How an Anode‐Sided Gap Influences the Electrooxidation of Phenols in Flow Reactors

Abstract Electroorganic synthesis offers a sustainable way to valorize chemical building blocks through renewable energy and environmentally friendly reagents. Substituted quinones, vital for manufacturing supplements, pharmaceuticals, and pesticides, are typically derived from phenols via thermoche...

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Main Authors: Jonas Wolf, Nijiati Yasheng, Dr. Julian Tobias Kleinhaus, Dr. Kevinjeorjios Pellumbi, Leon Wickert, Dr. Daniel Siegmund, Prof. Dr. Ulf‐Peter Apfel
Format: Article
Language:English
Published: Wiley-VCH 2025-05-01
Series:ChemElectroChem
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Online Access:https://doi.org/10.1002/celc.202400706
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author Jonas Wolf
Nijiati Yasheng
Dr. Julian Tobias Kleinhaus
Dr. Kevinjeorjios Pellumbi
Leon Wickert
Dr. Daniel Siegmund
Prof. Dr. Ulf‐Peter Apfel
author_facet Jonas Wolf
Nijiati Yasheng
Dr. Julian Tobias Kleinhaus
Dr. Kevinjeorjios Pellumbi
Leon Wickert
Dr. Daniel Siegmund
Prof. Dr. Ulf‐Peter Apfel
author_sort Jonas Wolf
collection DOAJ
description Abstract Electroorganic synthesis offers a sustainable way to valorize chemical building blocks through renewable energy and environmentally friendly reagents. Substituted quinones, vital for manufacturing supplements, pharmaceuticals, and pesticides, are typically derived from phenols via thermochemical oxidation with inorganic oxidizers and specialized catalysts. Electrochemistry's ability to omit such components highlights the appeal of electrifying this process. This study explores the electrochemical oxidation of 2,3,5‐trimethylphenol (TMP) into trimethyl‐1,4‐benzoquinone (TMQ) – a crucial intermediate for vitamin E production – using a zero‐gap electrolyzer. A TMQ yield of 18 % and selectivity of 22 % were achieved, improving to 35 % and 37 %, respectively, with an anode‐sided spacer. We sought to identify factors promoting TMQ formation in reactors with an anode‐sided gap, addressing limitations in zero‐gap configurations and investigating the dependency on half‐cell potential, local reactant concentrations, pH, and electrolyte convection. The results revealed that the local substrate concentration is interrelated with electrolyte convection and is the most critical factor responsible for the gap‐related effect. A TMQ yield and selectivity of 33 % and 32 % were achieved in continuous flow conditions in a zero‐gap electrolyzer at optimized conditions. These findings underscore the critical role of local reactant concentrations in scaling synthetic electrochemical reactions, providing a robust framework for tackling future challenges in the field.
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spelling doaj-art-68956fa2b17e4ec18ca6b11f0ac6ed642025-08-20T02:26:15ZengWiley-VCHChemElectroChem2196-02162025-05-011210n/an/a10.1002/celc.202400706How an Anode‐Sided Gap Influences the Electrooxidation of Phenols in Flow ReactorsJonas Wolf0Nijiati Yasheng1Dr. Julian Tobias Kleinhaus2Dr. Kevinjeorjios Pellumbi3Leon Wickert4Dr. Daniel Siegmund5Prof. Dr. Ulf‐Peter Apfel6Department of Electrosynthesis Fraunhofer Institute for Environmental, Safety and Energy Technology Osterfelder Straße 3 46047 OberhausenDepartment of Electrosynthesis Fraunhofer Institute for Environmental, Safety and Energy Technology Osterfelder Straße 3 46047 OberhausenActivation of Small Molecules / Technical Electrochemistry Faculty of Chemistry and Biochemistry Ruhr University Bochum Universitätsstraße 150 44801 BochumDepartment of Electrosynthesis Fraunhofer Institute for Environmental, Safety and Energy Technology Osterfelder Straße 3 46047 OberhausenActivation of Small Molecules / Technical Electrochemistry Faculty of Chemistry and Biochemistry Ruhr University Bochum Universitätsstraße 150 44801 BochumDepartment of Electrosynthesis Fraunhofer Institute for Environmental, Safety and Energy Technology Osterfelder Straße 3 46047 OberhausenDepartment of Electrosynthesis Fraunhofer Institute for Environmental, Safety and Energy Technology Osterfelder Straße 3 46047 OberhausenAbstract Electroorganic synthesis offers a sustainable way to valorize chemical building blocks through renewable energy and environmentally friendly reagents. Substituted quinones, vital for manufacturing supplements, pharmaceuticals, and pesticides, are typically derived from phenols via thermochemical oxidation with inorganic oxidizers and specialized catalysts. Electrochemistry's ability to omit such components highlights the appeal of electrifying this process. This study explores the electrochemical oxidation of 2,3,5‐trimethylphenol (TMP) into trimethyl‐1,4‐benzoquinone (TMQ) – a crucial intermediate for vitamin E production – using a zero‐gap electrolyzer. A TMQ yield of 18 % and selectivity of 22 % were achieved, improving to 35 % and 37 %, respectively, with an anode‐sided spacer. We sought to identify factors promoting TMQ formation in reactors with an anode‐sided gap, addressing limitations in zero‐gap configurations and investigating the dependency on half‐cell potential, local reactant concentrations, pH, and electrolyte convection. The results revealed that the local substrate concentration is interrelated with electrolyte convection and is the most critical factor responsible for the gap‐related effect. A TMQ yield and selectivity of 33 % and 32 % were achieved in continuous flow conditions in a zero‐gap electrolyzer at optimized conditions. These findings underscore the critical role of local reactant concentrations in scaling synthetic electrochemical reactions, providing a robust framework for tackling future challenges in the field.https://doi.org/10.1002/celc.202400706electrochemical oxidationelectrochemistryindustrial applicabilityoxidationreactor transferzero-gap electrolysis
spellingShingle Jonas Wolf
Nijiati Yasheng
Dr. Julian Tobias Kleinhaus
Dr. Kevinjeorjios Pellumbi
Leon Wickert
Dr. Daniel Siegmund
Prof. Dr. Ulf‐Peter Apfel
How an Anode‐Sided Gap Influences the Electrooxidation of Phenols in Flow Reactors
ChemElectroChem
electrochemical oxidation
electrochemistry
industrial applicability
oxidation
reactor transfer
zero-gap electrolysis
title How an Anode‐Sided Gap Influences the Electrooxidation of Phenols in Flow Reactors
title_full How an Anode‐Sided Gap Influences the Electrooxidation of Phenols in Flow Reactors
title_fullStr How an Anode‐Sided Gap Influences the Electrooxidation of Phenols in Flow Reactors
title_full_unstemmed How an Anode‐Sided Gap Influences the Electrooxidation of Phenols in Flow Reactors
title_short How an Anode‐Sided Gap Influences the Electrooxidation of Phenols in Flow Reactors
title_sort how an anode sided gap influences the electrooxidation of phenols in flow reactors
topic electrochemical oxidation
electrochemistry
industrial applicability
oxidation
reactor transfer
zero-gap electrolysis
url https://doi.org/10.1002/celc.202400706
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