Phosphorus-induced anti-growth of ruthenium clusters-single atoms for ultra-stable hydrogen evolution over 100,000 cycles

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 (RuSA/NP-PNCFs) for ultra-stable HER. The RuSA/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.