Rapid and Surfactant-Free Synthesis of Bimetallic Pt–Cu Nanoparticles Simply via Ultrasound-Assisted Redox Replacement

The synthesis of bimetallic nanoparticles (NPs) with well-defined morphology and a size of <5 nm remains an ongoing challenge. Here, we developed a facile and efficient approach to the design of bimetallic nanostructures by the galvanic replacement reaction facilitated by high-intensity ultrasound (100 W, 20 kHz) at low temperatures. As a model system, Pt–Cu NPs deposited on nitrogen-doped carbon nanotubes (NCNTs) were synthesized and characterized by spectroscopic and microscopic techniques. Transmission electron microscopy (TEM) inspection shows that the mean diameter of Pt–Cu NPs can be as low as ≈2.8 nm, regardless of the much larger initial Cu particle size, and that a significant increase in particle number density by a factor of 35 had occurred during the replacement process. The concentration of the Pt precursor solution as well as of the size of the seed particles were found to control the size of the bimetallic NPs. Energy dispersive X-ray spectroscopy performed in the scanning TEM mode confirmed the alloyed nature of the Pt–Cu NPs. Electrochemical oxygen reduction measurements demonstrated that the resulting Pt–Cu/NCNT catalysts exhibit an approximately 2-fold enhancement in both mass- and area-related activities compared with a commercial Pt/C catalyst.