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      Bifunctional CoNi/CoFe 2O 4 /Ni foam electrodes for efficient overall water splitting at a high current density

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          Abstract

          An electrocatalyst composed of CoNi(hydroxide) nanosheets and flower-like CoFe 2O 4 particles with multiple porous structure is successfully deposited on nickel foam and applied for overall water splitting.

          Abstract

          It is always a challenge to develop a kind of low-cost electrode with high activity and superior durability for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in the electrolysis of water at a high current density. In this study, a novel electrocatalyst composed of earth abundant metals of Ni, Fe, and Co with a three-dimensional (3D) nanostructure and high activity was successfully fabricated on a Ni foam (NF) substrate through a facile hydrothermal synthesis method followed by electrodeposition. The electrode had three levels of porous structures, including the bottom supermacroporous NF substrate, flower-like CoFe 2O 4 with a macroporous structure, and the topmost mesoporous nanosheets of CoNi(oxy)hydroxide. Since this hierarchical architecture of CoNi/CoFe 2O 4/NF was binder-free, more catalytic active sites could be exposed, leading to enhanced electron transport and providing open-channels for the effective release of gas. As a result, CoNi/CoFe 2O 4/NF showed highly efficient electrocatalytic activity toward OER with an overpotential of 360 (±5) mV to achieve a current density as high as 1000 mA cm −2 in an alkaline medium. Meanwhile, as a cathode catalyst, it also exhibited excellent performance toward HER with overpotentials as low as 82 (±3) and 189 (±3) mV to deliver current densities of 10 and 100 mA cm −2, respectively. Furthermore, when it was applied as a bifunctional catalyst for overall water splitting, current densities of 10 mA cm −2 and 100 mA cm −2 were obtained at applied potentials of 1.57 and 1.75 V, respectively, together with excellent durability.

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          Most cited references56

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          Noble metal-free hydrogen evolution catalysts for water splitting.

          Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.
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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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              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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                Author and article information

                Contributors
                Journal
                JMCAET
                Journal of Materials Chemistry A
                J. Mater. Chem. A
                Royal Society of Chemistry (RSC)
                2050-7488
                2050-7496
                October 9 2018
                2018
                : 6
                : 39
                : 19221-19230
                Affiliations
                [1 ]Department of Chemical Engineering
                [2 ]Taiyuan University of Technology
                [3 ]Taiyuan 030024
                [4 ]China
                [5 ]Energy Conversion Engineering Laboratory
                [6 ]Institute of Regional Innovation (IRI)
                [7 ]Hirosaki University
                [8 ]Aomori 030-0813
                [9 ]Japan
                [10 ]Graduate School of Science and Technology
                [11 ]Hirosaki 036-8560
                Article
                10.1039/C8TA08223E
                7b59c7d7-3e0d-4a33-85b6-20dab3e51ec1
                © 2018

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

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