Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts

Enman, Lisa J.; Stevens, Michaela Burke; Dahan, Meir Haim; Nellist, Michael R.; Toroker, Maytal Caspary; Boettcher, Shannon W.

doi:10.1002/ange.201808818

Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts

Journal Article · Tue Sep 04 00:00:00 EDT 2018 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201808818· OSTI ID:1468491

Enman, Lisa J. ^[1]; Stevens, Michaela Burke ^[1]; Dahan, Meir Haim ^[2]; Nellist, Michael R. ^[1]; ^[2]; ^[1]

Department of Chemistry &, Biochemistry and the Materials Science Institute University of Oregon Eugene OR 97403 USA
Department of Materials Science &, Engineering and The Nancy &, Stephen Grand Technion Energy Program Technion—Israel Institute of Technology Haifa 3200003 Israel

Abstract

Iron cations are essential for the high activity of nickel and cobalt‐based (oxy)hydroxides for the oxygen evolution reaction, but the role of iron in the catalytic mechanism remains under active investigation. Operando X‐ray absorption spectroscopy and density functional theory calculations are used to demonstrate partial Fe oxidation and a shortening of the Fe−O bond length during oxygen evolution on Co(Fe)O _x H _y . Cobalt oxidation during oxygen evolution is only observed in the absence of iron. These results demonstrate a different mechanism for water oxidation in the presence and absence of iron and support the hypothesis that oxidized iron species are involved in water‐oxidation catalysis on Co(Fe)O _x H _y .

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1468491

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 39 Vol. 130; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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