Identical Fe-N<sub>4</sub> Sites with Different Reactivity: Elucidating the Effect of Support Curvature
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216305%3A26620%2F26%3A0198066" target="_blank" >RIV/00216305:26620/26:0198066 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acsami.4c19913" target="_blank" >https://pubs.acs.org/doi/10.1021/acsami.4c19913</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acsami.4c19913" target="_blank" >10.1021/acsami.4c19913</a>
Alternative languages
Result language
angličtina
Original language name
Identical Fe-N<sub>4</sub> Sites with Different Reactivity: Elucidating the Effect of Support Curvature
Original language description
Detailed atomic-scale understanding is a crucial prerequisite for rational design of next-generation single-atom catalysts (SACs). However, the sub-& aring;ngstrom precision needed for systematic studies is challenging to achieve on common SACs. Here, we present a two-dimensional (2D) metal-organic system featuring Fe-N4 single-atom sites, where the metal-organic structure is modulated by 0.4 & Aring; corrugation of an inert graphene/Ir(111) support. Using scanning tunneling microscopy and density functional theory, we show that the support corrugation significantly affects the reactivity of the system, as the sites above the support "valleys" bind TCNQ (tetracyanoquinodimethane) significantly stronger than the sites above the "hills". The experimental temperature stability of TCNQ varies by more than 60 degrees C, while computations indicate more than 0.3 eV variation of TCNQ adsorption energy across the Fe-N4 sites placed atop different regions of the corrugated graphene unit cell. The origin of this effect is steric hindrance, which plays a role whenever large molecules interact with neighboring single-atom catalyst sites or when multiple reactants coadsorb on such sites. Our work demonstrates that such effects can be quantitatively studied using model SAC systems supported on chemically inert and physically corrugated supports.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
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Continuities
R - Projekt Ramcoveho programu EK
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
ACS Applied Materials & Interfaces
ISSN
1944-8244
e-ISSN
1944-8252
Volume of the periodical
17
Issue of the periodical within the volume
6
Country of publishing house
US - UNITED STATES
Number of pages
9
Pages from-to
10136-10144
UT code for WoS article
001409014000001
EID of the result in the Scopus database
2-s2.0-85217008709