Dual-anion regulation engineering enhances chloridion corrosion resistance for long-lasting industrial-scale seawater splitting

Developing non-precious metal electrocatalysts with high activity and high chlorine (Cl<sup>-</sup>) corrosion resistance at industrial current densities remains challenging for large-scale seawater splitting. To address this problem, we rationally design an amorphous cobalt-iron layered double hydroxide with intercalated borate anions (B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub> <sup>2-</sup>-CoFe-LDH) grown over crystalline sulfurized cobalt molybdate with a sulfate-rich surface (SO<sub>4</sub> <sup>2-</sup>-CoMoO<sub>4</sub>) nanohybrid (B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub> <sup>2-</sup>-CoFe-LDH/SO<sub>4</sub> <sup>2-</sup>-CoMoO<sub>4</sub>). Through sulfidation and amorphous/crystalline interface construction, multiple synergistic effects are induced, effectively modulating the electronic structure, increasing the number of accessible active sites, and promoting electron transfer. The density functional theory calculations and <i>in situ</i> spectroscopy measurements demonstrate that the integration of B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub> <sup>2-</sup>-CoFe-LDH and SO<sub>4</sub> <sup>2-</sup>-CoMoO<sub>4</sub> synergistically optimizes the adsorption energy of intermediates, lowers the reaction energy barrier, and facilitates the formation of CoOOH active species, enhancing the catalytic activity for the oxygen evolution reaction. The unique B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub> <sup>2-</sup>/SO<sub>4</sub> <sup>2-</sup> dual-anion layers block the unfavorable adsorption of Cl<sup>-</sup> and contribute to increased resistance to Cl<sup>-</sup>, enabling long-term corrosion protection for stable seawater splitting. Inspiringly, the B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub> <sup>2-</sup>-CoFe-LDH/SO<sub>4</sub> <sup>2-</sup>-CoMoO<sub>4</sub> nanohybrid stably sustains the industrial current density (1 A cm<sup>-2</sup>) in alkaline simulated seawater for 720 hours, with only a minimal concentration of hypochlorite (ClO<sup>-</sup>, 0.0003%) in the electrolyte.

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Publication Details

Journal
Chemical Science
Published
2025-01-01
DOI
https://doi.org/10.1039/d5sc03775a
Citations
9
Primary Topic
Advanced Photocatalysis Techniques
Type
article
Field-Weighted Citation Impact
3.27

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article

Dual-anion regulation engineering enhances chloridion corrosion resistance for long-lasting industrial-scale seawater splitting

Ze‐Nong Zhang, Tianqi Gao, Wanyu Li, Jiawei Liu et al.
9 citations
Chemical Science
Advanced Photocatalysis Techniques
3.27
article

Dual-anion regulation engineering enhances chloridion corrosion resistance for long-lasting industrial-scale seawater splitting

Ze‐Nong Zhang, Tianqi Gao, Wanyu Li, Jiawei Liu, Yu Chen, Xiao‐Jun Zhao, Wenzhe Wang, Huanhuan Gao, Zhihong Liu
article en
9 citations

Abstract

Developing non-precious metal electrocatalysts with high activity and high chlorine (Cl<sup>-</sup>) corrosion resistance at industrial current densities remains challenging for large-scale seawater splitting. To address this problem, we rationally design an amorphous cobalt-iron layered double hydroxide with intercalated borate anions (B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub> <sup>2-</sup>-CoFe-LDH) grown over crystalline sulfurized cobalt molybdate with a sulfate-rich surface (SO<sub>4</sub> <sup>2-</sup>-CoMoO<sub>4</sub>) nanohybrid (B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub> <sup>2-</sup>-CoFe-LDH/SO<sub>4</sub> <sup>2-</sup>-CoMoO<sub>4</sub>). Through sulfidation and amorphous/crystalline interface construction, multiple synergistic effects are induced, effectively modulating the electronic structure, increasing the number of accessible active sites, and promoting electron transfer. The density functional theory calculations and <i>in situ</i> spectroscopy measurements demonstrate that the integration of B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub> <sup>2-</sup>-CoFe-LDH and SO<sub>4</sub> <sup>2-</sup>-CoMoO<sub>4</sub> synergistically optimizes the adsorption energy of intermediates, lowers the reaction energy barrier, and facilitates the formation of CoOOH active species, enhancing the catalytic activity for the oxygen evolution reaction. The unique B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub> <sup>2-</sup>/SO<sub>4</sub> <sup>2-</sup> dual-anion layers block the unfavorable adsorption of Cl<sup>-</sup> and contribute to increased resistance to Cl<sup>-</sup>, enabling long-term corrosion protection for stable seawater splitting. Inspiringly, the B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub> <sup>2-</sup>-CoFe-LDH/SO<sub>4</sub> <sup>2-</sup>-CoMoO<sub>4</sub> nanohybrid stably sustains the industrial current density (1 A cm<sup>-2</sup>) in alkaline simulated seawater for 720 hours, with only a minimal concentration of hypochlorite (ClO<sup>-</sup>, 0.0003%) in the electrolyte.

Chemical ScienceVol. 16(34)
Xi'an University of Architecture and Technology (CN), Hong Kong University of Science and Technology (HK), Shaanxi Normal University (CN), University of Hong Kong (HK)
National Natural Science Foundation of China, Fundamental Research Funds for the Central Universities, Shaanxi Key Science and Technology Innovation Team Project
Life below water
Openalex Percentile: Top 7%
Advanced Photocatalysis Techniques
3.27
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