Electroreduction of Carbon Dioxide to Acetate using Heterogenized Hydrophilic Manganese Porphyrins

Electroreduction of Carbon Dioxide to Acetate using Heterogenized Hydrophilic Manganese Porphyrins

Abdinejad, M. (TU Delft ChemE/Materials for Energy Conversion and Storage)
Yuan, T. (University of Toronto)
Tang, Keith (University of Toronto)
Duangdangchote, Salatan (University of Toronto)
Iglesias van Montfort, H.P. (TU Delft ChemE/Materials for Energy Conversion and Storage)
Li, Mengran (TU Delft ChemE/Materials for Energy Conversion and Storage)
Middelkoop, J. (TU Delft ChemE/O&O groep)
Wolff, M.J. (TU Delft QN/Kavli Nanolab Delft)
Burdyny, T.E. (TU Delft ChemE/Materials for Energy Conversion and Storage)

2023

The electrochemical reduction of carbon dioxide (CO₂) to value-added chemicals is a promising strategy to mitigate climate change. Metalloporphyrins have been used as a promising class of stable and tunable catalysts for the electrochemical reduction reaction of CO₂ (CO₂RR) but have been primarily restricted to single-carbon reduction products. Here, we utilize functionalized earth-abundant manganese tetraphenylporphyrin-based (Mn-TPP) molecular electrocatalysts that have been immobilized via electrografting onto a glassy carbon electrode (GCE) to convert CO₂ with overall 94 % Faradaic efficiencies, with 62 % being converted to acetate. Tuning of Mn-TPP with electron-withdrawing sulfonate groups (Mn-TPPS) introduced mechanistic changes arising from the electrostatic interaction between the sulfonate groups and water molecules, resulting in better surface coverage, which facilitated higher conversion rates than the non-functionalized Mn-TPP. For Mn-TPP only carbon monoxide and formate were detected as CO₂ reduction products. Density-functional theory (DFT) calculations confirm that the additional sulfonate groups could alter the C−C coupling pathway from *CO→*COH→*COH-CO to *CO→*CO-CO→*COH-CO, reducing the free energy barrier of C−C coupling in the case of Mn-TPPS. This opens a new approach to designing metalloporphyrin catalysts for two carbon products in CO₂RR.

CO electroreduction
CO to acetate
CORR
manganese porphyrin
porphyrins

http://resolver.tudelft.nl/uuid:765f4cf7-8b36-445e-8c53-2e4d6bdff841

https://doi.org/10.1002/chem.202203977

0947-6539

Chemistry: A European Journal, 29 (14)

Institutional Repository

journal article

© 2023 M. Abdinejad, T. Yuan, Keith Tang, Salatan Duangdangchote, H.P. Iglesias van Montfort, Mengran Li, J. Middelkoop, M.J. Wolff, T.E. Burdyny, More Authors