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Hydrogen evolution at mixed α- Fe1-xCrxOOH

Journal article
Authors Patrik Larses
Adriano Gomes
Elisabet Ahlberg
Michael Busch
Published in Journal of Electroanalytical Chemistry
Volume 819
Pages 114-122
ISSN 0022-0728
Publication year 2018
Published at Department of Chemistry and Molecular Biology
Pages 114-122
Language en
Keywords Hydrogen evolution reaction Iron oxides Chromium oxides Electrocatalysis Chlorate process
Subject categories Electrochemistry


The activity of mixed α-Fe1 − xCrxOOH oxides towards hydrogen evolution in alkaline solution is discussed based on Density Functional Theory (DFT) calculations, cyclic voltammetry and steady state measurements. Thermogravimetric and XRD measurements indicate an isomorphic substitution of Fe by Cr. Electrochemical characterization shows increasingly sluggish hydrogen evolution reaction (HER) kinetics with increased Cr loadings. This decrease in activity is accompanied by the inhibition of the reduction of iron in α-Fe1 − xCrxOOH. To investigate the origin of this decrease in activity, DFT calculations were performed for mixtures of Fe and Cr placed at Fe(OH)2. Based on phase diagrams, the most stable structures under HER conditions are identified and used to estimate the theoretical overpotential. In contrast to experiment, no decrease in HER activity is observed. Instead, mixed FeCr sites display an overpotential comparable to that of Pt. Taking into account the inhibition of the bulk reduction in the presence of Cr, the activity decreases in agreement with experiment. These results are very important in the search for cathodes in the chlorate process that are active also in the absence of chromate in solution and may offer a new route for Pt free HER catalysts in alkaline solution.

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