Identical Fe-N<sub>4</sub> Sites with Different Reactivity: Elucidating the Effect of Support Curvature

Simple item page
dc.contributor.authorJakub, Zdeněkcs
dc.contributor.authorPlaner, Jakubcs
dc.contributor.authorHrůza, Dominikcs
dc.contributor.authorTrllová Shahsavar, Azincs
dc.contributor.authorPavelec, Jiřícs
dc.contributor.authorČechal, Jancs
dc.coverage.issue6cs
dc.coverage.volume17cs
dc.date.accessioned2025-08-01T13:59:09Z
dc.date.available2025-08-01T13:59:09Z
dc.date.issued2025-01-29cs
dc.description.abstractDetailed 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.en
dc.formattextcs
dc.format.extent10136-10144cs
dc.format.mimetypeapplication/pdfcs
dc.identifier.citationACS applied materials & interfaces. 2025, vol. 17, issue 6, p. 10136-10144.en
dc.identifier.doi10.1021/acsami.4c19913cs
dc.identifier.issn1944-8252cs
dc.identifier.orcid0000-0001-9538-9087cs
dc.identifier.orcid0009-0006-5439-1117cs
dc.identifier.orcid0000-0001-7120-7488cs
dc.identifier.orcid0000-0003-4745-8441cs
dc.identifier.other198066cs
dc.identifier.researcheridAAW-8780-2020cs
dc.identifier.researcheridKBR-1105-2024cs
dc.identifier.researcheridJ-5596-2014cs
dc.identifier.researcheridD-6994-2012cs
dc.identifier.scopus57070117100cs
dc.identifier.urihttps://hdl.handle.net/11012/255388
dc.language.isoencs
dc.publisherAMER CHEMICAL SOCcs
dc.relation.ispartofACS applied materials & interfacescs
dc.relation.urihttps://pubs.acs.org/doi/10.1021/acsami.4c19913cs
dc.rightsCreative Commons Attribution 4.0 Internationalcs
dc.rights.accessopenAccesscs
dc.rights.sherpahttp://www.sherpa.ac.uk/romeo/issn/1944-8252/cs
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/cs
dc.subjectsingle atom catalysisen
dc.subject2D metal-organic frameworksen
dc.subjectscanning tunneling microscopyen
dc.subjectdensity functional theoryen
dc.subjectadsorptionen
dc.subjectFe-N4 siteen
dc.titleIdentical Fe-N<sub>4</sub> Sites with Different Reactivity: Elucidating the Effect of Support Curvatureen
dc.type.driverarticleen
dc.type.statusPeer-revieweden
dc.type.versionpublishedVersionen
sync.item.dbidVAV-198066en
sync.item.dbtypeVAVen
sync.item.insts2025.08.01 15:59:09en
sync.item.modts2025.08.01 15:32:53en
thesis.grantorVysoké učení technické v Brně. Fakulta strojního inženýrství. Ústav fyzikálního inženýrstvícs
thesis.grantorVysoké učení technické v Brně. Středoevropský technologický institut VUT. Molekulární nanostruktury na površíchcs
Files
Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
jakubetal2025identicalfen4siteswithdifferentreactivityelucidatingtheeffectofsupportcurvature.pdf
Size:
9.91 MB
Format:
Adobe Portable Document Format
Description:
file jakubetal2025identicalfen4siteswithdifferentreactivityelucidatingtheeffectofsupportcurvature.pdf
Download
Collections
Ústav fyzikálního inženýrství
Molekulární nanostruktury na površích