Synergistic chloride resistance via hydrogen‒bond network dynamic optimization and electrostatic repulsion for alkaline seawater oxidation

doi:10.1016/S1872-2067(26)65100-5

Abstract

Abstract:

Seawater electrolysis, while promising for sustainable hydrogen production, is fundamentally challenged by the relentless chloride ions (Cl^-)-induced corrosion, which impairs catalyst stability during long-term operation. We report a polyhydroquinone (PHQ)-modified electrocatalyst, where the redox-active PHQ layer is firmly coated to CoFe layered double hydroxide (CoFe LDH) surface through a strong hydrogen-bond network. Theoretical calculations and characterization techniques collectively elucidate that the unique interface creates an in situ protective coating, which effectively optimizes the composition of the interfacial water and prevents Cl^- attack. Such a catalyst shows outstanding performance in alkaline seawater, requiring an overpotential of only 335 mV to reach 1 A cm^-2 and exhibiting remarkable durability for 2000 h even at high current densities (j = 1, 1.5, and 2 A cm^-2). Furthermore, the constructed alkaline anion exchange membrane water electrolyzer achieves a j of 1 A cm^-2 at a low voltage of 2.55 V, significantly outperforming the benchmark Pt/C/NF||RuO₂/NF.

Key words: CoFe layered double hydroxide, Alkaline seawater oxidation, Anodic corrosion, Electrostatic repulsion, Hydrogen?bond network

Wei Zuo, Mingyu Liu, Shengjun Sun, Yu Yang, Zixiao Li, Xixi Zhang, Chaoxin Yang, Hefeng Wang, Imran Shakir, Xuefei Liu, Qian Liu, Xuping Sun, Bo Tang. Synergistic chloride resistance via hydrogen‒bond network dynamic optimization and electrostatic repulsion for alkaline seawater oxidation[J]. Chinese Journal of Catalysis, 2026, 87: 295-304.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65100-5

https://www.cjcatal.com/EN/Y2026/V87/I8/295

Figures/Tables 5

Fig. 1. (a) Schematic illustration of the synthetic process of PHQ@CoFe LDH/NF. (b) Element analysis of electrolyte after electropolymerization. (c) XRD patterns. (d) FT-IR spectra. (e) SEM images of PHQ@CoFe LDH/NF. TEM (f) and high-resolution TEM (g) images of PHQ@CoFe LDH. (h) TEM image and corresponding elemental distributions of PHQ@CoFe LDH.

Fig. 2. (a) Co K-edge XANES spectra. (b) Co FT-EXAFS spectra. (c) High-resolution XPS spectra for PHQ@CoFe LDH and CoFe LDH in Co 2p regions. (d) Fe K-edge XANES spectra. (e) Fe FT-EXAFS spectra. (f) High-resolution XPS spectra for PHQ@CoFe LDH and CoFe LDH in Fe 2p regions.

Fig. 3. LSV curves (a) and Δη/Δlog|j| values (b) of three electrocatalysts in 1 mol L-1 KOH + seawater. (c) TOF and mass activities of three electrocatalysts. FTacV curves (d) and corresponding regions area (e). (f) In-situ Raman spectra. (g) Bode plots. (h) Eapp and Log (Aapp) values. (i) The free energy change diagram of OER process.

Fig. 4. (a) Long-term electrolysis of PHQ@CoFe LDH/NF and CoFe LDH/NF. (b) Comparison of electrolysis lifespans in alkaline seawater. (c) UV-vis absorption spectra of the electrolytes after stability test. (d) Zeta potentials. (e) Energy calculations for the adsorption of Cl*. (f) Schematic diagram of AEMWE. (g) Polarization curves. (h) Continuous stability measurement. (i) Intermittent electrolysis of Pt/C/NF||PHQ@CoFe LDH/NF with 12-h start-shutdown cycles.

Fig. 5. In-situ Raman spectra of PHQ@CoFe LDH/NF (a) and CoFe LDH/NF (b) at different potentials. The proportions of the water configuration for PHQ@CoFe LDH/NF (c) and CoFe LDH/NF (d). (e) Trends in interfacial water. LSV curves of PHQ@CoFe LDH/NF (f) and CoFe LDH/NF (g) in simulated alkaline seawater with different NaCl concentrations. (h) Comparison of electrolysis lifespan.

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