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

Journal Article · · Angewandte Chemie
 [1];  [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry &, Biochemistry and the Materials Science Institute University of Oregon Eugene OR 97403 USA
  2. 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 .

Sponsoring Organization:
USDOE
OSTI ID:
1468491
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 130 Journal Issue: 39; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (40)

Operando Analysis of NiFe and Fe Oxyhydroxide Electrocatalysts for Water Oxidation: Detection of Fe 4+ by Mössbauer Spectroscopy journal November 2015
EPR Evidence for Co(IV) Species Produced During Water Oxidation at Neutral pH journal May 2010
On the chemical state of Co oxide electrocatalysts during alkaline water splitting journal January 2013
X-ray Spectroscopic Characterization of Co(IV) and Metal–Metal Interactions in Co 4 O 4 : Electronic Structure Contributions to the Formation of High-Valent States Relevant to the Oxygen Evolution Reaction journal August 2016
Revised Oxygen Evolution Reaction Activity Trends for First-Row Transition-Metal (Oxy)hydroxides in Alkaline Media journal August 2015
Self-healing catalysis in water journal September 2017
Spectroscopic identification of active sites for the oxygen evolution reaction on iron-cobalt oxides journal December 2017
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces journal March 2011
Tracking Catalyst Redox States and Reaction Dynamics in Ni–Fe Oxyhydroxide Oxygen Evolution Reaction Electrocatalysts: The Role of Catalyst Support and Electrolyte pH journal January 2017
Molybdenum x-ray absorption edge spectra. The chemical state of molybdenum in nitrogenase journal March 1976
Nickel-iron catalysts for electrochemical water oxidation – redox synergism investigated by in situ X-ray spectroscopy with millisecond time resolution journal January 2018
Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst journal February 2014
Mechanistic Studies of the Oxygen Evolution Reaction by a Cobalt-Phosphate Catalyst at Neutral pH journal November 2010
Enhanced Catalysis of the Electrochemical Oxygen Evolution Reaction by Iron(III) Ions Adsorbed on Amorphous Cobalt Oxide journal December 2017
Characterization of La 0.8 Sr 0.2 Fe O 3 δ and La 0.7 Sr 0.2 Fe O 3 δ as a function of temperature by x-ray absorption spectroscopy journal March 2006
Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis journal July 2014
Hydrogen Bonds of gamma-FeOOH. journal January 1978
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal January 1998
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data journal October 2011
Trapping an Iron(VI) Water-Splitting Intermediate in Nonaqueous Media journal April 2018
Oxygen Evolution Reaction Dynamics, Faradaic Charge Efficiency, and the Active Metal Redox States of Ni–Fe Oxide Water Splitting Electrocatalysts journal April 2016
Identification of Highly Active Fe Sites in (Ni,Fe)OOH for Electrocatalytic Water Splitting journal January 2015
Cobalt–Iron (Oxy)hydroxide Oxygen Evolution Electrocatalysts: The Role of Structure and Composition on Activity, Stability, and Mechanism journal March 2015
Reactive Fe-Sites in Ni/Fe (Oxy)hydroxide Are Responsible for Exceptional Oxygen Electrocatalysis Activity journal August 2017
Edge reactivity and water-assisted dissociation on cobalt oxide nanoislands journal January 2017
Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation journal April 2014
Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy journal June 2017
Ab initiomolecular dynamics for liquid metals journal January 1993
Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting journal July 2017
Charge-Transfer Effects in Ni–Fe and Ni–Fe–Co Mixed-Metal Oxides for the Alkaline Oxygen Evolution Reaction journal December 2015
Iron Is the Active Site in Nickel/Iron Water Oxidation Electrocatalysts journal April 2018
Lateral-Size-Mediated Efficient Oxygen Evolution Reaction: Insights into the Atomically Thin Quantum Dot Structure of NiFe 2 O 4 journal July 2017
Charge disproportionation in La 1 x Sr x Fe O 3 probed by diffraction and spectroscopic experiments journal February 2008
Insights into the durability of Co–Fe spinel oxygen evolution electrocatalysts via operando studies of the catalyst structure journal January 2018
Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry journal March 2017
Solution-Cast Metal Oxide Thin Film Electrocatalysts for Oxygen Evolution journal October 2012
X-ray Absorption Spectroscopy Studies of the Local Atomic and Electronic Structure of Iron Incorporated into Electrodeposited Hydrous Nickel Oxide Films journal May 2000
Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films journal January 2017
The secret behind the success of doping nickel oxyhydroxide with iron journal January 2017