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      Highly active Ni–Fe double hydroxides as anode catalysts for electrooxidation of urea

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          Abstract

          Ni–Fe double hydroxide catalysts show the highest catalytic activity and excellent stability toward the electrooxidation of urea.

          Abstract

          Urea is a safe and sustainable chemical for electrochemical energy conversion and storage. However, the sluggish kinetic rates of the electrooxidation reaction of urea as well as catalyst stability still remain to be challenges. In this work, we investigated several catalysts for the electro-oxidation of urea by directly growing NiM double hydroxides (M = Cr, Mn, Fe, Co, Cu, Zn) on carbon fibre cloth and nickel foam electrodes through a facile one-step hydrothermal synthesis method. The results indicated that the activity was significantly related to the elemental composition. Among the investigated double hydroxides, the NiFe double hydroxide (DH) catalyst showed the highest activity, which achieved a specific current density of ∼95 mA cm −2 mg −1 at 0.5 V vs. Ag/AgCl, about 10 times larger than that of Ni(OH) 2. In addition, the NiFe DH also had a high activity when grown on a Ni foam substrate. This NiFe DH performs well in the aspect of urea oxidation stability, demonstrating it to be a promising low-cost and stable catalyst for the efficient electrooxidation of urea under alkaline conditions.

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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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            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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              Effects of Fe Electrolyte Impurities on Ni(OH)2/NiOOH Structure and Oxygen Evolution Activity

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                Author and article information

                Contributors
                Journal
                NJCHE5
                New Journal of Chemistry
                New J. Chem.
                Royal Society of Chemistry (RSC)
                1144-0546
                1369-9261
                2017
                2017
                : 41
                : 10
                : 4190-4196
                Affiliations
                [1 ]School of Engineering
                [2 ]University of Warwick
                [3 ]Coventry CV4 7AL
                [4 ]UK
                [5 ]Department of Environmental Engineering
                [6 ]State Key Laboratory of Clean Energy Utilization
                [7 ]Zhejiang University
                [8 ]Hangzhou 100044
                [9 ]China
                [10 ]Department of Chemical Engineering
                Article
                10.1039/C6NJ04060H
                1f2165a3-4ff3-460d-b0bf-8698265adb7e
                © 2017
                History

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