Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 111, Issue 26, Pages 9267-9274Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp071106k
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X-ray absorption spectroscopy (XAS) is utilized in situ to gain new insights into the electronic and chemical interactions of anions specifically adsorbed on Pt/C. A novel difference methodology was utilized, along with full-multiple scattering calculations using the FEFF8 code, to interpret the X-ray absorption near edge structure (XANES). Significant direct contact (specific) anion adsorption occurs in 1 M H2SO4 and 6 M TFMSA, while it does not in 1 M HClO4 and 1 M TFMSA. This specific anion adsorption significantly hinders O(H) chemisorption, particularly formation of subsurface O, causes the Pt nanoparticle to become more round, and weakens the Pt-Pt bonding at the surface. The specific anion adsorption becomes site-specific only after lateral interactions from other chemisorbed species such as OH on the surface force the anions to adsorb into specific sites. Alloying has a profound effect on the strength of the anion adsorption and whether site-specific or just specific adsorption occurs.
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