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    Water Splitting: A Hierarchical MoP Nanoflake Array Supported on Ni Foam: A Bifunctional Electrocatalyst for Overall Water Splitting (Small Methods 5/2018)
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    Abstract:
    In article number 1700369, Yizhong Lu, Zexiang Shen, and co-workers report a novel MoP nanoflake array grown on nickel foam, which can act as high-performance bifunctional electrocatalyst for water splitting. The bifunctional electrocatalyst behaves like two hands, one for the hydrogen evolution reaction (HER) and another for the oxygen evolution reaction (OER), respectively. With the two hands, the whole water splitting can be fulfilled efficiently.
    Keywords:
    Oxygen evolution
    The development of green energy conversion technologies and sophisticated energy storage devices are crucial for a sustainable future. Currently, metal-air batteries and fuel cells promise cost-effective, efficient and clean operation. However, highly active bifunctional noble-metal-free catalyst materials are needed to boost sluggish kinetics of oxygen electrode reactions for replacing conventional benchmark catalysts (Pt/C; RuO 2 /IrO 2 ). Herein, we report highly active manganese and cobalt containing metal-organic framework (MOF)-derived bifunctional electrocatalyst with rich porous and well-dispersed structure. Mn/Co-containing material displayed excellent electrocatalytic performance toward both oxygen evolution and reduction reactions (E j=10 =1.66 V; E 1/2 = 0.85 V vs RHE, 0.1 M KOH) due to the desired active sites and architecture. Proposed bifunctional electrocatalyst was also tested in Zn-air battery setup and demonstrated outstanding durability within 10 h cycling without any noticeable degradation and great efficiency with high power density.
    Oxygen evolution
    Noble metal
    Clark electrode
    Rechargeable zinc-air batteries call for high-performance bifunctional oxygen electrocatalysts. Transition metal single-atom catalysts constitute a promising candidate considering their maximum atom efficiency and high intrinsic activity. However, the fabrication of atomically dispersed transition metal sites is highly challenging, creating a need for for new design strategies and synthesis methods. Here, a clicking confinement strategy is proposed to efficiently predisperse transitional metal atoms in a precursor directed by click chemistry and ensure successful construction of abundant single-atom sites. Concretely, cobalt-coordinated porphyrin units are covalently clicked on the substrate for the confinement of the cobalt atoms and affording a Co-N-C electrocatalyst. The Co-N-C electrocatalyst exhibits impressive bifunctional oxygen electrocatalytic performances with an activity indicator Δ E of 0.79 V. This work extends the approach to prepare transition metal single-atom sites for efficient bifunctional oxygen electrocatalysis and inspires the methodology on precise synthesis of catalytic materials.
    Oxygen evolution
    Citations (180)
    Earth‐abundant, low‐cost, and highly active bifunctional electrocatalysts are of significant importance to the large‐scale production of hydrogen from water electrolysis. Herein, it is reported that novel FeNi 3 /NiFeO x nanohybrids display high electrocatalytic activities in both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). These FeNi 3 /NiFeO x nanohybrids are obtained with the unique hydrogenation treatment of NiFeO x nanosheets. Small onset potentials of ≈20 and 240 mV are obtained for HER and OER, respectively, benefited from the synergistic effect of FeNi 3 and NiFeO x . Only a small voltage of 1.55 V is needed to reach a current density of 10 mA cm −2 for the overall water splitting in an alkaline electrolyzer when using FeNi 3 /NiFeO x as both cathode and anode catalysts. This is one of the best performance of electrocatalysts for HER and OER, shining the bright future for earth‐abundant, low‐cost bifunctional electrocatalysts for large‐scale production of hydrogen from water electrolysis.
    Oxygen evolution
    Electrolysis of water
    Citations (98)
    Prussian blue analogues (PBAs), due to their high surface area, large density of catalytically active sites, and high porosity, are one of the potential bifunctional oxygen electrocatalysts for industrial applications. However, so far, only limited success has been achieved toward developing highly efficient PBA-based electrocatalysts. Therefore, unravelling the underlying structure–property–activity relationship and designing strategies or combination of tested strategies are crucial to this effect. In this work, we demonstrate a strategy to concurrently engineer the coordination sphere vacancies and Lewis acid sites, via atomically dispersed Zn2+ dopants in CoFe PBA that makes Con+ more electropositive, to boost the bifunctional oxygen electrocatalysis on PBA surfaces. The optimal Zn-doping (3 mole %) not only enhances the oxygen evolution reaction (OER) activity of CoFe PBAs to the comparable level of the IrO2 catalyst but also depicts an impressive bifunctional oxygen activity with a low reversible overvoltage of 0.84 V. This work also demonstrates that an in situ formation of Co3+ (CoOOH) and Fe3+ (FeOOH) during the OER plays a crucial role for the boosted activity in bifunctional oxygen electrocatalysis. Besides providing highly efficient and low-cost catalysts, this study also imparts important insights to improve the efficiency of PBA-based bifunctional oxygen electrocatalysis.
    Prussian blue
    Oxygen evolution
    Citations (13)
    In article number 1700369, Yizhong Lu, Zexiang Shen, and co-workers report a novel MoP nanoflake array grown on nickel foam, which can act as high-performance bifunctional electrocatalyst for water splitting. The bifunctional electrocatalyst behaves like two hands, one for the hydrogen evolution reaction (HER) and another for the oxygen evolution reaction (OER), respectively. With the two hands, the whole water splitting can be fulfilled efficiently.
    Oxygen evolution
    Citations (8)
    La 0.6 Ca 0.4 CoO 3 perovskite electrocatalyst had been synthesized by organic acid-aided method. The impact of the cal-cining conditions on the electrocatalyst preparation was studied by XRD, TEM and optimal results were given. The perfor-mance of bifunctional oxygen electrode electrocatalyst was evaluated preliminarily by galvanostatic polarization curve method. The results show that the electrocatalyst synthesized at 700 ℃for 2h has the characteristics of single phase, single crystal and smaller grain size, so the condition is optimal for preparing the electrocatalyst. The electrocatalyst made under that condition has better bifunctional oxygen electrode electrocatalytic activity and stability, which is promising as bifunctional oxygen elec-trode electrocatalyst for the MH-Air secondary battery application.
    Clark electrode
    Oxygen evolution
    Citations (0)
    A mesoporous MnCo2 O4 electrode material is made for bifunctional oxygen electrocatalysis. The MnCo2 O4 exhibits both Co3 O4 -like activity for oxygen evolution reaction (OER) and Mn2 O3 -like performance for oxygen reduction reaction (ORR). The potential difference between the ORR and OER of MnCo2 O4 is as low as 0.83 V. By XANES and XPS investigation, the notable activity results from the preferred MnIV - and CoII -rich surface. The electrode material can be obtained on large-scale with the precise chemical control of the components at relatively low temperature. The surface state engineering may open a new avenue to optimize the electrocatalysis performance of electrode materials. The prominent bifunctional activity shows that MnCo2 O4 could be used in metal-air batteries and/or other energy devices.
    Oxygen evolution
    Clark electrode
    XANES
    Citations (221)