Efficient alkaline seawater oxidation by a three-dimensional core-shell dendritic NiCo@NiFe layered double hydroxide electrode

Zhang, Fanghao; Liu, Yifei; Wu, Libo; Ning, Minghui; Song, Shaowei; Xiao, Xin; Hadjiev, V. G.; Fan, Donglei; Wang, Dezhi; Luo, Yu; Chen, Shuo; Ren, Zhifeng

doi:10.1016/j.mtphys.2022.100841

Cited by 29 publications

(22 citation statements)

References 37 publications

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“…Electrochemical oxygen evolution reaction (OER) is a critical step in many sustainable energy storage and conversion systems, but the kinetics is limited by the inherently sluggish four-electron/proton transition process; therefore, the process suffers from considerable energy loss. , Efforts have been devoted to developing earth-abundant transition metal (TM)-based electrocatalysts with low cost and superior catalytic performance to achieve activated OER. − In particular, multiple-cation based spinel oxides are promising OER catalysts due to their flexibility in engineering metal cations and structure stability. − In a normal AB 2 O 4 spinel structure, the O anions are in the form of face-centered cubic (fcc) packing, while the transition metal A and B cations occupy the tetrahedral ( T d ) and octahedral ( O h ) interstices, respectively . The e g occupancy of the cation in the octahedral site is considered as the activity descriptor for the OER of spinel oxides. − A near-unity e g electron occupancy can increase the hybridization between TM 3d- e g orbital and oxygen 2p orbital to form σ-bonds that are favorable to OER.…”

Section: Introductionmentioning

confidence: 99%

Oxidation State Engineering in Octahedral Ni by Anchored Sulfate to Boost Intrinsic Oxygen Evolution Activity

Zhang

Liu

et al. 2023

ACS Nano

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Promoting the electron occupancy of active sites to unity is an effective method to enhance the oxygen evolution reaction (OER) performance of spinel oxides, but it remains a great challenge. Here, an in situ approach is developed to modify the valence state of octahedral Ni cations in NiFe2O4 inverse spinel via surface sulfates (SO4 2–). Different from previous studies, SO4 2– is directly anchored on the spinel surface instead of forming from uncontrolled conversion or surface reconstruction. Experiment and theoretical calculations reveal the precise adsorption sites and spatial arrangement for SO4 2– species. As a main promoting factor, surface SO4 2– effectively converts the crystal field stable Ni state (t 2g 6 e g 2) to the near-unity e g electron state (t 2g 6 e g 1). Moreover, the inevitable oxygen vacancies (Vo) further optimize the energy barrier of the potential-determining step (from OH* to O*). This co-modification strategy enhances turnover frequency-based electrocatalytic activity about two orders higher than the control sample without surface sulfates. This work may provide insight into the OER activity enhancement mechanism by the oxyanion groups.

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Section: Introductionmentioning

confidence: 99%

Oxidation State Engineering in Octahedral Ni by Anchored Sulfate to Boost Intrinsic Oxygen Evolution Activity

Zhang

Liu

et al. 2023

ACS Nano

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“…Such stacked ionic layered structure makes LDHs have large interlayer space and flexible chemical property, enabling full exposure of active sites and great promotion of electronic kinetics [50][51][52][53] . Inspired by these inherent advantages, numerous LDHs have been explored as seawater oxidation electrocatalysts in recent years 44,[52][53][54] . For example, Ren's group proposed a one-step spontaneous growth method driven by Fe 2+ to fabricate NiFe LDH on Ni foam at room temperature 55 .…”

Section: Transition Metal (Oxy)hydroxidesmentioning

confidence: 99%

Recent Advances in Self-Supported Transition-Metal-Based Electrocatalysts for Seawater Oxidation

