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@ARTICLE{Cao:907459,
author = {Cao, Pengfei and Tang, Pengyi and Bekheet, Maged F. and Du,
Hongchu and Yang, Luyan and Haug, Leander and Gili, Albert
and Bischoff, Benjamin and Gurlo, Aleksander and Kunz,
Martin and Dunin-Borkowski, Rafal E. and Penner, Simon and
Heggen, Marc},
title = {{A}tomic-{S}cale {I}nsights into {N}ickel {E}xsolution on
{L}a{N}i{O} 3 {C}atalysts via {I}n {S}itu {E}lectron
{M}icroscopy},
journal = {The journal of physical chemistry / C},
volume = {126},
number = {1},
issn = {1932-7447},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2022-02051},
pages = {786 - 796},
year = {2022},
abstract = {Using a combination of insitu bulk and surface
characterization techniques, we provide atomic-scale insight
into the complex surface and bulk dynamics of a LaNiO3
perovskite material during heating in vacuo. Driven by the
outstanding activity LaNiO3 in the methane dry reforming
reaction (DRM), attributable to the decomposition of LaNiO3
during DRM operation into a Ni//La2O3 composite, we reveal
the Ni exsolution dynamics both on a local and global scale
by insitu electron microscopy, insitu X-ray diffraction and
insitu X-ray photoelectron spectroscopy. To reduce the
complexity and disentangle thermal from self-activation and
reaction-induced effects, we embarked on a heating
experiment in vacuo under comparable experimental conditions
in all methods. Associated with the Ni exsolution, the
remaining perovskite grains suffer a drastic shrinkage of
the grain volume and compression of the structure. Ni
particles mainly evolve at grain boundaries and stacking
faults. Sophisticated structure analysis of the elemental
composition by electron-energy loss mapping allows us to
disentangle the distribution of the different structures
resulting from LaNiO3 decomposition on a local scale.
Important for explaining the DRM activity, our results
indicate that most of the Ni moieties are oxidized and that
the formation of NiO occurs preferentially at grain edges,
resulting from the reaction of the exsolved Ni particles
with oxygen released from the perovskite lattice during
decomposition via a spillover process from the perovskite to
the Ni particles. Correlating electron microscopy and X-ray
diffraction data allows us to establish a sequential
two-step process in the decomposition of LaNiO3 via a
Ruddlesden–Popper La2NiO4 intermediate structure.
Exemplified for the archetypical LaNiO3 perovskite material,
our results underscore the importance of focusing on both
surface and bulk characterization for a thorough
understanding of the catalyst dynamics and set the stage for
a generalized concept in the understanding of state-of-the
art catalyst materials on an atomic level.},
cin = {ER-C-1},
ddc = {530},
cid = {I:(DE-Juel1)ER-C-1-20170209},
pnm = {5351 - Platform for Correlative, In Situ and Operando
Characterization (POF4-535)},
pid = {G:(DE-HGF)POF4-5351},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000739933000001},
doi = {10.1021/acs.jpcc.1c09257},
url = {https://juser.fz-juelich.de/record/907459},
}