Elucidating the Roles of Nafion/Solvent Formulations in Copper-Catalyzed CO2 Electrolysis

Pan Ding, Hongyu An, Philipp Zellner, Tianfu Guan, Jianyong Gao, Peter Müller-Buschbaum, Bert M. Weckhuysen, Ward van der Stam, Ian D. Sharp

Research output: Contribution to journalArticlepeer-review

12 Scopus citations


Nafion ionomer, composed of hydrophobic perfluorocarbon backbones and hydrophilic sulfonic acid side chains, is the most widely used additive for preparing catalyst layers (CLs) for electrochemical CO2 reduction, but its impact on the performance of CO2 electrolysis remains poorly understood. Here, we systematically investigate the role of the catalyst ink formulation on CO2 electrolysis using commercial CuO nanoparticles as the model pre-catalyst. We find that the presence of Nafion is essential for achieving stable product distributions due to its ability to stabilize the catalyst morphology under reaction conditions. Moreover, the Nafion content and solvent composition (water/alcohol fraction) regulate the internal structure of Nafion coatings, as well as the catalyst morphology, thereby significantly impacting CO2 electrolysis performance, resulting in variations of C2+ product Faradaic efficiency (FE) by >3×, with C2+ FE ranging from 17 to 54% on carbon paper substrates. Using a combination of ellipsometry and in situ Raman spectroscopy during CO2 reduction, we find that such selectivity differences stem from changes to the local reaction microenvironment. In particular, the combination of high water/alcohol ratios and low Nafion fractions in the catalyst ink results in stable and favorable microenvironments, increasing the local CO2/H2O concentration ratio and promoting high CO surface coverage to facilitate C2+ production in long-term CO2 electrolysis. Therefore, this work provides insights into the critical role of Nafion binders and underlines the importance of optimizing Nafion/solvent formulations as a means of enhancing the performance of electrochemical CO2 reduction systems.

Original languageEnglish
Pages (from-to)5336-5347
Number of pages12
JournalACS Catalysis
Issue number8
StatePublished - 21 Apr 2023


  • CO reduction
  • Cu catalyst
  • Raman spectroscopy
  • catalyst ink formulations
  • nafion ionomer
  • reaction microenvironment


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