Al3+ leaching induced Co4+ on CoFeAl layered double hydroxide for enhanced oxygen evolution reaction

Zhong, Jiayi; Chen, Qiming; Guo, Caixia; Peng, Wenchao; Li, Yang; Zhang, Fengbao; Fan, Xiaobin

doi:10.1016/j.ijhydene.2023.03.088

International Journal of Hydrogen Energy

2023

DOI: 10.1016/j.ijhydene.2023.03.088

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Al3+ leaching induced Co4+ on CoFeAl layered double hydroxide for enhanced oxygen evolution reaction

Jiayi Zhong

Qiming Chen

Caixia Guo

et al.

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2024

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Cited by 10 publications

References 45 publications

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Topological Synthesis of 2D High‐Entropy Multimetallic (Oxy)hydroxide for Enhanced Lattice Oxygen Oxidation Mechanism

Liu,

Jia,

Wang

et al. 2024

Advanced Materials

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Owing to sluggish reaction kinetics and high potential, oxygen evolution reaction (OER) electrocatalysts face a trade‐off between activity and stability. Herein, an innovative topological strategy is presented for preparing 2D multimetallic (oxy)hydroxide, including ternary CoFeZn, quaternary CoFeMnZn, and high‐entropy CoFeMnCuZn. The key to the synthesis lies in using Ca‐rich brownmillerite oxide as a precursor, which possesses inherent structural flexibility enabling tailored elemental adjustments and topologically transforms from a point‐shared structure of metal‐oxygen octahedrons into an edge‐shared structure under alkaline conditions. The presence of Zn in the catalysts causes a shift in the center of the O2p band toward the Fermi level, resulting in more Co4+ species, which drive holes into oxygen ligands to promote intramolecular oxygen coupling. The triggered lattice oxidation mechanism is identified by detecting peroxo‐like (O22−) negative species using tetramethylammonium chemical probe, along with 18O isotope labeling experiments. As a result, the catalyst demonstrates an overpotential of 267 mV at 10 mA cm−2, ranking it among the top‐performing non‐Ni‐based catalysts. Importantly, the catalysts also show high Fe‐leaching resistance during OER compared to conventional NiFe and CoFe hydroxides/(oxy)hydroxides. The assembled zinc‐air battery enables stable operation for over 225 h at a low charging voltage of 1.93 V.

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Topological Synthesis of 2D High‐Entropy Multimetallic (Oxy)hydroxide for Enhanced Lattice Oxygen Oxidation Mechanism

Liu,

Jia,

Wang

et al. 2024

Advanced Materials

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Unraveling the Dynamic Reconstruction of Active Co(IV)‐O Sites on Ultrathin Amorphous Cobalt‐Iron Hydroxide Nanosheets for Efficient Oxygen‐Evolving

Wang,

Zhuang,

Yang

et al. 2024

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Highly‐efficient and cost‐effective electrocatalysts toward the oxygen evolution reaction (OER) are crucial for advancing sustainable energy technologies. Herein, a novel approach leveraging corrosion engineering is presented to facilitate the in situ growth of amorphous cobalt‐iron hydroxides on nickel‐iron foam (CoFe(OH)x‐m/NFF) within a NaCl‐CoCl2 aqueous solution. By adjusting the concentration of the solution, the compositions can tailored and morphologies of these hydroxides to optimize the OER electrocatalytic performance. Specifically, the CoFe(OH)x‐500/NFF electrode manifests as distinctive 3D flower‐like clusters composed of remarkably thin nanosheets, measuring a mere 1 nm in thickness. By virtue of the amorphous and ultrathin nanosheet structure, the CoFe(OH)x‐500/NFF electrode exhibits superior OER activity, characterized by notably low overpotentials (η100, 274 mV) and an exceptionally small Tafel slope of 40.54 mV dec−1. Moreover, the electrode's performance remains robust, maintaining low overpotentials for 168 h at 100 mA cm−2. In situ Raman spectroscopy indicates that the hydroxides experience surface structural reconstruction and transform into high‐valent CoFeO2 with active Co(IV)‐O sites during the OER. Theoretical calculations underscore the critical role of the NiFe substrate in enhancing the electrode's OER activity by improving electrical conductivity and modifying the adsorption energy of reaction intermediates, thereby reducing the energy barrier for the reaction.

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High‐Valence Co Stabilized by In‐Situ Growth of ZIF‐67 on NiCo‐LDH for Enhanced Performance in Oxygen Evolution Reaction

Huang,

Li,

Feng

et al. 2024

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The application of metal–organic frameworks (MOFs) in the electro‐catalysis of heterogeneous structures is limited by the problems of low electrical conductivity and poor mechanical strength due to the complex synthesis process, although their high specific surface area and controllable structure. In this study, a method involving metal precipitation and ligand reaction is used during the electrochemical corrosion of hydroxides/oxy‐hydroxides to obtain ZIF‐67 in situ. The in situ growth technology not only effectively addresses the bonding strength and material conductivity challenges in the heterostructure between MOFs and the substrate but also enhances the catalyst's surface area and activity. Additionally, the exposure and protection of Co4+ by ZIF‐67 contribute to the electrocatalyst's performance, demonstrating a low overpotential (η100) of 293 mV, a Tafel slope of 25.8 mV dec−1, and a charge transfer resistance of 3.9 Ω, with long‐term robustness proven in continuous stability test exceeding 75 000 s under the superhigh current density of 500 mA cm−2. This work on binder‐free in situ growth of MOFs not only provides relevant theoretical insights and experimental experience for cost‐effective and controllable production of MOF‐based catalysts but also offers ideas for the development of future electrocatalysts by exploring the exposure and protection of active site using MOFs materials.

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Al3+ leaching induced Co4+ on CoFeAl layered double hydroxide for enhanced oxygen evolution reaction

Cited by 10 publications

References 45 publications

Topological Synthesis of 2D High‐Entropy Multimetallic (Oxy)hydroxide for Enhanced Lattice Oxygen Oxidation Mechanism

Topological Synthesis of 2D High‐Entropy Multimetallic (Oxy)hydroxide for Enhanced Lattice Oxygen Oxidation Mechanism

Unraveling the Dynamic Reconstruction of Active Co(IV)‐O Sites on Ultrathin Amorphous Cobalt‐Iron Hydroxide Nanosheets for Efficient Oxygen‐Evolving

High‐Valence Co Stabilized by In‐Situ Growth of ZIF‐67 on NiCo‐LDH for Enhanced Performance in Oxygen Evolution Reaction

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