The preparation of alloyed bimetallic nanoparticles (BNPs) between immiscible elements is always a huge challenge due to the lack of thermodynamic driving forces. W–Cu is a typical immiscible binary system, and it is difficult to alloy them under conventional circumstances. Here, we used the bond energy model (BEM) to calculate the effect of size on the alloying ability of W–Cu systems. The prediction results show that reducing the synthesis size (the original size of W and Cu) to less than 10 nm can obtain alloyed W–Cu BNPs. Moreover, we prepared alloyed W50Cu50 BNPs with a face-centered-cubic (FCC) crystalline structure via the nano in situ composite method. Energy-dispersive X-ray spectroscopy (EDS) coupled with scan transmission electron microscopy (STEM) confirmed that W and Cu are well mixed in a single-phase particle, instead of a phase segregation into a core-shell or other heterostructures. The present results suggest that the nanoscale size effect can overcome the immiscibility in immiscible binary systems. In the meantime, this work provided a high-yield and universal method for preparing alloyed BNPs between immiscible elements.
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