The
effect of phosphate anion poisoning of cathodic Pt-based catalysts
in phosphoric acid fuel cells was investigated by observing the kinetics
of the oxygen reduction reaction (ORR) in the presence of varied concentrations
of H3PO4. In an attempt to reduce phosphate
anion poisoning, a Pt-based Ni alloy catalyst was synthesized. Detailed
electrochemical and X-ray absorption spectroscopy investigations have
been carried out on both Pt and PtNi electrocatalysts under in situ
conditions. It was found that the phosphate poisoning effect on the
ORR is much less severe on PtNi/C than on Pt/C. The Δμ
X-ray absorption near-edge spectroscopy analysis suggests that the
adsorbed phosphate anions actually remain to higher potential on PtNi
than on Pt, and this inhibits OH adsorption from water activation
and the conversion from OH to O, thus allowing more sites for the
ORR. Due to the presence of phosphate anions on the atop sites of
PtNi/C, OH cannot occupy such sites now either due to steric hindrance
or just lower availability of atop sites, and thus, it appears to
keep the remaining sites (2-fold and 3-fold) free for molecular oxygen
to undergo the ORR.
Structural changes of precipitates in an Mg-5 at%Gd (Mg 95 Gd 5 ) alloy by aging at 200 C and 250 C have been studied by ordinary highresolution transmission electron microscopy (HRTEM) and high-angle annular detector dark-field scanning transmission electron microscopy (HAADF-STEM). In the early stage of precipitation by aging at 200 C up to 5 h, a short-range ordered structure exists in Gd-enriched regions with an about 2 nm size, and nuclei of an Mg 7 Gd structure ( 0 phase) occur in the short-range ordered structure by aging at 200 C for 5 h. The C for 100 h.
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