Qian¹,

Qingping²,

Shu³

et al. 2023

Acta Physico Chimica Sinica

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Seawater electrolysis is a promising and sustainable technology for green hydrogen production. However, some disadvantages include sluggish kinetics, competitive chlorine evolution reaction at the anode, chloride ion corrosion, and surface poisoning, which has led to a decline in activity and durability and low oxygen evolution reaction (OER) selectivity of the anodic electrodes. Benefiting from the lower interface resistance, larger active surface, and superior stability, the self-supported nanoarrays have emerged as advanced catalysts compared to conventional powder catalysts. Self-supported catalysts have more advantages than powder catalysts, particularly in practical large-scale hydrogen production applications requiring high current density. During electrolysis, due to the influx of bubbles generated on the electrode surface, the powdered nanomaterial is peeled off easily, resulting in reduced catalytic activity and even frequent replacement of the catalyst. In contrast, self-supported nanoarray possessing strong adhesion between the active species and the substrates ensures good electronic conductivity and high mechanical stability, which is conducive to long-term use and recycling. This minireview summarizes the recent progress of selfsupported transition-metal-based catalysts for seawater oxidation, including (oxy)hydroxides, nitrides, phosphides, and chalcogenides, emphasizing the strategies in response to the corrosion and competitive reactions to ensure high activity and selectivity in OER processes. In general, constructing three-dimensional porous nanostructures with high porosity and roughness can enlarge the surface areas to expose more active sites for oxygen evolution, which is an efficient strategy for improving mass transfer and catalytic efficiency. Furthermore, the Cl − barrier layer on the surface of catalyst, particularly that with both catalytic activity and protection, can effectively inhibit the competitive oxidation and corrosion of Cl − , thereby delivering enhanced catalytic activity, selectivity, and stability of the catalysts. Moreover, developing super hydrophilic and hydrophobic surfaces is a promising strategy to increase the permeability of electrolytes and avoid the accumulation of large amounts of bubbles on the surface of the self-supported electrodes, thus promoting the effective utilization of active sites. Finally, perspectives and suggestions for future research in OER catalysts for seawater electrolysis are provided. In particular, the medium for seawater electrolysis should be transferred from simulated saline water to natural seawater. Considering the challenges faced in natural seawater splitting, in addition to designing and synthesizing self-supported catalysts with high activities, selectivity, and stability, developing simple and low-cost natural seawater pretreatment

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“…31 The band of NiMoS x @NiFe-LDH/NF at 554.7 cm −1 corresponds to the lattice vibrations of β-Ni 1− x Fe x (OH) 2 . 32 As shown in Fig. S4,† the scanning electron microscopy (SEM) image of NiMoO 4 · x H 2 O/NF shows numerous microcolumns with smooth surfaces.…”

mentioning

confidence: 94%

“…3a presents the Raman spectra of NiFe-LDH/NF at increasing oxidation potentials (1.2 V to 1.9 V) related to seawater oxidation reaction. The initial bands at 455 cm −1 and 525 cm −1 , related to Ni-O(H) and Ni-O vibrations in NiFe-LDH phases, 32,43,44 can be observed. Raman peak at 455 cm −1 gradually shifts to a higher wavenumber of 473 cm −1 , and the peak at 473 cm −1 intensifies with increasing applied bias.…”

mentioning

confidence: 96%

Highly efficient and stable oxygen evolution from seawater enabled by a hierarchical NiMoS_x microcolumn@NiFe-layered double hydroxide nanosheet array

Zhang

Liu

et al. 2023

Inorg. Chem. Front.

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Efficient alkaline seawater oxidation by a three-dimensional core-shell dendritic NiCo@NiFe layered double hydroxide electrode

Cited by 29 publications

References 37 publications

Oxidation State Engineering in Octahedral Ni by Anchored Sulfate to Boost Intrinsic Oxygen Evolution Activity

Oxidation State Engineering in Octahedral Ni by Anchored Sulfate to Boost Intrinsic Oxygen Evolution Activity

Recent Advances in Self-Supported Transition-Metal-Based Electrocatalysts for Seawater Oxidation

Highly efficient and stable oxygen evolution from seawater enabled by a hierarchical NiMoS_x microcolumn@NiFe-layered double hydroxide nanosheet array

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Efficient alkaline seawater oxidation by a three-dimensional core-shell dendritic NiCo@NiFe layered double hydroxide electrode

Cited by 29 publications

References 37 publications

Oxidation State Engineering in Octahedral Ni by Anchored Sulfate to Boost Intrinsic Oxygen Evolution Activity

Oxidation State Engineering in Octahedral Ni by Anchored Sulfate to Boost Intrinsic Oxygen Evolution Activity

Recent Advances in Self-Supported Transition-Metal-Based Electrocatalysts for Seawater Oxidation

Highly efficient and stable oxygen evolution from seawater enabled by a hierarchical NiMoSx microcolumn@NiFe-layered double hydroxide nanosheet array

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Highly efficient and stable oxygen evolution from seawater enabled by a hierarchical NiMoS_x microcolumn@NiFe-layered double hydroxide nanosheet array