Liquid-liquid electro-organo-synthetic processes in a carbon nanofibre membrane microreactor: Triple phase boundary effects in the absence of intentionally added electrolyte

John D Watkins, Sunyhik D Ahn, James E Taylor, Steven D Bull, Philip C Bulman-Page, Frank Marken

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Abstract

An amphiphilic carbon nanofibre membrane electrode (ca. 50 nm fibre diameter, 50-100 m membrane thickness) is employed as an active working electrode and separator between an aqueous electrolyte phase (with reference and counter electrode) and an immiscible organic acetonitrile phase (containing only the redox active material). Potential control is achieved with a reference and counter electrode located in the aqueous electrolyte phase, but the electrolysis is conducted in the organic acetonitrile phase in the absence of intentionally added supporting electrolyte. For the one-electron oxidation of n-butylferrocene coupled to perchlorate anion transfer from aqueous to organic phase effective electrolysis is demonstrated with an apparent mass transfer coefficient of m = 4 10-5 m s-1 and electrolysis of typically 1 mg n-butylferrocene in a 100 L volume. For the two-electron reduction of tetraethyl-ethylenetetracarboxylate the apparent mass transfer coefficient m = 4 10-6 m s-1 is lower due to a less extended triple phase boundary reaction zone in the carbon nanofibre membrane. Nevertheless, effective electrolysis of up to 6 mg tetraethyl-ethylenetetracarboxylate in a 100 L volume is demonstrated. Deuterated products are formed in the presence of D2O electrolyte media. The triple phase boundary dominated mechanism and future microreactor design improvements are discussed.
Original languageEnglish
Pages (from-to)6764-6770
Number of pages7
JournalElectrochimica Acta
Volume56
Issue number19
DOIs
Publication statusPublished - 30 Jul 2011

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Carbon nanofibers
Phase boundaries
Electrolysis
Electrolytes
Membranes
Electrodes
Liquids
Acetonitrile
Mass transfer
Electrons
Separators
Anions
Negative ions
Oxidation
Fibers
acetonitrile

Cite this

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title = "Liquid-liquid electro-organo-synthetic processes in a carbon nanofibre membrane microreactor: Triple phase boundary effects in the absence of intentionally added electrolyte",
abstract = "An amphiphilic carbon nanofibre membrane electrode (ca. 50 nm fibre diameter, 50-100 m membrane thickness) is employed as an active working electrode and separator between an aqueous electrolyte phase (with reference and counter electrode) and an immiscible organic acetonitrile phase (containing only the redox active material). Potential control is achieved with a reference and counter electrode located in the aqueous electrolyte phase, but the electrolysis is conducted in the organic acetonitrile phase in the absence of intentionally added supporting electrolyte. For the one-electron oxidation of n-butylferrocene coupled to perchlorate anion transfer from aqueous to organic phase effective electrolysis is demonstrated with an apparent mass transfer coefficient of m = 4 10-5 m s-1 and electrolysis of typically 1 mg n-butylferrocene in a 100 L volume. For the two-electron reduction of tetraethyl-ethylenetetracarboxylate the apparent mass transfer coefficient m = 4 10-6 m s-1 is lower due to a less extended triple phase boundary reaction zone in the carbon nanofibre membrane. Nevertheless, effective electrolysis of up to 6 mg tetraethyl-ethylenetetracarboxylate in a 100 L volume is demonstrated. Deuterated products are formed in the presence of D2O electrolyte media. The triple phase boundary dominated mechanism and future microreactor design improvements are discussed.",
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AU - Ahn, Sunyhik D

AU - Taylor, James E

AU - Bull, Steven D

AU - Bulman-Page, Philip C

AU - Marken, Frank

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N2 - An amphiphilic carbon nanofibre membrane electrode (ca. 50 nm fibre diameter, 50-100 m membrane thickness) is employed as an active working electrode and separator between an aqueous electrolyte phase (with reference and counter electrode) and an immiscible organic acetonitrile phase (containing only the redox active material). Potential control is achieved with a reference and counter electrode located in the aqueous electrolyte phase, but the electrolysis is conducted in the organic acetonitrile phase in the absence of intentionally added supporting electrolyte. For the one-electron oxidation of n-butylferrocene coupled to perchlorate anion transfer from aqueous to organic phase effective electrolysis is demonstrated with an apparent mass transfer coefficient of m = 4 10-5 m s-1 and electrolysis of typically 1 mg n-butylferrocene in a 100 L volume. For the two-electron reduction of tetraethyl-ethylenetetracarboxylate the apparent mass transfer coefficient m = 4 10-6 m s-1 is lower due to a less extended triple phase boundary reaction zone in the carbon nanofibre membrane. Nevertheless, effective electrolysis of up to 6 mg tetraethyl-ethylenetetracarboxylate in a 100 L volume is demonstrated. Deuterated products are formed in the presence of D2O electrolyte media. The triple phase boundary dominated mechanism and future microreactor design improvements are discussed.

AB - An amphiphilic carbon nanofibre membrane electrode (ca. 50 nm fibre diameter, 50-100 m membrane thickness) is employed as an active working electrode and separator between an aqueous electrolyte phase (with reference and counter electrode) and an immiscible organic acetonitrile phase (containing only the redox active material). Potential control is achieved with a reference and counter electrode located in the aqueous electrolyte phase, but the electrolysis is conducted in the organic acetonitrile phase in the absence of intentionally added supporting electrolyte. For the one-electron oxidation of n-butylferrocene coupled to perchlorate anion transfer from aqueous to organic phase effective electrolysis is demonstrated with an apparent mass transfer coefficient of m = 4 10-5 m s-1 and electrolysis of typically 1 mg n-butylferrocene in a 100 L volume. For the two-electron reduction of tetraethyl-ethylenetetracarboxylate the apparent mass transfer coefficient m = 4 10-6 m s-1 is lower due to a less extended triple phase boundary reaction zone in the carbon nanofibre membrane. Nevertheless, effective electrolysis of up to 6 mg tetraethyl-ethylenetetracarboxylate in a 100 L volume is demonstrated. Deuterated products are formed in the presence of D2O electrolyte media. The triple phase boundary dominated mechanism and future microreactor design improvements are discussed.

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