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Electrolysis of seawater is a promising approach to address freshwater scarcity and indirectly mitigate the energy crisis. In this context, the oxygen evolution reaction (OER) plays a crucial role as one of the half−reactions in water electrolysis. However, the development of cost−effective non−precious metal catalysts for OER remains a challenging issue. In this study, we present a facile method for synthesizing Prussian blue sulfides supported on nickel foam (NF) at ambient temperature. The resulting S−FeNi@NF catalyst demonstrates remarkable electrocatalytic performance with an overpotential of only 330 mV at a current density of 100 mA cm⁻² in simulated seawater. Notably, the catalyst exhibits excellent corrosion resistance and electrochemical stability, maintaining its effectiveness for over 120 h following vulcanization. Furthermore, we assessed the catalysts for their resistance to chloride ion corrosion in natural seawater and observed no significant signs of etching for more than 30 days. This outstanding stability of the S−FeNi@NF material can be attributed to its dual protective mechanisms against chloride ions, which encompass both corrosion resistance and the repulsion of chloride ions during electrochemical processes. Our findings offer a fresh perspective on catalyst design, particularly in the context of shielding against chloride−induced degradation in direct seawater electrolysis. • The negatively charged surface of the vulcanised catalyst effectively resists chloride etching. • No visible structural damage after 30 days of immersion in natural seawater. • In situ growth of PBA materials on NF effectively enhances conductivity and facilitates the four-electron transfer process. • The self-supporting electrocatalysts derived from PBA exhibit dual resistance to the effects of chloride ions. [ABSTRACT FROM AUTHOR]

• The structure and morphology of FeCoNi-S@NF were tuned by cation etching strategy. • The 3D nanoflower structure of FeCoNi-S@NF enhances the number of active sites. • The FeCoNi-S@NF exhibits high FE FDCA in a wide potential from 1.45 to 1.60 V. • The FeCoNi-S@NF exhibits bifunctionality for highly efficient HMFOR and HER. To achieve clean and sustainable energy development, the thermodynamically favourable electrocatalytic oxidation reaction of biomass derivatives can be combined with electrolysis for hydrogen production. This process simultaneously generates high-value 2,5-furandicarboxylic acid and green energy (i.e., hydrogen). The present thesis focuses on the synthesis of a novel Fe-Co-Ni nanosheet catalyst foam using impregnation methods and one-pot hydrothermal techniques. Subsequently, the 3D nanoflower FeCoNi-S@NF catalysts are subsequently prepared by sulfurizing the FeCoNi-LDH@NF precursors. These catalysts were then employed for electrolytic seawater hydrogen production coupled with the electrocatalytic oxidation of 5-hydroxymethylfurfural (HMFOR). This strategy is expected to address the slow kinetics of the oxygen evolution reaction (OER). The 3D nanoflower structure of the FeCoNi-S@NF catalyst enhances the exposure of catalytically active sites, while sulfur doping further improves the electron transfer ability. At a low reaction potential of 1.45 V vs. RHE, FeCoNi-S@NF exhibited remarkable performance with a 95.68 % conversion rate for 5-hydroxymethylfurfural (HMF), a 94.83 % yield for 2,5-furandicarboxylic acid (FDCA), and a Faraday efficiency of 94.71 %. Furthermore, FeCoNi-S@NF exhibits a remarkable response in terms of hydrogen evolution in seawater. By utilizing HMFOR as the anodic reaction and low-cost seawater as the cathodic electrolyte for the hydrogen evolution reaction (HER), simultaneous biomass upgrading and hydrogen production can be achieved. Incorporating HMFOR into a two-electrode system for the electrolytic seawater hydrogen production process significantly reduces the needed voltage (1.70 V@10 mA cm−2), thereby potentially decreasing the cost of this process. [ABSTRACT FROM AUTHOR]