Changing the action of iron from stoichiometric to electrocatalytic in the hydrogenation of ketones in aqueous acidic media

Marina Gottardo, Max E Easton, Viktoria Fabos, SiXuan Guo, Jie Zhang, Alvise Perosa, Maurizio Selva, Alan Maxwell Bond, Anthony Frederick Masters, Thomas Maschmeyer

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Cyclohexanone, a model compound chosen to conveniently represent small oxygenates present in the aqueous phase of biomass hydrothermal upgrading streams, was hydrogenated in the presence of electrodeposited iron(0) using aqueous formic or sulfuric acid as a hydrogen donor. Under these conditions, zero-valent iron is consumed stoichiometrically and serves as both a formic acid decomposition site and a hydrogen transfer agent. However, the resulting iron(II) can be used to continuously regenerate iron(0) when a potential is applied to the glassy carbon working electrode. Controlled potential electrolysis experiments show a 17 % conversion of cyclohexanone (over 1000 seconds) to cyclohexanol with >80 % efficiency of iron deposition from an iron(II) sulfate solution containing formic or sulfuric acid. In the absence of electrodeposited iron, formation of cyclohexanol could not be detected. Reduce, reuse, recycle: Cyclohexanone, a model compound for oxygenates present in biomass hydrothermal upgrading streams, is hydrogenated in the presence of electrodeposited iron using formic or sulfuric acid as the hydrogen donor. Zero-valent iron operates as an effective electrocatalyst (17 % conversion, 1000 s, >80 % efficiency) that can be continuously regenerated.
Original languageEnglish
Pages (from-to)3712-3717
Number of pages6
JournalChemSusChem
Volume8
Issue number21
DOIs
Publication statusPublished - 2015

Keywords

  • electrocatalysis
  • hydrothermal upgrading
  • iron
  • ketones
  • renewable

Cite this

Gottardo, Marina ; Easton, Max E ; Fabos, Viktoria ; Guo, SiXuan ; Zhang, Jie ; Perosa, Alvise ; Selva, Maurizio ; Bond, Alan Maxwell ; Masters, Anthony Frederick ; Maschmeyer, Thomas. / Changing the action of iron from stoichiometric to electrocatalytic in the hydrogenation of ketones in aqueous acidic media. In: ChemSusChem. 2015 ; Vol. 8, No. 21. pp. 3712-3717.
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abstract = "Cyclohexanone, a model compound chosen to conveniently represent small oxygenates present in the aqueous phase of biomass hydrothermal upgrading streams, was hydrogenated in the presence of electrodeposited iron(0) using aqueous formic or sulfuric acid as a hydrogen donor. Under these conditions, zero-valent iron is consumed stoichiometrically and serves as both a formic acid decomposition site and a hydrogen transfer agent. However, the resulting iron(II) can be used to continuously regenerate iron(0) when a potential is applied to the glassy carbon working electrode. Controlled potential electrolysis experiments show a 17 {\%} conversion of cyclohexanone (over 1000 seconds) to cyclohexanol with >80 {\%} efficiency of iron deposition from an iron(II) sulfate solution containing formic or sulfuric acid. In the absence of electrodeposited iron, formation of cyclohexanol could not be detected. Reduce, reuse, recycle: Cyclohexanone, a model compound for oxygenates present in biomass hydrothermal upgrading streams, is hydrogenated in the presence of electrodeposited iron using formic or sulfuric acid as the hydrogen donor. Zero-valent iron operates as an effective electrocatalyst (17 {\%} conversion, 1000 s, >80 {\%} efficiency) that can be continuously regenerated.",
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author = "Marina Gottardo and Easton, {Max E} and Viktoria Fabos and SiXuan Guo and Jie Zhang and Alvise Perosa and Maurizio Selva and Bond, {Alan Maxwell} and Masters, {Anthony Frederick} and Thomas Maschmeyer",
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Changing the action of iron from stoichiometric to electrocatalytic in the hydrogenation of ketones in aqueous acidic media. / Gottardo, Marina; Easton, Max E; Fabos, Viktoria; Guo, SiXuan; Zhang, Jie; Perosa, Alvise; Selva, Maurizio; Bond, Alan Maxwell; Masters, Anthony Frederick; Maschmeyer, Thomas.

In: ChemSusChem, Vol. 8, No. 21, 2015, p. 3712-3717.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Changing the action of iron from stoichiometric to electrocatalytic in the hydrogenation of ketones in aqueous acidic media

AU - Gottardo, Marina

AU - Easton, Max E

AU - Fabos, Viktoria

AU - Guo, SiXuan

AU - Zhang, Jie

AU - Perosa, Alvise

AU - Selva, Maurizio

AU - Bond, Alan Maxwell

AU - Masters, Anthony Frederick

AU - Maschmeyer, Thomas

PY - 2015

Y1 - 2015

N2 - Cyclohexanone, a model compound chosen to conveniently represent small oxygenates present in the aqueous phase of biomass hydrothermal upgrading streams, was hydrogenated in the presence of electrodeposited iron(0) using aqueous formic or sulfuric acid as a hydrogen donor. Under these conditions, zero-valent iron is consumed stoichiometrically and serves as both a formic acid decomposition site and a hydrogen transfer agent. However, the resulting iron(II) can be used to continuously regenerate iron(0) when a potential is applied to the glassy carbon working electrode. Controlled potential electrolysis experiments show a 17 % conversion of cyclohexanone (over 1000 seconds) to cyclohexanol with >80 % efficiency of iron deposition from an iron(II) sulfate solution containing formic or sulfuric acid. In the absence of electrodeposited iron, formation of cyclohexanol could not be detected. Reduce, reuse, recycle: Cyclohexanone, a model compound for oxygenates present in biomass hydrothermal upgrading streams, is hydrogenated in the presence of electrodeposited iron using formic or sulfuric acid as the hydrogen donor. Zero-valent iron operates as an effective electrocatalyst (17 % conversion, 1000 s, >80 % efficiency) that can be continuously regenerated.

AB - Cyclohexanone, a model compound chosen to conveniently represent small oxygenates present in the aqueous phase of biomass hydrothermal upgrading streams, was hydrogenated in the presence of electrodeposited iron(0) using aqueous formic or sulfuric acid as a hydrogen donor. Under these conditions, zero-valent iron is consumed stoichiometrically and serves as both a formic acid decomposition site and a hydrogen transfer agent. However, the resulting iron(II) can be used to continuously regenerate iron(0) when a potential is applied to the glassy carbon working electrode. Controlled potential electrolysis experiments show a 17 % conversion of cyclohexanone (over 1000 seconds) to cyclohexanol with >80 % efficiency of iron deposition from an iron(II) sulfate solution containing formic or sulfuric acid. In the absence of electrodeposited iron, formation of cyclohexanol could not be detected. Reduce, reuse, recycle: Cyclohexanone, a model compound for oxygenates present in biomass hydrothermal upgrading streams, is hydrogenated in the presence of electrodeposited iron using formic or sulfuric acid as the hydrogen donor. Zero-valent iron operates as an effective electrocatalyst (17 % conversion, 1000 s, >80 % efficiency) that can be continuously regenerated.

KW - electrocatalysis

KW - hydrothermal upgrading

KW - iron

KW - ketones

KW - renewable

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