Suppressing oxygen-vacancy-mediated chlorine corrosion for high-current stable seawater electrolysis

NiFe layered double hydroxide (NiFe LDH) is an efficient seawater oxygen evolution reaction (OER) catalyst. However, its long-term stability is severely limited by Cl<sup>-</sup>-induced corrosion. To address this issue, an innovative vanadate modification strategy is developed to mitigate Cl<sup>-</sup> corrosion in NiFe LDH. The resulting VO<sub>4</sub> <sup>3-</sup>-NiFe LDH/VO <sub><i>x</i></sub> /NF catalyst exhibits excellent activity and durability in alkaline seawater, maintaining a current density of 1000 mA cm<sup>-2</sup> for 3500 h, which is significantly longer than the 300 h achieved by the single NiFe LDH. Through <i>in situ</i> characterization and theoretical studies, it is revealed that on the NiFe LDH, Cl<sup>-</sup> preferentially adsorbs onto oxygen vacancies (O<sub>v</sub>) generated <i>via</i> the lattice oxygen mechanism. This adsorption induces M-Cl coordination and further accelerates the formation of O<sub>v</sub>, thereby driving a self-reinforcing corrosion cycle. By contrast, the VO <sub><i>x</i></sub> on the surface of VO<sub>4</sub> <sup>3-</sup>-NiFe LDH/VO <sub><i>x</i></sub> /NF undergoes <i>in situ</i> conversion to VO<sub>4</sub> <sup>3-</sup>, combining with intercalated VO<sub>4</sub> <sup>3-</sup> to form a dynamically adaptive VO<sub>4</sub> <sup>3-</sup> species. These species generate a strong electrostatic field that repels Cl<sup>-</sup>, while simultaneously stabilizing OH<sup>-</sup> through a hydrogen-bonding network. As a result, it effectively suppresses metal-Cl coordination and optimizes the adsorption behavior of OH<sup>-</sup>, thereby sustaining high catalytic activity and stability.

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Publication Details

Journal
Chemical Science
Published
2025-11-10
DOI
https://doi.org/10.1039/d5sc07816d
Citations
3
Primary Topic
Electrocatalysts for Energy Conversion
Type
article
Field-Weighted Citation Impact
1.09

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article

Suppressing oxygen-vacancy-mediated chlorine corrosion for high-current stable seawater electrolysis

Fangyuan Guan, Zihui Ning, Zhixiang Zhai, Jialin Wu et al.
3 citations
Chemical Science
Electrocatalysts for Energy Conversion
1.09
article

Suppressing oxygen-vacancy-mediated chlorine corrosion for high-current stable seawater electrolysis

Fangyuan Guan, Zihui Ning, Zhixiang Zhai, Jialin Wu, Shuang Yin, Zelong Sun, Lin Luo, Wenjie Jiang
article en
3 citations

Abstract

NiFe layered double hydroxide (NiFe LDH) is an efficient seawater oxygen evolution reaction (OER) catalyst. However, its long-term stability is severely limited by Cl<sup>-</sup>-induced corrosion. To address this issue, an innovative vanadate modification strategy is developed to mitigate Cl<sup>-</sup> corrosion in NiFe LDH. The resulting VO<sub>4</sub> <sup>3-</sup>-NiFe LDH/VO <sub><i>x</i></sub> /NF catalyst exhibits excellent activity and durability in alkaline seawater, maintaining a current density of 1000 mA cm<sup>-2</sup> for 3500 h, which is significantly longer than the 300 h achieved by the single NiFe LDH. Through <i>in situ</i> characterization and theoretical studies, it is revealed that on the NiFe LDH, Cl<sup>-</sup> preferentially adsorbs onto oxygen vacancies (O<sub>v</sub>) generated <i>via</i> the lattice oxygen mechanism. This adsorption induces M-Cl coordination and further accelerates the formation of O<sub>v</sub>, thereby driving a self-reinforcing corrosion cycle. By contrast, the VO <sub><i>x</i></sub> on the surface of VO<sub>4</sub> <sup>3-</sup>-NiFe LDH/VO <sub><i>x</i></sub> /NF undergoes <i>in situ</i> conversion to VO<sub>4</sub> <sup>3-</sup>, combining with intercalated VO<sub>4</sub> <sup>3-</sup> to form a dynamically adaptive VO<sub>4</sub> <sup>3-</sup> species. These species generate a strong electrostatic field that repels Cl<sup>-</sup>, while simultaneously stabilizing OH<sup>-</sup> through a hydrogen-bonding network. As a result, it effectively suppresses metal-Cl coordination and optimizes the adsorption behavior of OH<sup>-</sup>, thereby sustaining high catalytic activity and stability.

Chemical ScienceVol. 17(1)
Guangxi University (CN)
National Natural Science Foundation of China, Guangxi University
Openalex Percentile: Top 21%
Electrocatalysts for Energy Conversion
1.09
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