Balancing atomic mixing and surface segregation in Ag-M nanostructures for cooperative nitrate reduction.

Carbon-nanofiber-supported Ag-M nanoparticles (M = Fe, Co, Ni, Cu, and Pd) were synthesized via electrospinning-assisted thermal conversion. Controlled by mixing enthalpy, surface energy, and interfacial energy, they form Ag-Pd alloy, Janus Ag-Cu, and core-satellite Ag-Fe/Co/Ni structures. The Ag-Fe/CNFs achieves NH3 faradaic efficiency of 90.1% and yield rate of 563.7 µmol h-1 cm-2 for nitrate reduction. In situ measurements support a cooperative cascade pathway, linking thermodynamic phase organization with heterointerfacial catalysis.