title: Size and composition distribution dynamics of alloy nanoparticle electrocatalysts probed by anomalous small angle X-ray scattering (ASAXS).
abstract: Anomalous small angle X-ray scattering (ASAXS) is shown to be an ideal technique to investigate the particle size and particle composition dynamics of carbon-supported alloy nanoparticle electrocatalysts at the atomic scale. In this technique, SAXS data are obtained at different X-ray energies close to a metal absorption edge, where the metal scattering strength changes, providing element specificity. ASAXS is used to, first, establish relationships between annealing temperature and the resulting particle size distribution for Pt25Cu75 alloy nanoparticle electrocatalyst precursors. The Pt specific ASAXS profiles were fitted with log-normal distributions. High annealing temperatures during alloy synthesis caused a significant shift in the alloy particle size distribution towards larger particle diameters. Second, ASAXS was used to characterize electrochemical Cu dissolution and dealloying processes of a carbon-supported Pt25Cu75 electrocatalyst precursor in acidic electrolytes. By performing ASAXS at both the Pt and Cu absorption edges, the unique power of this technique is demonstrated for probing composition dynamics at the atomic scale. These ASAXS measurements provided detailed information on the changes in the size distribution function of the Pt atoms and Cu atoms. A shift in the Cu scattering profile towards larger scattering vectors indicated the removal of Cu atoms from the alloy particle surface suggesting the formation of a Pt enriched Pt shell surrounding a Pt-Cu core. Together with XRD and TEM, ASAXS is proposed to play an increasingly important role in the mechanistic study of degradation phenomena of alloy nanoparticle electrocatalysts at the atomic scale.
authors.affiliation: Department of Chemical and Biomolecular Engineering, University of Houston, Houston, TX 77204-4004, USA.
authors.forename: Chengfei
authors.initials: C
authors.lastname: Yu
authors.forename: Shirlaine
authors.initials: S
authors.lastname: Koh
authors.forename: Jennifer E
authors.initials: JE
authors.lastname: Leisch
authors.forename: Michael F
authors.initials: MF
authors.lastname: Toney
authors.forename: Peter
authors.initials: P
authors.lastname: Strasser
mesh_terms: D002384:Catalysis; D003198:Computer Simulation; D004563:Electrochemistry / Q000379:methods*; D004566:Electrodes; D004579:Electron Transport; D008956:Models, Chemical; D053758:Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure*; D010084:Oxidation-Reduction; D010316:Particle Size; D010984:Platinum / Q000737:chemistry*; D053838:Scattering, Small Angle; D013499:Surface Properties; D014961:X-Ray Diffraction / Q000379:methods*
chemical_list: D010984:Platinum