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@ARTICLE{Schiller:620134,
author = {Schiller, Frederik and Ali, Khadiza and Makarova, Anna A.
and Auras, Sabine V. and Garcia Martinez, Fernando and
Mohammed Idris Bakhit, Alaa and Castrillo Bodero, Rodrigo
and Villar-García, Ignacio J. and Ortega, J. Enrique and
Pérez-Dieste, Virginia},
title = {{N}ear-{A}mbient {P}ressure {O}xidation of {S}ilver in the
{P}resence of {S}teps: {E}lectrophilic {O}xygen and {S}ulfur
{I}mpurities},
journal = {ACS catalysis},
volume = {14},
number = {17},
issn = {2155-5435},
address = {Washington, DC},
publisher = {ACS},
reportid = {PUBDB-2025-00051},
pages = {12865 − 12874},
year = {2024},
abstract = {The oxidation of Ag crystal surfaces has recently triggered
strong controversies around the presence of sulfur
impurities that may catalyze reactions, such as the alkene
epoxidations, especially the ethylene epoxidation. A
fundamental challenge to achieve a clear understanding is
the variety of procedures and setups involved as well as the
particular history of each sample. Especially, for the
often-used X-ray photoemission technique, product detection,
or photoemission peak position overlap are problematic. Here
we investigate the oxidation of the Ag(111) surface and its
vicinal crystal planes simultaneously, using a curved
crystal sample and in situ X-ray photoelectron spectroscopy
at 1 mbar O$_2$ near-ambient pressure conditions to further
investigate surface species. The curved geometry allows a
straightforward comparative analysis of the surface
oxidation kinetics at different crystal facets, so as to
precisely correlate the evolution of different oxygen
species, namely nucleophilic and electrophilic oxygen, and
the buildup of sulfur as a function of the crystal
orientation. We observed that emission from both surface and
bulk oxide contributes to the characteristic nucleophilic
oxygen core-level peak, which arises during oxygen dosing
and rapidly saturates below temperatures of 180 °C. The
electrophilic oxygen peak appears later, growing at a slower
but constant rate, at the expenses of the surface oxide.
Electrophilic oxygen and sulfur core-levels evolve in
parallel in all crystal facets, although faster and stronger
at vicinal surfaces featuring B-type steps with {111}
microfacets. Our study confirms the intimate connection of
the electrophilic species with the formation of adsorbed
SO$_4$, and points to a higher catalytic activity of B-type
stepped silver surfaces for alkene epoxidation or methane to
formaldehyde conversion.},
cin = {FS-PETRA-S},
ddc = {540},
cid = {I:(DE-H253)FS-PETRA-S-20210408},
pnm = {632 - Materials – Quantum, Complex and Functional
Materials (POF4-632) / CURVEO - Selective ethylene oxidation
on novel curved model catalysts (101066965)},
pid = {G:(DE-HGF)POF4-632 / G:(EU-Grant)101066965},
experiment = {EXP:(DE-MLZ)External-20140101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:39263542},
UT = {WOS:001293062700001},
doi = {10.1021/acscatal.4c02985},
url = {https://bib-pubdb1.desy.de/record/620134},
}