Core–Shell Compositional Fine Structures of Dealloyed Pt_<i>x</i>Ni_1–<i>x</i> Nanoparticles and Their Impact on Oxygen Reduction Catalysis

Using aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy line profiles with Ångstrom resolution, we uncover novel core–shell fine structures in a series of catalytically active dealloyed Pt_<i>x</i>Ni_1–<i>x</i> core–shell nanoparticles, showing the formation of unusual near-surface Ni-enriched inner shells. The radial location and the composition of the Ni-enriched inner shells were sensitively dependent on the initial alloy compositions. We further discuss how these self-organized Ni-enriched inner shells play a key role in maintaining surface lattice strain and thus control the surface catalytic activity for oxygen reduction

<i>In Situ</i> Study of Atomic Structure Transformations of Pt–Ni Nanoparticle Catalysts during Electrochemical Potential Cycling

When exposed to corrosive anodic electrochemical environments, Pt alloy nanoparticles (NPs) undergo selective dissolution of the less noble component, resulting in catalytically active bimetallic Pt-rich core–shell structures. Structural evolution of PtNi₆ and PtNi₃ NP catalysts during their electrochemical activation and catalysis was studied by <i>in situ</i> anomalous small-angle X-ray scattering to obtain insight in element-specific particle size evolution and time-resolved insight in the intraparticle structure evolution. <i>Ex situ</i> high-energy X-ray diffraction coupled with pair distribution function analysis was employed to obtain detailed information on the atomic-scale ordering, particle phases, structural coherence lengths, and particle segregation. Our studies reveal a spontaneous electrochemically induced formation of PtNi particles of ordered Au₃Cu-type alloy structures from disordered alloy phases (solid solutions) concomitant with surface Ni dissolution, which is coupled to spontaneous residual Ni metal segregation during the activation of PtNi₆. Pt-enriched core–shell structures were not formed using the studied Ni-rich nanoparticle precursors. In contrast, disordered PtNi₃ alloy nanoparticles lose Ni more rapidly, forming Pt-enriched core–shell structures with superior catalytic activity. Our X-ray scattering results are confirmed by STEM/EELS results on similar nanoparticles