Identification of Highly Active Fe Sites in (Ni,Fe)OOH for Electrocatalytic Water Splitting
Top Cited Papers
- 5 January 2015
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 137 (3), 1305-1313
- https://doi.org/10.1021/ja511559d
Abstract
Highly active catalysts for the oxygen evolution reaction (OER) are required for the development of photoelectrochemical devices that generate hydrogen efficiently from water using solar energy. Here, we identify the origin of a 500-fold OER activity enhancement that can be achieved with mixed (Ni,Fe)oxyhydroxides (Ni1–xFexOOH) over their pure Ni and Fe parent compounds, resulting in one of the most active currently known OER catalysts in alkaline electrolyte. Operando X-ray absorption spectroscopy (XAS) using high energy resolution fluorescence detection (HERFD) reveals that Fe3+ in Ni1–xFexOOH occupies octahedral sites with unusually short Fe–O bond distances, induced by edge-sharing with surrounding [NiO6] octahedra. Using computational methods, we establish that this structural motif results in near optimal adsorption energies of OER intermediates and low overpotentials at Fe sites. By contrast, Ni sites in Ni1–xFexOOH are not active sites for the oxidation of water.Funding Information
- University of California
- Office of Science
- Solvay S.A.
This publication has 72 references indexed in Scilit:
- Theoretical Investigation of the Activity of Cobalt Oxides for the Electrochemical Oxidation of WaterJournal of the American Chemical Society, 2013
- An Investigation of Thin-Film Ni–Fe Oxide Catalysts for the Electrochemical Evolution of OxygenJournal of the American Chemical Society, 2013
- X-ray absorption investigation of the valence state and electronic structure of La1−xCaxCoO3−δ in comparison with La1−xSrxCoO3−δ and La1−xSrxFeO3−δJournal of Solid State Chemistry, 2011
- Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysisJournal of Electroanalytical Chemistry, 2011
- Kβ-Detected XANES of Framework-Substituted FeZSM-5 ZeolitesThe Journal of Physical Chemistry B, 2004
- Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U studyPhysical Review B, 1998
- Electrochemical Behavior of Reactively Sputtered Iron‐Doped Nickel OxideJournal of the Electrochemical Society, 1997
- A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron ComplexesJournal of the American Chemical Society, 1997
- Electrocatalysis in the anodic evolution of oxygen and chlorineElectrochimica Acta, 1984
- Zur kenntnis der nickelhydroxidelektrode—IV. Kristallstrukturuntersuchung des hochoxidierten γ1-NickelhydroxidsElectrochimica Acta, 1971