4.6 Article

(Non-)Kolbe Chemistry Going with the Flow: The Continuous Electrolysis of Biogenic Acids

Journal

ACS SUSTAINABLE CHEMISTRY & ENGINEERING
Volume 9, Issue 3, Pages 1229-1234

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acssuschemeng.0c06982

Keywords

electrochemical synthesis; Kolbe electrolysis; biomass; electrocatalysis; flow electrochemistry; bioderived acids; 3D printing; biofuels

Funding

  1. Excellence Initiative by the German federal and state governments [EXC 236, EXC 2186, 390919832]
  2. Studienstiftung des deutschen Volkes e.V

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This article discusses the concept of transforming Kolbe chemistry into flow processes, achieving continuous production through recirculation and single-pass systems. Non-Kolbe electrolysis was found to be better suited for continuous production, and an example was presented using different flow cells to convert chemicals.
Aiming at a circular carbon economy, electrosynthesis is gaining in importance. The conversion of bioderived materials using green electrons from renewable energy sources tackles challenges like fluctuating energy production and the integration into the already existing supply networks. Herein, we discuss concepts for transforming 150-year old Kolbe chemistry into flow processes. In a recirculation setup, levulinic acid is converted to the Kolbe product 2,7-octanedione with up to 75% yield. Single-pass setups allow for continuous production, for which conversion scales linearly with contact time. It was found that non-Kolbe electrolysis is even better suited toward continuous production because of the possibility to use lower substrate concentrations. We present an example of an n-alkyl acid converted using different flow cells including a 3D printed vessel for a semibatch non-Kolbe reaction. The electrochemically more challenging beta-hydroxy-acid is selectively converted to a drop-in oxygenate fuel, increasing the hourly production compared to the batch process by five times.

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