The Concentration Determines Reaction Efficiency of Hetero‐Coupling of Bio‐Based Medium Chain Carboxylic Acids by Kolbe Electrolysis
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Wiley
2026
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| author | Max Pohl Katharina Röhring Micjel Chávez Morejón Falk Harnisch |
| author_facet | Max Pohl Katharina Röhring Micjel Chávez Morejón Falk Harnisch Max Pohl Katharina Röhring Micjel Chávez Morejón Falk Harnisch |
| collection | Wiley Open Access |
| contents | The Concentration Determines Reaction Efficiency of Hetero‐Coupling of Bio‐Based Medium Chain Carboxylic Acids by Kolbe Electrolysis Max Pohl Katharina Röhring Micjel Chávez Morejón Falk Harnisch ChemSusChem Mixtures of seven n‐ carboxylic acids ( n‐ CA), ranging from acetic acid to n‐ octanoic acid, that can be gained from the microbial conversion of waste biomass, were converted into liquid drop‐in fuel via Kolbe electrolysis. We demonstrate a strong, sigmoidal correlation between the total n ‐CA concentration and the Coulombic efficiency for fuel‐like liquid products (CE fuel ). Crucially, only above an apparent threshold concentration of 0.1 mol L −1 n‐ CA, Kolbe electrolysis takes place, whereas at lower concentrations the oxygen evolution reaction (OER) dominates. Optimal performance was achieved at the highest concentration tested, 1.5 mol L −1 , yielding a maximum CE fuel of 63.8 ± 1.4%, whereas for n‐ CA to 0.1 mol L −1 and 0.5 mol L −1 , the chain shortening reaction (CSR) strongly affects CE fuel . Furthermore, the study provides valuable insights into reaction selectivity, demonstrating that longer‐chain n ‐CA react preferentially compared to shorter‐chain n ‐CA, a phenomenon that is attributed to their higher hydrophobicity and hence accumulation in the hydrophobic layer formed on the electrode. Using a one‐chamber cell system at optimized concentration significantly lowered energy demand to 2.92 ± 0.04 kWhL −1 of fuel produced, representing a 40% reduction compared to similar two‐chamber setups. 10.1002/cssc.70753 http://creativecommons.org/licenses/by/4.0/ |
| doi_str_mv | 10.1002/cssc.70753 |
| format | Artículo Open Access |
| id | wiley_oa_10_1002_cssc_70753 |
| institution | Wiley Open Access |
| license_str_mv | http://creativecommons.org/licenses/by/4.0/ |
| publishDate | 2026 |
| publisher | Wiley |
| record_format | wiley_oa |
| spellingShingle | The Concentration Determines Reaction Efficiency of Hetero‐Coupling of Bio‐Based Medium Chain Carboxylic Acids by Kolbe Electrolysis Max Pohl Katharina Röhring Micjel Chávez Morejón Falk Harnisch ChemSusChem The Concentration Determines Reaction Efficiency of Hetero‐Coupling of Bio‐Based Medium Chain Carboxylic Acids by Kolbe Electrolysis Max Pohl Katharina Röhring Micjel Chávez Morejón Falk Harnisch ChemSusChem Mixtures of seven n‐ carboxylic acids ( n‐ CA), ranging from acetic acid to n‐ octanoic acid, that can be gained from the microbial conversion of waste biomass, were converted into liquid drop‐in fuel via Kolbe electrolysis. We demonstrate a strong, sigmoidal correlation between the total n ‐CA concentration and the Coulombic efficiency for fuel‐like liquid products (CE fuel ). Crucially, only above an apparent threshold concentration of 0.1 mol L −1 n‐ CA, Kolbe electrolysis takes place, whereas at lower concentrations the oxygen evolution reaction (OER) dominates. Optimal performance was achieved at the highest concentration tested, 1.5 mol L −1 , yielding a maximum CE fuel of 63.8 ± 1.4%, whereas for n‐ CA to 0.1 mol L −1 and 0.5 mol L −1 , the chain shortening reaction (CSR) strongly affects CE fuel . Furthermore, the study provides valuable insights into reaction selectivity, demonstrating that longer‐chain n ‐CA react preferentially compared to shorter‐chain n ‐CA, a phenomenon that is attributed to their higher hydrophobicity and hence accumulation in the hydrophobic layer formed on the electrode. Using a one‐chamber cell system at optimized concentration significantly lowered energy demand to 2.92 ± 0.04 kWhL −1 of fuel produced, representing a 40% reduction compared to similar two‐chamber setups. 10.1002/cssc.70753 http://creativecommons.org/licenses/by/4.0/ |
| title | The Concentration Determines Reaction Efficiency of Hetero‐Coupling of Bio‐Based Medium Chain Carboxylic Acids by Kolbe Electrolysis |
| topic | ChemSusChem |
| url | https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cssc.70753 |