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      A Gibeon meteorite yields a high-performance water oxidation electrocatalyst

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          Abstract

          A natural material of extra-terrestrial origin yields a high-performance electrocatalyst for alkaline water oxidation.

          Abstract

          Examining the electrocatalytic performance of naturally-occurring metallic minerals is of interest for energy conversion applications given their unique atomic composition and formation history. Herein, we report the electrocatalytic function of an iron-based Gibeon meteorite for the oxygen evolution reaction (OER). After ageing under operational conditions in an alkaline electrolyte, an activity matching or possibly slightly superior to the best performing OER catalysts emerges, with stable overpotentials as low as 270 mV (for 10 mA cm −2) and Tafel slopes of 37 mV decade −1. The Faradaic efficiency for the OER was unity and no deterioration in performance was detected during 1000 hours of OER operation at 500 mA cm −2. Mechanistic studies suggest an operando surface modification involving the formation of a 3D oxy(hydroxide) layer with a metal atom composition of Co 0.11Fe 0.33Ni 0.55, as indicated by Raman and XPS studies and trace Ir as indicated via elemental analysis. The growth of the catalyst layer was self-limiting to <200 nm after ca. 300 hours of operation as indicated through XPS depth profiling and cyclic voltammetry. The unique composition and structure of the Gibeon meteorite suggest that further investigation of Ir–Co–Ni–Fe systems or other alloys inspired by natural materials for water oxidation are of interest.

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          Most cited references42

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          Nickel-iron oxyhydroxide oxygen-evolution electrocatalysts: the role of intentional and incidental iron incorporation.

          Fe plays a critical, but not yet understood, role in enhancing the activity of the Ni-based oxygen evolution reaction (OER) electrocatalysts. We report electrochemical, in situ electrical, photoelectron spectroscopy, and X-ray diffraction measurements on Ni(1-x)Fe(x)(OH)2/Ni(1-x)Fe(x)OOH thin films to investigate the changes in electronic properties, OER activity, and structure as a result of Fe inclusion. We developed a simple method for purification of KOH electrolyte that uses precipitated bulk Ni(OH)2 to absorb Fe impurities. Cyclic voltammetry on rigorously Fe-free Ni(OH)2/NiOOH reveals new Ni redox features and no significant OER current until >400 mV overpotential, different from previous reports which were likely affected by Fe impurities. We show through controlled crystallization that β-NiOOH is less active for OER than the disordered γ-NiOOH starting material and that previous reports of increased activity for β-NiOOH are due to incorporation of Fe-impurities during the crystallization process. Through-film in situ conductivity measurements show a >30-fold increase in film conductivity with Fe addition, but this change in conductivity is not sufficient to explain the observed changes in activity. Measurements of activity as a function of film thickness on Au and glassy carbon substrates are consistent with the hypothesis that Fe exerts a partial-charge-transfer activation effect on Ni, similar to that observed for noble-metal electrode surfaces. These results have significant implications for the design and study of Ni(1-x)Fe(x)OOH OER electrocatalysts, which are the fastest measured OER catalysts under basic conditions.
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            Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis.

            Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of a-Fe(100-y-z)Co(y)Ni(z)O(x) are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers.
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              A mini review of NiFe-based materials as highly active oxygen evolution reaction electrocatalysts

                Author and article information

                Journal
                EESNBY
                Energy & Environmental Science
                Energy Environ. Sci.
                Royal Society of Chemistry (RSC)
                1754-5692
                1754-5706
                2016
                2016
                : 9
                : 11
                : 3448-3455
                Affiliations
                [1 ]Institute of Chemical Sciences and Engineering (ISIC)
                [2 ]Ecole Polytechnique Fédérale de Lausanne (EPFL)
                [3 ]1015-Lausanne
                [4 ]Switzerland
                [5 ]Institute of Physics (IPHYS)
                Article
                10.1039/C6EE02375D
                fde617b3-8455-4bf6-a98b-04667bab4bd4
                © 2016
                History

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