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Changing the Action of Iron from Stoichiometric to Electrocatalytic in the Hydrogenation of Ketones in Aqueous Acidic Media
Author(s) -
Gottardo Marina,
Easton Max,
Fabos Viktoria,
Guo SiXuan,
Zhang Jie,
Perosa Alvise,
Selva Maurizio,
Bond Alan M.,
Masters Anthony. F.,
Maschmeyer Thomas
Publication year - 2015
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201500624
Subject(s) - aqueous solution , aqueous medium , chemistry , stoichiometry , action (physics) , inorganic chemistry , electrocatalyst , catalysis , ruthenium , electrochemistry , organic chemistry , electrode , physics , quantum mechanics
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.