Advancing sustainable hydrogen production relies on the creation of effective electrocatalysts for the hydrogen evolution reaction (HER). Ruthenium (Ru) is a potential alternative to platinum due to its lower cost and high activity, yet its performance in alkaline HER remains limited by sluggish reaction kinetics. Herein, we propose a strategy to modulate electronic asymmetry within Ru clusters by anchoring Ru nanoclusters on N-doped graphene (Ru-NC), optimizing the charge distribution between high-valent Run+ and metallic Ru0 sites. The Ru-NC catalyst, having a Ruⁿ+/Ru0 ratio of 57.1%, demonstrates superior HER activity with an overpotential of merely 29 mV at 10 mA·cm−2 and a Tafel slope of 46 mV·dec−1 in 1.0 M KOH, surpassing the performance of Pt/C catalyst. Experimental and structural analyses reveal that the asymmetric electronic configuration facilitates H2O dissociation at Run+ sites and efficient H adsorption/desorption at Ru0 sites, synergistically lowering energy barriers for HER intermediates. Furthermore, Ru-NC demonstrates remarkable stability, retaining its activity after 5000 cycles and operating continuously for 80 h at 100 mA·cm−2 with minimal degradation. This work highlights the pivotal role of electronic asymmetry in enhancing HER kinetics and provides a rational design principle for high-performance Ru-based electrocatalysts.
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Nano Research 2025, 18(9): 94907689
Published: 02 September 2025
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