Strong electrostatic adsorption-engaged fabrication of sub-3.0 nm PtRu alloy nanoparticles as synergistic electrocatalysts toward hydrogen evolution.

Alloying of Pt with Ru to form ultrafine and well-defined PtRu alloy nanoparticles (NPs) for synergistically electrocatalytic hydrogen evolution is highly desirable but remains a synthetic challenge. Here, we report a strong electrostatic adsorption (SEA)-assisted fabrication of ultrafine and homogeneously distributed PtRu alloy NPs using ethylenediaminetetraacetic acid tetrasodium-derived carbon (EC) as a matrix. The O, N-rich EC with a hierarchically macro/meso/microporous structure and the SEA-assisted formation of the [Ru(bpy)][PtCl] complex ensure the successful generation of ultrasmall PtRu alloy NPs (2.93 nm in diameter) with high dispersion. The optimal PtRu/EC-700 delivers excellent electrocatalytic properties with an ultralow overpotential (η = 18 mV), robust durability and good long-term stability for the alkaline hydrogen evolution reaction (HER). The ultrasmall PtRu alloy NPs with rich surface sites, the synergistic catalysis effect between Pt and Ru and the hierarchically macro/meso/microporous structure of O, N-rich EC cooperatively enhance the HER performance of PtRu/EC-700. This study provides an easy but effective way to construct metal alloy NPs with an ultrafine size and high dispersity for catalytic applications.