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@ARTICLE{PulparayilMathew:622021,
author = {Pulparayil Mathew, Jikson and Seno, Carlotta and Jaiswal,
Mohit and Simms, Charlotte and Reichholf, Nico and Van den
Eynden, Dietger and Parac-Vogt, Tatjana N. and De Roo,
Jonathan},
title = {{T}he {C}entral {R}ole of {O}xo {C}lusters in
{Z}irconium‐{B}ased {E}sterification {C}atalysis},
journal = {Small science},
volume = {5},
number = {1},
issn = {2688-4046},
address = {Weinheim},
publisher = {Wiley-VCH GmbH},
reportid = {PUBDB-2025-00133},
pages = {2400369},
year = {2024},
abstract = {Oxo clusters are a unique link between oxide nanocrystals
and Metal-Organic Frameworks (MOFs), representing the limit
of downscaling each of the respective crystals. Herein, the
superior catalytic activity of clusters, compared to
zirconium MOF UiO-66 and nanocrystals is shown. Focus is on
esterification reactions given their general importance in
consumer products and the challenge of converting large
substrates. Oxo clusters have a higher surface-to-volume
ratio than nanocrystals, rendering them more active. For
large substrates, for example, oleic acid, MOF UiO-66 has
negligible catalytic activity while clusters provide almost
quantitative conversion, a fact we ascribe to limited
diffusion of large substrates through the MOF pores.
Clusters do not suffer from limited mass transfer and we
also obtain high conversion in solvent-free reactions with
sterically hindered alcohols (hexanol, 2-ethyl hexanol,
benzyl alcohol, and neopentyl alcohol). The cluster catalyst
can be recovered and shows identical activity when reused.
The structural integrity of the cluster is confirmed using
X-ray total scattering and pair distribution function
analysis. Moreover, when homogeneous zirconium alkoxides are
used as catalysts, the same oxo cluster is retrieved,
showing that oxo clusters are the active catalytic species,
even in previously assumed homogeneously catalyzed
reactions.},
cin = {FS DOOR-User},
ddc = {500},
cid = {$I:(DE-H253)FS_DOOR-User-20241023$},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3) / FS-Proposal: I-20231114
EC (I-20231114-EC)},
pid = {G:(DE-HGF)POF4-6G3 / G:(DE-H253)I-20231114-EC},
experiment = {EXP:(DE-H253)P-P21.1-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {40212644},
UT = {WOS:001318139600001},
doi = {10.1002/smsc.202400369},
url = {https://bib-pubdb1.desy.de/record/622021},
}