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@ARTICLE{Gashnikova:626128,
author = {Gashnikova, Daria and Maurer, Florian and Bauer, Miriam R.
and Bernart, Sarah and Jelic, Jelena and Lützen, Mads and
Maliakkal, Carina B. and Dolcet, Paolo and Studt, Felix and
Kübel, Christian and Damsgaard, Christian D. and Casapu,
Maria and Grunwaldt, Jan-Dierk},
title = {{L}ifecycle of {P}d {C}lusters: {F}ollowing the {F}ormation
and {E}volution of {A}ctive {P}d {C}lusters on {C}eria
{D}uring {CO} {O}xidation by {I}n {S}itu/{O}perando
{C}haracterization {T}echniques},
journal = {ACS catalysis},
volume = {14},
number = {19},
issn = {2155-5435},
address = {Washington, DC},
publisher = {ACS},
reportid = {PUBDB-2025-01319},
pages = {14871 - 14886},
year = {2024},
note = {(DFG) through grant no. INST 40/575-1 FUGG (JUSTUS2, RVs
bw17D011).},
abstract = {For maximizing the atomic efficiency in noble metal-based
catalysts, dedicated preparation routes and high lifetime
are essential. Both aspects require an in-depth
understanding of the fate of noble metal atoms under
reaction conditions. For this purpose, we used a combination
of complementary in situ/operando characterization
techniques to follow the lifecycle of the Pd sites in a
$0.5\%$ $Pd/5\%$ CeO2–Al2O3 catalyst during oxygen-rich CO
oxidation. Time-resolved X-ray absorption spectroscopy
showed that Pd cluster formation under reaction conditions
is important for a high CO oxidation activity. In
combination with density functional theory calculations, we
concluded that the ideal Pd cluster size amounts to about
10–30 Pd atoms. The cluster formation and stability were
affected by the applied temperature and reaction conditions.
Already short pulses of 1000 ppm CO in the lean reaction
feed were found to trigger sintering of Pd at temperatures
below 200 °C, while at higher temperatures oxidation
processes prevailed. Environmental transmission electron
microscopy unraveled redispersion at higher temperatures
(400–500 °C) in oxygen atmosphere, leading to the
formation of single sites and thus the loss of activity.
However, due to the reductive nature of CO, clusters formed
again upon cooling in reaction atmosphere, thus closing the
catalytic cycle. Exploiting the gained knowledge on the
lifecycle of Pd clusters, we systematically investigated the
effect of catalyst composition on the cluster formation
tendency. As uncovered by DRIFTS measurements, the Pd to
CeO2 ratio seems to be a key descriptor for Pd agglomeration
under reaction conditions. While for higher Pd loadings, the
probability of cluster formation increased, a higher CeO2
content leads to the formation of oxidized dispersed Pd
species. According to our results, a Pd:CeO2 weight ratio of
1:10 for CeO2–Al2O3-supported catalysts leads to the
highest CO oxidation activity under lean conditions
independent of the applied synthesis method.},
cin = {FS DOOR-User},
ddc = {540},
cid = {$I:(DE-H253)FS_DOOR-User-20241023$},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3) / SFB 1441 A03 -
Reaktivität und hochentwickelte Elektronenmikroskopie von
massenselektierten Clustern auf Oxidträgern (A03)
(446697387) / SFB 1441 B01 - Synthese und Charakterisierung
von Metalloxidträgern mit hoher Oberfläche (B01)
(446700158) / SFB 1441 B02 - Systematische Synthese und
katalytische Tests von definierten Edelmetallspezies auf
Pulverträgern (B02) (446700275) / SFB 1441 B03 - In
situ/operando-Charakterisierung von Edelmetallclustern und
Partikeln auf Metalloxiden unter Reaktionsbedingungen (B03)
(446701131) / SFB 1441 B04 - DFT-Gestützte Mikrokinetische
Modellierung der Oxidativen Beseitigung von Schadstoffen
(B04) (446701677) / DFG project G:(GEPRIS)460248799 -
DAPHNE4NFDI - DAten aus PHoton- und Neutronen Experimenten
für NFDI (460248799)},
pid = {G:(DE-HGF)POF4-6G3 / G:(GEPRIS)446697387 /
G:(GEPRIS)446700158 / G:(GEPRIS)446700275 /
G:(GEPRIS)446701131 / G:(GEPRIS)446701677 /
G:(GEPRIS)460248799},
experiment = {EXP:(DE-H253)P-P65-20150101},
typ = {PUB:(DE-HGF)16},
UT = {WOS:001325925200001},
doi = {10.1021/acscatal.4c02077},
url = {https://bib-pubdb1.desy.de/record/626128},
}