An Investigation of Thin-Film Ni–Fe Oxide Catalysts for the Electrochemical Evolution of Oxygen

Louie, Mary W.; Bell, Alexis T.

doi:10.1021/ja405351s

Title: An Investigation of Thin-Film Ni–Fe Oxide Catalysts for the Electrochemical Evolution of Oxygen

Journal Article · Tue Jul 16 00:00:00 EDT 2013 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja405351s· OSTI ID:1511368

Louie, Mary W. ^[1]; Bell, Alexis T. ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

A detailed investigation has been carried out of the structure and electrochemical activity of electrodeposited Ni-Fe films for the oxygen evolution reaction (OER) in alkaline electrolytes. Ni-Fe films with a bulk and surface composition of 40% Fe exhibit OER activities that are roughly 2 orders of magnitude higher than that of a freshly deposited Ni film and about 3 orders of magnitude higher than that of an Fe film. The freshly deposited Ni film increases in activity by as much as 20-fold during exposure to the electrolyte (KOH); however, all films containing Fe are stable as deposited. The oxidation of Ni(OH)₂ to NiOOH in Ni films occurs at potentials below the onset of the OER. Incorporation of Fe into the film increases the potential at which Ni(OH)₂/NiOOH redox occurs and decreases the average oxidation state of Ni in NiOOH. The Tafel slope (40 mV dec-1) and reaction order in OH-(1) for the mixed Ni-Fe films (containing up to 95% Fe) are the same as those for aged Ni films. In situ Raman spectra acquired in 0.1 M KOH at OER potentials show two bands characteristic of NiOOH. The relative intensities of these bands vary with Fe content, indicating a change in the local environment of Ni-O. Similar changes in the relative intensities of the bands and an increase in OER activity are observed when pure Ni films are aged. These observations suggest that the OER is catalyzed by Ni in Ni-Fe films and that the presence of Fe alters the redox properties of Ni, causing a positive shift in the potential at which Ni(OH)₂/NiOOH redox occurs, a decrease in the average oxidation state of the Ni sites, and a concurrent increase in the activity of Ni cations for the OER.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1511368

Journal Information:: Journal of the American Chemical Society, Vol. 135, Issue 33; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 1822 works

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