Self-supported partially crystallized nanoporous metallic glass for ultra-stable and efficient electrocatalytic hydrogen evolution

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.