Faraday Discussions (RSC) - up to Jan. 20, 2009

Faraday Disc. (RSC) - up to Jan. 20, 2009

Faraday Discuss., 2009, 140, 139 - 153, DOI: 10.1039/b803073a
A comparative in situ195Pt electrochemical-NMR investigation of PtRu nanoparticles supported on diverse carbon nanomaterials

Fatang Tan, Bingchen Du, Aaron L. Danberry, In-Su Park, Yung-Eun Sung and YuYe Tong
This paper reports a detailed in situ195Pt electrochemical-nuclear magnetic resonance (EC-NMR) study of PtRu nanoparticles (NPs) that had a nominal atomic ratio of Pt : Ru = 1 : 1 and were supported on carbon nanocoils and carbon black (Vulcan XC-72) respectively. The particle sizes of the two samples were determined by X-ray diffraction using the Sherrer equation: 3.6 nm for the former and 3.2 nm for the latter, which were further corroborated by transmission electron microscope measurements. By taking advantage of a unique correlation between the spectral frequency of the 195Pt NMR resonance and the radial atomic position in a particle, qualitatively- and spatially-resolved local Pt atomic fractions in the particles were deduced by using a Ruderman–Kittel–Kasuya–Yosida (RKKY) J-coupling-based method as a function of different electrode potentials. The results indicated that both samples had Pt-enriched cores and Pt-deprived surfaces and, most importantly, the local Pt concentration varied as the electrochemical environment changed. The spatially-resolved Fermi level local densities of states (Ef-LDOS), which are a measure of the electronic frontier orbitals in metals, were deduced across the NMR spectrum and correlated with the EC activity in methanol electro-oxidation. The results were also compared to those obtained previously from Pt/Ru NPs supported respectively on carbon and graphite nanofibers.

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Faraday Discuss., 2009, 140, 69 - 80, DOI: 10.1039/b802919a
Bridging the gap between nanoparticles and single crystal surfaces

Payam Kaghazchi, Felice C. Simeone, Khaled A. Soliman, Ludwig A. Kibler and Timo Jacob
Using density functional theory calculations and the extended ab initio atomistic thermodynamics approach, we studied the adsorption of oxygen on the different surface faces, which are involved in the faceting of Ir(210). Constructing the (p,T)-surface phase diagrams of the corresponding surfaces in contact with an oxygen atmosphere, we find that at high temperatures the planar surfaces are stable, while lowering the temperature stabilizes those nano-facets found experimentally. Afterwards, we constructed the (a,T,)-phase diagram for Ir(210) in contact with an aqueous electrolyte and found that the same nano-facets should be stable under electrochemical conditions. Motivated by this prediction from theory, experiments were performed using cyclic voltammetry and in-situ scanning tunneling microscopy. The presence of nanofacets for Ir(210) gives rise to a characteristic current-peak in the hydrogen adsorption region for sulfuric acid solution. Furthermore, first results on the electrocatalytic behavior of nano-faceted Ir(210) are presented.