This manuscript investigates the degradation of a Pt/Vulcan
fuel
cell catalyst under simulated start–stop conditions in an electrochemical
half-cell. Identical location transmission electron microscopy (IL-TEM)
is used to visualize the several different degradation pathways occurring
on the same catalyst material under potential cycling conditions.
The complexity of degradation on the nanoscale leading to macroscopic
active surface area loss is demonstrated and discussed. Namely, four
different degradation pathways at one single Pt/Vulcan aggregate are
clearly observed. Furthermore, inhomogeneous degradation behavior
for different catalyst locations is shown, and trends in degradation
mechanisms related to the platinum particle size are discussed in
brief. Attention is drawn to the vast field of parameters influencing
catalyst stability. We also present the development of a new technique
to study changes of the catalyst not only with 2D projections of standard
TEM images but also in 3D. For this purpose, identical location tomography
(IL-tomography) is introduced, which visualizes the 3D structure of
an identical catalyst location before and after degradation.
Grain refinement through severe plastic deformation enables synthesis of ultrahigh-strength nanostructured materials. Two challenges exist in that context: First, deformation-driven grain refinement is limited by dynamic dislocation recovery and crystal coarsening due to capillary driving forces; second, grain boundary sliding and hence softening occur when the grain size approaches several nanometers. Here, both challenges have been overcome by severe drawing of a pearlitic steel wire (pearlite: lamellar structure of alternating iron and iron carbide layers). First, at large strains the carbide phase dissolves via mechanical alloying, rendering the initially two-phase pearlite structure into a carbon-supersaturated iron phase. This carbon-rich iron phase evolves into a columnar nanoscaled subgrain structure which topologically prevents grain boundary sliding. Second, Gibbs segregation of the supersaturated carbon to the iron subgrain boundaries reduces their interface energy, hence reducing the driving force for dynamic recovery and crystal coarsening. Thus, a stable cross-sectional subgrain size <10 nm is achieved. These two effects lead to a stable columnar nanosized grain structure that impedes dislocation motion and enables an extreme tensile strength of 7 GPa, making this alloy the strongest ductile bulk material known.
In this study the performance enhancement effect of structural ordering for the oxygen reduction reaction (ORR) is systematically studied. Two samples of PtCu3 nanoparticles embedded on a graphitic carbon support are carefully prepared with identical initial composition, particle dispersion and size distribution, yet with different degrees of structural ordering. Thus we can eliminate all coinciding effects and unambiguously relate the improved activity of the ORR and more importantly the enhanced stability to the ordered nanostructure. Interestingly, the electrochemically induced morphological changes are common to both ordered and disordered samples. The observed effect could have a groundbreaking impact on the future directions in the rational design of active and stable platinum alloyed ORR catalysts.
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