Electroreduction of Carbon Dioxide to Acetate using Heterogenized Hydrophilic Manganese Porphyrins

Maryam Abdinejad*, Tiange Yuan, Keith Tang, Salatan Duangdangchote, Hugo Pieter Iglesias van Montfort, Mengran Li, Joost Middelkoop, Mädchen Wolff, Thomas Burdyny, More Authors

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

3 Citations (Scopus)
3 Downloads (Pure)


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.

Original languageEnglish
Article numbere202203977
Number of pages7
JournalChemistry - A European Journal
Issue number14
Publication statusPublished - 2023


  • CO electroreduction
  • CO to acetate
  • CORR
  • manganese porphyrin
  • porphyrins

Cite this