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Spectroscopic in situ Measurements of the Relative Pt Skin Thicknesses and Porosities of Dealloyed PtMn (Ni, Co) Electrocatalysts
Ist Teil von
Journal of physical chemistry. C, 2015-01, Vol.119 (1), p.757-765
Ort / Verlag
United States: American Chemical Society
Erscheinungsjahr
2015
Link zum Volltext
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
X-ray adsorption near edge structure (XANES) data at the Co or Ni K-edge, analyzed using the Δ
μ
difference procedure, are reported for dealloyed PtCo
x
and PtNi
x
catalysts (six different catalysts at different stages of life). All catalysts meet the 2017 DOE beginning of life target Pt mass activity target (>0.44 A mg
Pt
−1
), but exhibit varying activities and durabilities. The variance factors include different initial precursors, dealloying in HNO
3
vs H
2
SO
4
, if a postdealloying thermal annealing step was performed, and different morphologies (some with a multi PtM
x
core and porous Pt skin, some single core with nonporous skin). Data are obtained at the initial beginning of life (BOL, ~200 voltage cycles) and after 10k and 30k (end of life, EOL) voltage cycles following DOE protocol (0.6–1.0 V vs reversible hydrogen electrode). The Δ
μ
data are used to determine at what potential (
V
pen
) the Pt skin is penetrated by O. The durability, related to a drop in the electrochemical surface areas (ECSAs) after extensive voltage cycling, directly correlates with the
V
pen
at BOL. The data indicate that cycling produces a “characteristic” Pt skin robustness (porosity or thickness). When the Pt skin at BOL is “thin” (
V
pen
< 0.9 V) it grows to a “characteristic” thickness consistent with a
V
pen
of ≈1.1 V, and if it begins very thick, it thins to the same “characteristic” thickness. Particles dealloyed in H
2
SO
4
appear to have a thicker Pt skin at BOL than those dealloyed in HNO
3
, and a postdealloying annealing procedure appears to produce a particularly nonporous skin with high
V
pen
, but not necessarily thicker. Furthermore, the PtM
3
catalysts exhibited a fast skin “healing” process whereby the initial porous skin appears to become more nonporous after holding the potential at 0.9 V. This work is believed to be the first
in situ
XAS study to shed light on the nature of the Pt skin, its thickness, and/or porosity, and how it changes with respect to operating electrochemical conditions.