Metal aggregation, caused by high current density or long-cycling catalysis, severely affects the stability of ruthenium (Ru)-based catalysts toward hydrogen evolution reaction (HER). Herein, we constructed an anti-growth strategy of phosphorus (P)-induced Ru clusters (1.3 nm) integrated with adjacent Ru single atoms on nitrogen (N)-doped carbon fibers (Ru_SA/NP-PNCFs) for ultra-stable HER. The Ru_SA/NP-PNCFs exhibit outstanding activity (8 and 132 mV at 10 and 1,000 mA cm⁻²) and record durability (100,000 cycles and 1,000 h at 600 mA cm⁻²). Thanks to the optimized binding energy and orbital interaction between Ru and P/N, the size variation is only 0.8 nm, and single atoms are also well preserved. Both experiments and theoretical simulations indicate that the heteroatom P can not only boost the capacity of H₂O dissociation but also suppress the aggregation of Ru clusters and single atoms during HER. This work provides an effective strategy for designing stable metal cluster-single-atom systems for advanced electrocatalysts.

高电流密度或长循环催化引起的金属聚集严重影响钌（Ru）基催化剂的析氢反应（HER）稳定性。在此，我们构建了磷（P）诱导的Ru簇（1.3 nm）与氮（N）掺杂碳纤维（Ru _SA/NP -PNCF）上相邻Ru单原子集成的抗生长策略，以实现超稳定的HER 。 Ru _{SA/NP -PNCF 表现出出色的活性（在 10 和 1,000 mA cm} ^-2下为 8 和 132 mV ）和创纪录的耐久性（在 600 mA cm ^-2下为 100,000 次循环和 1,000 小时）。由于Ru和P/N之间优化的结合能和轨道相互作用，尺寸变化仅为0.8 nm，并且单个原子也得到了很好的保存。实验和理论模拟均表明，杂原子P不仅可以提高H ₂ O解离能力，还可以抑制HER过程中Ru簇和单原子的聚集。这项工作为设计先进电催化剂的稳定金属簇单原子系统提供了有效的策略。