± 1% toward the conversion of styrene to 2-phenylpropanal at 5 bar CO and 25 °C. Infrared and UV-visible spectroscopies suggested that the initial Rh2Cl2(CO)4 precatalyst undergoes pressure-dependent speciation to Rh(I)-CO species in the presence of CO. Kinetic experiments revealed a complex mechanism in which the rate-determining step likely shifts between electron transfer, substrate coordination, and Rh-H bond cleavage in different substrate concentration and overpotential regimes. Looking forward, the insight from this work informs future strategies to improve the rate and selectivity of electrochemical hydroformylation and other electrochemical C-C bond formation reactions.
SN - 0002-7863
SN - 1520-5126
ER -