American Chemical Society, Journal of the American Chemical Society, 26(136), p. 9320-9326, 2014
DOI: 10.1021/ja4126998
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We investigated changes in the Pt-Pt bond distance, particle size, crystallinity, and coordination of Pt nanoparticles as a function of particle size (1-3 nm) and adsorbate (H2, CO) using synchrotron radiation pair distribution function (PDF) and X-ray absorption spectroscopy (XAS) measurements. The ~1 nm Pt nanoparticles showed a Pt-Pt bond distance contraction of ~1.4%. The adsorption of H2 and CO at room temperature relaxed the Pt-Pt bond distance con-traction to a value close to that of bulk fcc Pt. The adsorption of H2 improved the crystallinity of the small Pt nanoparticles. However, CO adsorption generated a more disordered fcc structure for the 1-3 nm Pt nanoparticles compared to the H2 adsorption Pt nanoparticles. In situ XANES measurements revealed that this disorder results from the electron back donation of the Pt nanoparticles to CO, leading to a higher degree of rehybridization of the metal orbitals in the Pt-adsorbate system.