Publication detail
Identical Fe-N4 Sites with Different Reactivity: Elucidating the Effect of Support Curvature
JAKUB, Z. PLANER, J. HRŮZA, D. TRLLOVÁ SHAHSAVAR, A. PAVELEC, J. ČECHAL, J.
Original Title
Identical Fe-N4 Sites with Different Reactivity: Elucidating the Effect of Support Curvature
Type
journal article in Web of Science
Language
English
Original 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.
Keywords
single atom catalysis; 2D metal-organic frameworks; scanning tunneling microscopy; density functional theory; adsorption; Fe-N4 site
Authors
JAKUB, Z.; PLANER, J.; HRŮZA, D.; TRLLOVÁ SHAHSAVAR, A.; PAVELEC, J.; ČECHAL, J.
Released
29. 1. 2025
Publisher
AMER CHEMICAL SOC
Location
WASHINGTON
ISBN
1944-8252
Periodical
ACS applied materials & interfaces
Year of study
17
Number
6
State
United States of America
Pages from
10136
Pages to
10144
Pages count
9
URL
BibTex
@article{BUT198066,
author="Zdeněk {Jakub} and Jakub {Planer} and Dominik {Hrůza} and Jiří {Pavelec} and Jan {Čechal} and Azin {Trllová Shahsavar}",
title="Identical Fe-N4 Sites with Different Reactivity: Elucidating the Effect of Support Curvature",
journal="ACS applied materials & interfaces",
year="2025",
volume="17",
number="6",
pages="10136--10144",
doi="10.1021/acsami.4c19913",
issn="1944-8252",
url="https://pubs.acs.org/doi/10.1021/acsami.4c19913"
}