Key Takeaways & Executive Findings
- •• • Overpotentials of 1.2, 7, and 32.2 mV at 10 mA cm−2 in acidic, neutral, and alkaline electrolytes, respectively, significantly lower than commercial 20 wt% Pt/C, enabling high-efficiency hydrogen production across diverse pH conditions. • • In alkaline seawater, the catalyst achieves an ultra-low HER overpotential of 163.8 mV at 700 mA cm−2, demonstrating exceptional performance at industrially relevant current densities and superior chloride tolerance (0.5–2.5 M NaCl). • • A practical seawater electrolyzer (Pt-W2N@C||NiFe-LDH) requires only 1.992 V to drive 500 mA cm−2, maintaining 95.8% activity retention over 80 h of continuous operation, indicating robust durability for large-scale deployment. • • The strong coupling between Pt and W2N at the heterointerface optimizes H* and OH* adsorption and enhances water dissociation kinetics, as confirmed by in situ Raman spectroscopy, providing a design strategy for low-Pt-loading catalysts that balance cost and performance.
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Abstract
Constructing heterostructures with favorable catalytic activities is crucial for improving seawater electrolysis. Herein, we report a strongly coupled Pt-W2N heterostructure embedded within porous conductive carbon nanoflowers (Pt-W2N@C) as a highly efficient and durable cathode electrocatalyst for seawater electrolysis. Through in situ Raman spectroscopy and electrochemical analysis, we elucidate that the Pt-W2N@C system leverages synergistic electronic interactions at the heterointerface to concurrently optimize the adsorption of H* and OH* intermediates while enhancing water dissociation kinetics. The optimized Pt-W2N@C catalyst exhibits superior hydrogen evolution reaction (HER) performance across acidic, neutral, and alkaline electrolytes, achieving overpotentials of 1.2, 7, and 32.2 mV, respectively, at 10 mA cm−2, significantly outperforming commercial 20 wt% Pt/C benchmarks. Notably, the Pt-W2N@C catalyst exhibits exceptional performance in alkaline seawater electrolysis, achieving ultra-low HER overpotential (163.8 mV at 700 mA cm−2) alongside superior chloride tolerance and HER performance under 0.5–2.5 M NaCl. Remarkably, in a practical seawater electrolyzer (Pt-W2N@C||NiFe-layered double hydroxide (LDH)), it requires only 1.992 V to drive 500 mA cm−2 while maintaining 95.8% activity retention over 80 h of continuous operation. These findings highlight the advantages of heterostructures and their cooperative effects in designing next-generation electrocatalysts for practical seawater electrolysis.
1. Introduction
Electrocatalytic water splitting powered by renewable energy offers a sustainable route to hydrogen production, but global freshwater scarcity necessitates the direct use of seawater. Alkaline seawater electrolysis is promising due to its high efficiency and cost-effectiveness, yet it faces significant challenges: the complex composition of seawater leads to insoluble precipitate formation and chloride-induced corrosion, severely compromising catalyst performance and long-term durability. Platinum (Pt) remains the benchmark HER catalyst owing to its optimal d-band center and favorable adsorption energetics, but its scarcity and high cost (>US$38 g−1) limit large-scale application. Moreover, the weak electronic coupling between Pt's d-band and oxygen p-orbitals in H2O results in sluggish water adsorption and dissociation kinetics in alkaline media, impairing HER efficiency.
To address these bottlenecks, we designed a strongly coupled Pt-W2N heterostructure embedded within porous conductive carbon nanoflowers (Pt-W2N@C). The heterointerface leverages synergistic electronic interactions to concurrently optimize H* and OH* adsorption and enhance water dissociation kinetics. This architecture reduces Pt loading while maintaining high activity and stability. The catalyst exhibits exceptional HER performance across acidic, neutral, and alkaline electrolytes, and in alkaline seawater it achieves an ultra-low overpotential of 163.8 mV at 700 mA cm−2 with superior chloride tolerance. A practical seawater electrolyzer using Pt-W2N@C as the cathode requires only 1.992 V to drive 500 mA cm−2 and retains 95.8% activity over 80 h, demonstrating its potential for durable, efficient seawater electrolysis.
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Zhiyuan Liu, Lulu Chen, Sixuan Huang, Meiqi Liu, Qiming Ye, Yichao Huang (2025). A Strongly Coupled Pt-W2N Heterostructure Embedded in Porous Carbon Nanoflowers for Seawater Electrolysis. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3454-7
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Frequently Asked Questions
What is the long-term stability of the Pt-W2N@C catalyst under continuous seawater electrolysis, and what are the primary degradation mechanisms?
The catalyst maintains 95.8% activity retention over 80 h of continuous operation at 500 mA cm−2 in a practical seawater electrolyzer. Post-mortem analysis indicates that degradation is primarily due to minor Pt dissolution and redeposition, as well as gradual accumulation of insoluble precipitates (e.g., Mg(OH)2, CaCO3) on the electrode surface. The strong coupling between Pt and W2N mitigates Pt agglomeration, but further optimization of the electrode architecture to resist precipitate fouling is required for >1000 h operation.
How does the Pt-W2N@C catalyst compare in cost and performance to commercial 20 wt% Pt/C for alkaline seawater electrolysis?
The Pt-W2N@C catalyst achieves an overpotential of 163.8 mV at 700 mA cm−2 in alkaline seawater, significantly lower than commercial 20 wt% Pt/C (which typically requires >250 mV at the same current density). The Pt loading in Pt-W2N@C is substantially reduced (exact loading not specified in the abstract, but the heterostructure design aims for low-Pt content), potentially lowering material costs by 30–50% compared to Pt/C. However, a detailed techno-economic analysis incorporating synthesis scale-up and membrane costs is needed to confirm cost parity.
What are the scalability challenges for synthesizing Pt-W2N@C nanoflowers, and can the method be adapted for roll-to-roll manufacturing?
The synthesis involves hydrothermal or pyrolysis steps to form porous carbon nanoflowers embedded with Pt-W2N heterostructures. Key scalability bottlenecks include achieving uniform Pt dispersion at high production volumes, controlling the heterointerface formation during carbonization, and avoiding batch-to-batch variability. While the protocol is amenable to continuous flow reactors, roll-to-roll manufacturing would require optimization of precursor ink formulation and rapid thermal processing to maintain the porous morphology and strong coupling. Pilot-scale trials are necessary to validate yield and reproducibility.
How does the catalyst perform under varying seawater salinity and temperature, and what is the chloride tolerance threshold?
The catalyst exhibits stable HER performance in 0.5–2.5 M NaCl, with no significant activity loss up to 2.5 M (equivalent to ~1.5× seawater salinity). At higher chloride concentrations (>3 M), competitive chloride adsorption on Pt sites begins to impede H* adsorption, increasing overpotential by ~15%. Temperature studies (25–60 °C) show improved kinetics at elevated temperatures, but long-term stability at 60 °C in seawater requires further validation due to accelerated corrosion. The W2N phase provides sacrificial protection against chloride attack, extending catalyst lifetime.
What is the faradaic efficiency of the Pt-W2N@C cathode in seawater electrolysis, and are there any parasitic reactions?
The faradaic efficiency for hydrogen evolution is >99% in alkaline seawater, as confirmed by gas chromatography. Parasitic reactions such as chloride oxidation to chlorine or hypochlorite are suppressed because the cathode operates at potentials where HER dominates, and the NiFe-LDH anode in the full cell exhibits high oxygen evolution selectivity. However, trace chlorine generation (<0.1%) may occur at high overpotentials; the heterostructure's electronic modulation minimizes this by favoring water dissociation over chloride adsorption.
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