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@ARTICLE{Dionigi:878638,
author = {Dionigi, F. and Weber, C. Cesar and Primbs, M. and Gocyla,
M. and Bonastre, A. Martinez and Spöri, C. and Schmies, H.
and Hornberger, E. and Kühl, S. and Drnec, J. and Heggen,
M. and Sharman, J. and Dunin-Borkowski, R. Edward and
Strasser, P.},
title = {{C}ontrolling {N}ear-{S}urface {N}i {C}omposition in
{O}ctahedral {P}t{N}i({M}o) {N}anoparticles by {M}o {D}oping
for a {H}ighly {A}ctive {O}xygen {R}eduction {R}eaction
{C}atalyst},
journal = {Nano letters},
volume = {19},
number = {10},
issn = {1530-6992},
address = {Washington, DC},
publisher = {ACS Publ.},
reportid = {FZJ-2020-02966},
pages = {6876 - 6885},
year = {2019},
abstract = {We report and study the translation of exceptionally high
catalytic oxygen electroreduction activities of
molybdenum-doped octahedrally shaped PtNi(Mo) nanoparticles
from conventional thin-film rotating disk electrode
screenings (3.43 ± 0.35 A mgPt–1 at 0.9 VRHE) to membrane
electrode assembly (MEA)-based single fuel cell tests with
sustained Pt mass activities of 0.45 A mgPt–1 at 0.9
Vcell, one of the highest ever reported performances for
advanced shaped Pt alloys in real devices. Scanning
transmission electron microscopy with energy dispersive
X-ray analysis (STEM-EDX) reveals that Mo preferentially
occupies the Pt-rich edges and vertices of the
element-anisotropic octahedral PtNi particles. Furthermore,
by combining in situ wide-angle X-ray spectroscopy, X-ray
fluorescence, and STEM-EDX elemental mapping with
electrochemical measurements, we finally succeeded to
realize high Ni retention in activated PtNiMo nanoparticles
even after prolonged potential-cycling stability tests.
Stability losses at the anodic potential limits were mainly
attributed to the loss of the octahedral particle shape.
Extending the anodic potential limits of the tests to the Pt
oxidation region induced detectable Ni losses and structural
changes. Our study shows on an atomic level how Mo adatoms
on the surface impact the Ni surface composition, which, in
turn, gives rise to the exceptionally high experimental
catalytic ORR reactivity and calls for strategies on how to
preserve this particular surface composition to arrive at
performance stabilities comparable with state-of-the-art
spherical dealloyed Pt core–shell catalysts.},
cin = {ER-C-1},
ddc = {660},
cid = {I:(DE-Juel1)ER-C-1-20170209},
pnm = {143 - Controlling Configuration-Based Phenomena (POF3-143)
/ DFG project 257727131 - Nanoskalige Pt
Legierungselektrokatalysatoren mit definierter Morphologie:
Synthese, Electrochemische Analyse, und ex-situ/in-situ
Transmissionselektronenmikroskopische (TEM) Studien
(257727131)},
pid = {G:(DE-HGF)POF3-143 / G:(GEPRIS)257727131},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:31510752},
UT = {WOS:000490353500021},
doi = {10.1021/acs.nanolett.9b02116},
url = {https://juser.fz-juelich.de/record/878638},
}