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      X20CoCrWMo10-9//Co3O4: a metal–ceramic composite with unique efficiency values for water-splitting in the neutral regime

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          Abstract

          The intrinsic, “from within itself” formation of Co 3O 4 on a hot work tool steel resulted in an outstanding electrocatalyst.

          Abstract

          Water splitting allows the storage of solar energy into chemical bonds (H 2 + O 2) and will help to implement the urgently needed replacement of limited available fossil fuels. In particular, in a neutral environment electrochemically initiated water splitting suffers from low efficiency due to high overpotentials ( η) caused by the anode. Electro-activation of X20CoCrWMo10-9, a Co-based tool steel resulted in a new composite material (X20CoCrWMo10-9//Co 3O 4) that catalyzes the anode half-cell reaction of water electrolysis with a so far, unequalled effectiveness. The current density achieved with this new anode in pH 7 corrected 0.1 M phosphate buffer is over a wide range of η around 10 times higher compared to recently developed, up-to-date electrocatalysts and represents the benchmark performance which advanced catalysts show in regimes that support water splitting significantly better than pH 7 medium. X20CoCrWMo10-9//Co 3O 4 exhibited electrocatalytic properties not only at pH 7, but also at pH 13, which are much superior to the ones of IrO 2–RuO 2, single-phase Co 3O 4- or Fe/Ni-based catalysts. Both XPS and FT-IR experiments unmasked Co 3O 4 as the dominating compound on the surface of the X20CoCrWMo10-9//Co 3O 4 composite. By performing a comprehensive dual beam FIB-SEM (focused ion beam-scanning electron microscopy) study, we could show that the new composite does not exhibit a classical substrate-layer structure due to the intrinsic formation of the Co-enriched outer zone. This structural particularity is basically responsible for the outstanding electrocatalytic OER performance.

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          Most cited references55

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          A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles.

          The efficiency of many energy storage technologies, such as rechargeable metal-air batteries and hydrogen production from water splitting, is limited by the slow kinetics of the oxygen evolution reaction (OER). We found that Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than that of the state-of-the-art iridium oxide catalyst in alkaline media. The high activity of BSCF was predicted from a design principle established by systematic examination of more than 10 transition metal oxides, which showed that the intrinsic OER activity exhibits a volcano-shaped dependence on the occupancy of the 3d electron with an e(g) symmetry of surface transition metal cations in an oxide. The peak OER activity was predicted to be at an e(g) occupancy close to unity, with high covalency of transition metal-oxygen bonds.
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            Heterogeneous photocatalyst materials for water splitting.

            This critical review shows the basis of photocatalytic water splitting and experimental points, and surveys heterogeneous photocatalyst materials for water splitting into H2 and O2, and H2 or O2 evolution from an aqueous solution containing a sacrificial reagent. Many oxides consisting of metal cations with d0 and d10 configurations, metal (oxy)sulfide and metal (oxy)nitride photocatalysts have been reported, especially during the latest decade. The fruitful photocatalyst library gives important information on factors affecting photocatalytic performances and design of new materials. Photocatalytic water splitting and H2 evolution using abundant compounds as electron donors are expected to contribute to construction of a clean and simple system for solar hydrogen production, and a solution of global energy and environmental issues in the future (361 references).
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              Solar water splitting cells.

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                Author and article information

                Journal
                EESNBY
                Energy & Environmental Science
                Energy Environ. Sci.
                Royal Society of Chemistry (RSC)
                1754-5692
                1754-5706
                2016
                2016
                : 9
                : 8
                : 2609-2622
                Affiliations
                [1 ]Institute of Chemistry of New Materials and Center of Physics and Chemistry of New Materials
                [2 ]Universität Osnabrück
                [3 ]49076 Osnabrück
                [4 ]Germany
                [5 ]Department of Chemistry
                [6 ]Dalhousie University
                [7 ]Halifax
                [8 ]Canada B3H 4J3
                [9 ]Department of Physics
                [10 ]49069 Osnabrück
                [11 ]Faculty of Agricultural Science and Landscape Architecture
                [12 ]Laboratory of Plant Nutrition and Chemistry
                [13 ]Osnabrück University of Applied Sciences
                [14 ]49090 Osnabrück
                [15 ]Institute of Materials Design and Structural Integrity University of Applied Sciences Osnabrück
                [16 ]University of Würzburg
                [17 ]Institute of Inorganic Chemistry Julius-Maximilians-Universität Würzburg
                [18 ]97074 Würzburg
                Article
                10.1039/C6EE01304J
                56b3cb47-250f-4e4f-9d49-cf74914b200f
                © 2016
                History

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