Key Takeaways & Executive Findings
- •• • The C-NPMG catalyst achieves overpotentials of 18.0 mV (0.5 M H2SO4), 42.2 mV (1 M KOH), and 88.0 mV (1 M PBS) at 10 mA cm−2, outperforming Pt benchmarks across all pH conditions; this pH universality is critical for integration into diverse electrolyzer systems without pH-specific catalyst replacement. • • Stability exceeds 1000 h in alkaline electrolyte with negligible decay, addressing the chronic durability bottleneck of non-noble catalysts; this longevity is essential for industrial water electrolysis where catalyst replacement costs dominate operational expenses. • • The nanoporous architecture and crystallite-amorphous interfaces lower the H2 desorption energy barrier, as confirmed by computational analysis; this mechanistic insight enables rational design of high-activity MG catalysts beyond trial-and-error. • • The hierarchical super-hydrophilic/super-hydrophobic wettability optimizes mass transport and corrosion resistance, a dual function that reduces ohmic losses and extends catalyst lifetime, directly impacting energy efficiency and maintenance cycles in practical electrolyzers.
Abstract
Metallic glasses (MGs) often suffer from sluggish hydrogen evolution reaction (HER) kinetics in neutral and alkaline media, with their catalytic performance predominantly confined to acidic environments. Herein, we reported a novel thermoplastic forming technique to fabricate a self-supported partially crystallized nanoporous Pt56.2Ni5.2Cu16.8P21.8 metallic glass (C-NPMG). The C-NPMG catalyst delivers ultralow overpotentials of 18.0 mV (0.5 M H2SO4), 42.2 mV (1 M KOH), and 88.0 mV (1 M phosphate-buffered saline (PBS)) at a current density of 10 mA cm−2, outperforming most state-of-the-art non-noble MGs and Pt-based benchmarks across all pH conditions. Notably, it maintains negligible performance decay for over 1000 h in alkaline electrolytes, showcasing superior stability. Experimental and computational analyses reveal that the enhanced HER activity arises from three synergistic effects: (1) the high-specific-surface-area nanoporous architecture that maximizes active site exposure; (2) the formation of crystallite-amorphous interfaces during partial crystallization, which lowers the energy barrier for H2 desorption; (3) the hierarchical super-hydrophilic and super-hydrophobic wettability of the C-NPMG, which optimizes mass transport and prevents electrolyte-induced corrosion. This work establishes a novel design paradigm for developing high-performance, pH-universal HER electrocatalysts by integrating structural nano-engineering and crystallite-amorphous phase synergy in metallic glass systems to overcome the trade-offs between performance and stability in electrochemical water splitting.
1. Introduction
Conventional HER catalysts, particularly noble metals like Pt, exhibit superior activity in acidic media but suffer from sluggish kinetics in neutral and alkaline electrolytes due to energy-intensive water dissociation and unfavorable hydrogen adsorption-desorption dynamics. For instance, the hydrogen binding energy on Pt surfaces deviates from the optimal range in alkaline environments, leading to a two to three order of magnitude activity decline compared to acidic conditions. Non-noble metal catalysts offer cost advantages but their stability and pH universality remain inadequate. Moreover, most state-of-the-art catalysts are powder-based, requiring binder-assisted electrode fabrication that buries active sites, impedes electron transport, and causes structural degradation during operation.
Metallic glasses (MGs), with their disordered atomic structure and tunable properties, have emerged as promising electrocatalysts. However, their catalytic performance has been largely confined to acidic media, and achieving high activity and stability across all pH ranges remains a critical challenge. This work introduces a thermoplastic forming technique to fabricate a self-supported partially crystallized nanoporous metallic glass (C-NPMG). The approach integrates structural nano-engineering with crystallite-amorphous phase synergy, directly addressing the trade-off between performance and stability. The resulting catalyst demonstrates ultralow overpotentials and exceptional durability, offering a new paradigm for pH-universal HER electrocatalysis.
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Jihan Jiang, Wenqing Ruan, Shenghao Zeng, Jiaqing Lin, Xingran Zhao, Jianan Fu, Qing Chen, Xiaodi Liu, Jiang Ma (2026). Self-supported partially crystallized nanoporous metallic glass for ultra-stable and efficient electrocatalytic hydrogen evolution. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3506-3
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Frequently Asked Questions
What is the specific composition of the metallic glass and how does partial crystallization contribute to the enhanced HER activity?
The metallic glass composition is Pt56.2Ni5.2Cu16.8P21.8. Partial crystallization creates crystallite-amorphous interfaces that lower the energy barrier for H2 desorption, as confirmed by computational analysis. This synergistic effect, combined with the nanoporous architecture, results in overpotentials as low as 18.0 mV in 0.5 M H2SO4 and 42.2 mV in 1 M KOH at 10 mA cm−2.
How does the C-NPMG catalyst achieve stability for over 1000 hours in alkaline media without significant performance decay?
The hierarchical super-hydrophilic and super-hydrophobic wettability of the C-NPMG optimizes mass transport and prevents electrolyte-induced corrosion. This dual functionality, along with the self-supported nature that eliminates binder-related degradation, ensures negligible performance decay over 1000 h in 1 M KOH, a critical requirement for industrial electrolyzers.
What are the overpotential values at 10 mA cm−2 in different pH conditions, and how do they compare to Pt-based benchmarks?
The C-NPMG catalyst achieves overpotentials of 18.0 mV in 0.5 M H2SO4, 42.2 mV in 1 M KOH, and 88.0 mV in 1 M PBS at 10 mA cm−2. These values outperform most state-of-the-art non-noble MGs and Pt-based benchmarks across all pH conditions, demonstrating pH-universal activity.
What is the role of the thermoplastic forming technique in fabricating the self-supported nanoporous structure?
The thermoplastic forming technique enables the fabrication of a self-supported nanoporous structure without the need for binders or conductive additives. This approach maximizes active site exposure and ensures efficient electron transport, directly addressing the limitations of powder-based catalysts that suffer from active site burial and structural degradation.
How does the nanoporous architecture and crystallite-amorphous interface affect the hydrogen desorption kinetics?
The high-specific-surface-area nanoporous architecture maximizes active site exposure, while the crystallite-amorphous interfaces formed during partial crystallization lower the energy barrier for H2 desorption. Computational analyses confirm that this synergistic effect enhances HER kinetics, contributing to the ultralow overpotentials observed across all pH conditions.
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