Identical Fe-N₄ Sites with Different Reactivity: Elucidating the Effect of Support Curvature

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Identical Fe-N₄ Sites with Different Reactivity: Elucidating the Effect of Support Curvature

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Identical Fe-N₄ Sites with Different Reactivity: Elucidating the Effect of Support Curvature

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

R - Projekt Ramcoveho programu EK

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

ACS Applied Materials & Interfaces

ISSN

1944-8244

e-ISSN

1944-8252

Svazek periodika

17

Číslo periodika v rámci svazku

6

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

10136-10144

Kód UT WoS článku

001409014000001

EID výsledku v databázi Scopus

2-s2.0-85217008709