Dual-Site Interaction Tailoring Dynamic Reconstruction of Pt-Ni Dual-Site Catalysts for Advanced Zn-Urea-Air Batteries.

Dynamic reconstruction of single-atom sites generates high-activity species but typically leads to irreversible aggregation and degradation during prolonged operation, presenting a fundamental dilemma for durable electrocatalysis. Here, we propose and demonstrate a strategy to master this reconstruction by constructing synergistic dual single-atom sites, where one stable site guides the evolution of a neighboring reconstruction-prone site. Using an underpotential electrodeposition method, a Pt-Ni dual single-atom (DSA) catalyst with locally coupled PtO4 and NiO6 sites was fabricated. In situ characterizations and theoretical calculations reveal that the Pt-Ni interaction guides a self-optimizing reconstruction for enhanced activity. During oxygen evolution and urea oxidation reactions (OER/UOR), Ni sites are dynamically transformed into ultrafine and stabilized NiOOH clusters anchored around PtO4-SA sites, forming an integrated PtO4-SA/NiOOH active center; while PtO4 sites demonstrate enhanced oxygen reduction reaction (ORR) activity due to the dual-site electronic interaction. When deployed in a zinc-urea-air battery (ZUAB), the catalyst enables a superior energy efficiency (61%) and long-term durability (> 500 h). This work not only offers fundamental insights into the dual-site interaction guiding the self-optimization in DSAs, but also provides a generalizable design principle for creating active and stable catalysts by proactively tailoring dynamic site reconstruction.