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@INPROCEEDINGS{Heggen:827180,
author = {Heggen, Marc and Gocyla, Martin and Gan, Lin and Strasser,
Peter and Dunin-Borkowski, Rafal},
title = {{G}rowth and degradation of advanced octahedral {P}t-alloy
nanoparticle catalysts for fuel cells},
address = {Weinheim, Germany},
publisher = {Wiley-VCH Verlag GmbH $\&$ Co. KGaA},
reportid = {FZJ-2017-01378},
pages = {800 - 801},
year = {2016},
comment = {European Microscopy Congress 2016: Proceedings},
booktitle = {European Microscopy Congress 2016:
Proceedings},
abstract = {Octahedral Pt-Ni nanoparticles are highly attractive as
fuel-cell catalysts due to their extraordinarily high
activity for the oxygen-reduction-reaction (ORR). A deep
understanding of their atomic-scale structure, degradation
and formation is a prerequisite for their use as rationally
designed nanoparticle catalysts with high activity and
long-term stability.Here we present an extensive
microstructural study of the growth and degradation behavior
of various octahedral Pt-alloy nanoparticles using in situ
transmission electron microscopy (TEM) and Cs-corrected
high-angle annular dark-field scanning transmission electron
microscopy (HAADF-STEM) combined with electron energy-loss
spectroscopy (EELS) and energy-dispersive X-ray spectroscopy
(EDX). We show that octahedral nanoparticles often show
compositional anisotropy with Ni-rich {111} facets leading
to complex structural degradation during ORR
electrocatalysis. The Ni-rich {111} facets are
preferentially etched, resulting in the formation of first
concave octahedra and then Pt-rich skeletons that have less
active facets (Figure 1)[1]. Furthermore, we reveal
element-specific anisotropic growth as the reason for the
compositional anisotropy and the limited stability. During
the solvothermal synthesis, a Pt-rich nucleus evolves into
precursor nanohexapods, followed by the slower step-induced
deposition of Ni on the concave hexapod surface, to form
octahedral facets (Figure 2)[2]. While the growth of Pt-rich
hexapod is a ligand-controlled kinetic process, the
step-induced deposition of the Ni-rich phase at the concave
surface resembles a thermodynamically controlled process
accomplished in much longer time. In order to tune the
atomic-scale microstructure of the octahedra for long-term
stability, we illustrate the effect of varying the growth
conditions on morphology and compositional segregation by
producing trimetallic PtNiCo nanooctahedra and comparing
“one-step” and newly-developed “two-step” synthesis
routes [3]. Furthermore we demonstrate how Pt atom surface
diffusion may produce a protective Pt surface layer on top
of the Ni-rich facets, resulting in advanced and more stable
octahedral catalysts. Figure 3 shows a sequence of
structural changes taking place on an octahedral
nanoparticle during in situ heating up to 800°C using a
MEMS chip heating holder (DENSsolutions, Delft, NL). It can
be observed that Pt-rich corner atoms diffuse and
subsequently fill the concave Ni-rich {111} facets, forming
perfectly octahedral nanoparticles with flat Pt-rich {111}
surfaces (Figure 3) [4].},
month = {Aug},
date = {2016-08-28},
organization = {16th European Microscopy Congress (EMC
2016), Lyon (France), 28 Aug 2016 - 2
Sep 2016},
cin = {PGI-5 / ER-C-1},
cid = {I:(DE-Juel1)PGI-5-20110106 / I:(DE-Juel1)ER-C-1-20170209},
pnm = {143 - Controlling Configuration-Based Phenomena (POF3-143)},
pid = {G:(DE-HGF)POF3-143},
typ = {PUB:(DE-HGF)8 / PUB:(DE-HGF)7},
doi = {10.1002/9783527808465.EMC2016.6030},
url = {https://juser.fz-juelich.de/record/827180},
}