Identical Fe-N<sub>4</sub> Sites with Different Reactivity: Elucidating the Effect of Support Curvature
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Date
2025-01-29
Authors
Jakub, Zdeněk
Planer, Jakub
Hrůza, Dominik
Trllová Shahsavar, Azin
Pavelec, Jiří
Čechal, Jan
0000-0001-9538-9087Advisor
Referee
Mark
Journal Title
Journal ISSN
Volume Title
Publisher
AMER CHEMICAL SOC
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Abstract
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.
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Citation
ACS applied materials & interfaces. 2025, vol. 17, issue 6, p. 10136-10144.
https://pubs.acs.org/doi/10.1021/acsami.4c19913
https://pubs.acs.org/doi/10.1021/acsami.4c19913
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Peer-reviewed
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en