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      An in situ anion exchange induced high-performance oxygen evolution reaction catalyst for the pH-near-neutral potassium borate electrolyte

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          Abstract

          A high-performance NiFe LDH oxygen evolution reaction catalyst for the pH-near-neutral potassium borate electrolyte obtained by an in situ anion exchange process.

          Abstract

          Research and development of highly efficient electrocatalysts for the kinetically sluggish oxygen evolution reaction (OER) under neutral or near-neutral pH conditions is urgent and challenging. Herein, for the first time we show that the anion exchange properties of sebacate anion intercalated NiFe layered double hydroxide (NiFe LDH Seb) can be taken advantage of to make NiFe LDHs a highly efficient OER catalyst for the pH-near-neutral potassium borate electrolyte (K-B i, pH = 9.2). The NiFe LDH Seb nanosphere delivered a 1 mA cm −2 current density with an overpotential of 376 mV on a fluorine doped tin oxide (FTO) electrode in 0.1 M K-B i (pH = 9.2) which is lower than that of RuO 2 (393 mV) and all other reported earth-abundant OER catalysts on FTO electrodes. More importantly, a chronoamperometry test showed that for 24 hours, NiFe LDH Seb did not show any decay in its performance as an OER catalyst and always outperformed RuO 2. To the best of our knowledge, this is the first time that anyone has reported a better performance of an earth-abundant OER catalyst than that of precious RuO 2 in K-B i (pH = 9.2). Besides, it also showed good OER performance under alkaline conditions. The excellent OER performance of NiFe LDH Seb was attributed to its large electrochemically active surface area and the in situ anion exchange induced large-scale exposure of Ni in the interior layers to the borate anions, which facilitates the activation of more Ni sites in the LDH. This work opens up a new path to develop LDH type OER catalysts for pH-neutral or pH-near-neutral electrolytes.

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          Most cited references47

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          Solar water splitting cells.

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            Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction.

            Objective evaluation of the activity of electrocatalysts for water oxidation is of fundamental importance for the development of promising energy conversion technologies including integrated solar water-splitting devices, water electrolyzers, and Li-air batteries. However, current methods employed to evaluate oxygen-evolving catalysts are not standardized, making it difficult to compare the activity and stability of these materials. We report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts. In particular, we focus on methods for determining electrochemically active surface area and measuring electrocatalytic activity and stability under conditions relevant to an integrated solar water-splitting device. Our primary figure of merit is the overpotential required to achieve a current density of 10 mA cm(-2) per geometric area, approximately the current density expected for a 10% efficient solar-to-fuels conversion device. Utilizing the aforementioned surface area measurements, one can determine electrocatalyst turnover frequencies. The reported protocol was used to examine the oxygen-evolution activity of the following systems in acidic and alkaline solutions: CoO(x), CoPi, CoFeO(x), NiO(x), NiCeO(x), NiCoO(x), NiCuO(x), NiFeO(x), and NiLaO(x). The oxygen-evolving activity of an electrodeposited IrO(x) catalyst was also investigated for comparison. Two general observations are made from comparing the catalytic performance of the OER catalysts investigated: (1) in alkaline solution, every non-noble metal system achieved 10 mA cm(-2) current densities at similar operating overpotentials between 0.35 and 0.43 V, and (2) every system but IrO(x) was unstable under oxidative conditions in acidic solutions.
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              An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.

              Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.
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                Author and article information

                Contributors
                (View ORCID Profile)
                (View ORCID Profile)
                Journal
                JMCAET
                Journal of Materials Chemistry A
                J. Mater. Chem. A
                Royal Society of Chemistry (RSC)
                2050-7488
                2050-7496
                March 19 2019
                2019
                : 7
                : 12
                : 6995-7005
                Affiliations
                [1 ]Department of Materials Science and Engineering
                [2 ]The Pennsylvania State University
                [3 ]University Park
                [4 ]USA
                [5 ]Department of Ecosystem Science and Management
                [6 ]Materials Research Institute
                [7 ]204 Energy and the Environment Laboratory
                [8 ]Center for Applied Chemistry
                [9 ]University of Electronic Science and Technology of China
                [10 ]Chengdu 610054
                [11 ]China
                Article
                10.1039/C8TA11734A
                806882ce-1ace-42ed-9262-5818866c129a
                © 2019

                http://rsc.li/journals-terms-of-use

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