title: Changing the Action of Iron from Stoichiometric to Electrocatalytic in the Hydrogenation of Ketones in Aqueous Acidic Media.
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.
authors.affiliation: School of Chemistry - F11, The University of Sydney, NSW, 2006, Australia.|Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, Via Torino 155, 30172, Venezia Mestre, Italy.
authors.forename: Marina
authors.initials: M
authors.lastname: Gottardo
authors.affiliation: School of Chemistry - F11, The University of Sydney, NSW, 2006, Australia.
authors.forename: Max
authors.initials: M
authors.lastname: Easton
authors.affiliation: School of Chemistry - F11, The University of Sydney, NSW, 2006, Australia.
authors.forename: Viktoria
authors.initials: V
authors.lastname: Fabos
authors.affiliation: School of Chemistry, Monash University, Building 23, Clayton Campus, Wellington Road, Clayton, VIC, 3800, Australia.
authors.forename: Si-Xuan
authors.initials: SX
authors.lastname: Guo
authors.affiliation: School of Chemistry, Monash University, Building 23, Clayton Campus, Wellington Road, Clayton, VIC, 3800, Australia.
authors.forename: Jie
authors.initials: J
authors.lastname: Zhang
authors.affiliation: Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, Via Torino 155, 30172, Venezia Mestre, Italy.
authors.forename: Alvise
authors.identifier: http://orcid.org/0000-0003-4544-8709
authors.initials: A
authors.lastname: Perosa
authors.affiliation: Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, Via Torino 155, 30172, Venezia Mestre, Italy.
authors.forename: Maurizio
authors.initials: M
authors.lastname: Selva
authors.affiliation: School of Chemistry, Monash University, Building 23, Clayton Campus, Wellington Road, Clayton, VIC, 3800, Australia.
authors.forename: Alan M
authors.initials: AM
authors.lastname: Bond
authors.affiliation: School of Chemistry - F11, The University of Sydney, NSW, 2006, Australia.
authors.forename: Anthony F
authors.initials: AF
authors.lastname: Masters
authors.affiliation: School of Chemistry - F11, The University of Sydney, NSW, 2006, Australia. th.maschmeyer@chem.usyd.edu.au.
authors.forename: Thomas
authors.initials: T
authors.lastname: Maschmeyer
mesh_terms: D002384:Catalysis; D003511:Cyclohexanols / Q000737:chemistry*; D003512:Cyclohexanones / Q000737:chemistry*; D004563:Electrochemistry; D004566:Electrodes; D004572:Electrolysis; D005561:Formates / Q000737:chemistry*; D006865:Hydrogenation; D007501:Iron / Q000737:chemistry*; D008855:Microscopy, Electron, Scanning; D013464:Sulfuric Acids / Q000737:chemistry*; D013499:Surface Properties; D014867:Water / Q000737:chemistry*
chemical_list: D003511:Cyclohexanols; D003512:Cyclohexanones; D005561:Formates; D013464:Sulfuric Acids; D014867:Water; C030544:formic acid; C036468:cyclohexanone; D007501:Iron; C033158:sulfuric acid
keywords: electrocatalysis; hydrothermal upgrading; iron; ketones; renewable