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.
Authors
- Ze‐Nong Zhang
- Tianqi Gao (ORCID: https://orcid.org/0000-0002-0577-1352)
- Wanyu Li
- Jiawei Liu (ORCID: https://orcid.org/0000-0002-7516-5008)
- Yu Chen (ORCID: https://orcid.org/0000-0001-9545-6761)
- Xiao‐Jun Zhao (ORCID: https://orcid.org/0000-0002-5931-1335)
- Wenzhe Wang (ORCID: https://orcid.org/0009-0001-6195-3484)
- Huanhuan Gao
- Zhihong Liu (ORCID: https://orcid.org/0000-0002-3554-7992)
Institutions
- 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)
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
Funders
- National Natural Science Foundation of China
- Fundamental Research Funds for the Central Universities
- Shaanxi Key Science and Technology Innovation Team Project