Spatially resolved 195Pt NMR of carbon-supported PtRu electrocatalysts: local electronic properties, elemental composition, and catalytic activity

While bimetallic nanoparticles (NPs) offer greater tunability of their catalytic performance than their monometallic counterparts, their detailed mechanistic characterizations are still of a great challenging prospect, particularly at nanoscale. In this paper, we describe a unique (195)Pt nuclear magnetic resonance (NMR) based in situ technique that in principle enables us to access local elemental composition and electronic information across the dimension of the Pt-based NPs with decent spatial resolution. When combined with electrochemical analysis, it opens a way to correlate the local elemental composition and electronic properties with the catalytic activity of the bimetallic NPs. Specifically, from the (195)Pt NMR analysis we concluded that (1) for the PtRu/carbon nanofibers, Ru segregates at the surface while Pt does so inside the NPs; (2) alloying Ru substantially reduces the E(F) local density of states (LDOS) at the Pt atoms; (3) the larger variation in s-like E(F) LDOS at the surface region of the PtRu/graphite nanofibers may imply a higher diversity of catalytic sites available for reactions, therefore explains the observed higher reactivity in methanol electro-oxidation.