Interfacial engineering of cobalt phosphide heterostructures confined in N,P-doped carbon for efficient bifunctional electrocatalysis in Zn–air batteries
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The current focus of research lies in the advancement of electrocatalysts based on phosphides, which exhibit exceptional features and robust stability in alkaline environments.Keywords:
Phosphide
Carbon fibers
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
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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
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The bifunctional catalysts for the hydrogen and oxygen evolution reactions (HER and OER) with high efficiency, low cost, and easy integration for future renewable energy systems are highly desirable. Here, on the basis of first-principles calculations, we predicted a two-dimensional (2D) metal–organic framework (MOF) bifunctional electrocatalyst, namely, bis(iminothiolato)nickel (NiIT) monolayer, for overall water splitting. The semi-metallic properties and low HER/OER overpotentials (−0.15/0.50 V) ensure the remarkable electrocatalytic performance of the 2D MOF electrocatalyst. The spatially separated HER and OER active sites with different electronegativities facilitate the electrocatalytic processes. Our findings highlight a promising precious-metal-free bifunctional electrocatalyst for efficient overall water splitting, as well as a novel strategy in catalyst design.
Oxygen evolution
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Herein, a brush-like Cu2O-CoO core-shell nanoarray on copper foam (Cu2O-CoO/CF) can achieve efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance in alkaline seawater electrolyte. This Cu2O-CoO/CF shows overpotentials as low as 315 and 295 mV at 100 mA cm-2 for the OER and HER, respectively. Moreover, it could also be operated at 1.82 V with 100 mA cm-2 in a two-electrode electrolyzer and exhibits strong stability for at least 50 hours of electrolysis. The excellent performance and hierarchical structure advantages of Cu2O-CoO/CF provide new ideas for designing efficient seawater splitting electrocatalysts.
Oxygen evolution
Electrolysis of water
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Oxygen evolution
Bifunctional catalyst
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Oxygen evolution
Alkaline earth metal
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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
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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.
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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
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