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Title: Electrochemical oxidation of methanol on tin-modified platinum single-crystal surfaces

Journal Article · · Journal of Physical Chemistry; (United States)
DOI:https://doi.org/10.1021/j100162a056· OSTI ID:5988480
;  [1]
  1. Lawrence Berkeley Lab., CA (United States)

To understand the role of tin as a promoter in the electrochemical oxidation of methanol, the authors have studied the geometric and electronic effect of tin atoms in different chemical states on/in the platinum surface by using single-crystal faces of the ordered alloy Pt{sub 3}Sn and single-crystal faces of pure Pt modified by electrodeposited/adsorbed tin, i.e., the so-called adatom state. They found that none of the alloy surfaces were more effective catalysts than any of the pure platinum surfaces under the conditions of measurement employed here and that alloying platinum with tin to any extent significantly reduced the activity. As reported previously by others, they observed tin to spontaneously adsorb on platinum surfaces from dilute sulfuric acid supporting electrolyte containing Sn(II) in concentrations above ca. 5 {mu}M. At a given concentration, the coverage by tin decreased as the atomic density of the platinum surface increased. However, they did not observe any enhancement of methanol oxidation on any platinum modified by this irreversibly adsorbed tin. They did observe a diffusion-limited enhancement on Pt(111) and on Pt(100) due to Sn(II) in the electrolyte at 1 {mu}M concentration. At this concentration, tin did not appear to be adsorbed to any observable extent, and the catalysis appeared to occur via the direct interaction of a dissolved tin species with the surface. They propose a mechanism of catalysis that is a hybrid homogeneous-heterogeneous sequence based on known homogeneous Pt-Sn catalysts.

DOE Contract Number:
AC03-76SF00098
OSTI ID:
5988480
Journal Information:
Journal of Physical Chemistry; (United States), Vol. 95:9; ISSN 0022-3654
Country of Publication:
United States
Language:
English

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