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      Utilizing ion leaching effects for achieving high oxygen-evolving performance on hybrid nanocomposite with self-optimized behaviors

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          Abstract

          Ion leaching from pure-phase oxygen-evolving electrocatalysts generally exists, leading to the collapse and loss of catalyst crystalline matrix. Here, different from previous design methodologies of pure-phase perovskites, we introduce soluble BaCl 2 and SrCl 2 into perovskites through a self-assembly process aimed at simultaneously tuning dual cation/anion leaching effects and optimizing ion match in perovskites to protect the crystalline matrix. As a proof-of-concept, self-assembled hybrid Ba 0.35Sr 0.65Co 0.8Fe 0.2O 3- δ (BSCF) nanocomposite (with BaCl 2 and SrCl 2) exhibits the low overpotential of 260 mV at 10 mA cm -2 in 0.1 M KOH. Multiple operando spectroscopic techniques reveal that the pre-leaching of soluble compounds lowers the difference of interfacial ion concentrations and thus endows the host phase in hybrid BSCF with abundant time and space to form stable edge/face-sharing surface structures. These self-optimized crystalline structures show stable lattice oxygen active sites and short reaction pathways between Co–Co/Fe metal active sites to trigger favorable adsorption of OH species.

          Abstract

          Water oxidation catalysis may provide the electrons needed for sustainable fuel production, but catalysts often degrade under working conditions. Here, authors introduce soluble species into perovskites to exert positive ion leaching effects for enhancing perovskite stability and activity.

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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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            Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution

            Understanding how oxygen-evolution reaction (OER) catalysts work is important for the development of efficient energy storage technologies. It has now been shown that lattice oxygen participates in O2 generation during the OER on some highly active metal oxides and that this behaviour becomes more prevalent with greater metal–oxygen covalency.
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              Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution.

              The electronic structure of transition metal oxides governs the catalysis of many central reactions for energy storage applications such as oxygen electrocatalysis. Here we exploit the versatility of the perovskite structure to search for oxide catalysts that are both active and stable. We report double perovskites (Ln₀.₅Ba₀.₅)CoO(₃-δ) (Ln=Pr, Sm, Gd and Ho) as a family of highly active catalysts for the oxygen evolution reaction upon water oxidation in alkaline solution. These double perovskites are stable unlike pseudocubic perovskites with comparable activities such as Ba₀.₅Sr₀.₅Co₀.₈Fe₀.₂O(₃-δ) which readily amorphize during the oxygen evolution reaction. The high activity and stability of these double perovskites can be explained by having the O p-band centre neither too close nor too far from the Fermi level, which is computed from ab initio studies.
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                Author and article information

                Contributors
                zhouwei1982@njtech.edu.cn
                shaozp@njtech.edu.cn
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                6 July 2020
                6 July 2020
                2020
                : 11
                : 3376
                Affiliations
                [1 ]ISNI 0000 0000 9389 5210, GRID grid.412022.7, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, , Nanjing Tech University, ; Nanjing, 211800 China
                [2 ]ISNI 0000 0004 0491 351X, GRID grid.419507.e, Max-Planck-Institute for Chemical Physics of Solids, ; Nöthnitzer Str. 40, Dresden, 01187 Germany
                [3 ]ISNI 0000000119573309, GRID grid.9227.e, Shanghai Institute of Applied Physics, , Chinese Academy of Sciences, ; Shanghai, 201204 China
                [4 ]ISNI 0000 0004 1937 1055, GRID grid.264580.d, Department of Physics, , Tamkang University, ; 151 Yingzhuan Rd., New Taipei City, 25137 Taiwan
                [5 ]ISNI 0000 0004 0375 4078, GRID grid.1032.0, WA School of Mines: Minerals, Energy and Chemical Engineering (WASM-MECE), , Curtin University, ; Perth, WA 6845 Australia
                [6 ]ISNI 0000 0001 0749 1496, GRID grid.410766.2, National Synchrotron Radiation Research Center, ; 101 Hsin-Ann Road, Hsinchu, 30076 Taiwan
                Author information
                http://orcid.org/0000-0001-5393-2301
                http://orcid.org/0000-0003-0324-2227
                http://orcid.org/0000-0003-0322-095X
                http://orcid.org/0000-0002-4538-4218
                Article
                17108
                10.1038/s41467-020-17108-5
                7338502
                32632311
                cb3c5736-1ef2-4dd4-822a-6862e390acfb
                © The Author(s) 2020

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 29 January 2020
                : 9 June 2020
                Funding
                Funded by: We thank the financial support from the National Nature Science Foundation of China (No. 21878158 and 21576135), the Jiangsu Natural Science Foundation for Distinguished Young Scholars (No. BK20170043), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), the Defense Industrial Technology Development Program (No. JCKY2018605B006), and the National Key R&D Program of China (No. 2018YFB0905400). We also acknowledge the support from the Max Planck-POSTECH-Hsinchu Center for Complex Phase Materials.
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                © The Author(s) 2020

                Uncategorized
                electrocatalysis,nanoparticles
                Uncategorized
                electrocatalysis, nanoparticles

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