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Title: Site-Specific vs Specific Adsorption of Anions on Pt and Pt-Based Alloys

Abstract

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 H{sub 2}SO{sub 4} and 6 M TFMSA, while it does not in 1 M HClO{sub 4} 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.

Authors:
; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
929998
Report Number(s):
BNL-80608-2008-JA
TRN: US200822%%956
DOE Contract Number:  
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry C; Journal Volume: 111
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; ADSORPTION; PLATINUM; PLATINUM ALLOYS; ANIONS; CHEMICAL BONDS; SURFACE PROPERTIES; INTERACTIONS; POSITIONING; national synchrotron light source

Citation Formats

Teliska,M., Murthi, V., Mukerjee, S., and Ramaker, D.. Site-Specific vs Specific Adsorption of Anions on Pt and Pt-Based Alloys. United States: N. p., 2007. Web. doi:10.1021/jp071106k.
Teliska,M., Murthi, V., Mukerjee, S., & Ramaker, D.. Site-Specific vs Specific Adsorption of Anions on Pt and Pt-Based Alloys. United States. doi:10.1021/jp071106k.
Teliska,M., Murthi, V., Mukerjee, S., and Ramaker, D.. Mon . "Site-Specific vs Specific Adsorption of Anions on Pt and Pt-Based Alloys". United States. doi:10.1021/jp071106k.
@article{osti_929998,
title = {Site-Specific vs Specific Adsorption of Anions on Pt and Pt-Based Alloys},
author = {Teliska,M. and Murthi, V. and Mukerjee, S. and Ramaker, D.},
abstractNote = {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 H{sub 2}SO{sub 4} and 6 M TFMSA, while it does not in 1 M HClO{sub 4} 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.},
doi = {10.1021/jp071106k},
journal = {Journal of Physical Chemistry C},
number = ,
volume = 111,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}