H2 Evolution Reaction Pathway of a Cobalt Bis-bipyridyl Planar Catalyst Revealed by Ab Initio Simulations

Basit Öğe Kaydı
dc.authoridGurdal, Yeliz/0000-0002-6245-891X
dc.contributor.authorGüçlü, Ipek
dc.contributor.authorKiser, Ayas
dc.contributor.authorGurdal, Yeliz
dc.date.accessioned2025-01-06T17:44:56Z
dc.date.available2025-01-06T17:44:56Z
dc.date.issued2024
dc.description.abstractLigand type and ligand coordination around cobalt photocatalysts influence the reaction mechanism of H2 production via water splitting. We investigated the H2 production mechanisms of a cobalt bis-bipyridyl planar water reduction catalyst in an aqueous solution using ab initio molecular dynamics, metadynamics, density functional theory, and free energy perturbation theory. Modeling each intermediate step of the reaction mechanism reveals that the cobalt-based planar catalyst exhibits a preference for a pathway involving two successive reductions, followed by two protonation steps. The reason for this preference is the presence of an energy barrier for the conformational change of water molecules in the first solvation shell following the first reduction. This barrier prevents direct coordination of cobalt with protons, which is necessary for the initial protonation step in the sequential electron- and proton-transfer mechanisms. In the mechanism involving two successive reductions followed by two protonations, however, the second reduction step facilitates direct interaction between cobalt and protons, enabling the initial protonation. Following the second protonation of this mechanism, H2 is produced and released into the solvent. Reduction free energy calculations reveal that, following the first reduction, the singlet spin state of the system is more favorable than the triplet spin state. The reduction free energy of the second electron transfer is 0.19 eV less energetic than that of the first reduction reaction.
dc.description.sponsorshipT?rkiye Bilimsel ve Teknolojik Arastirma Kurumu; Scientific and Technological Research Council of Turkiye (TUBITAK) [120Z240]; TUBITAK
dc.description.sponsorshipY.G. acknowledges the Scientific and Technological Research Council of Turkiye (TUBITAK). This study has received funding from the TUBITAK under the 3501 Career Development Program (grant agreement No. 120Z240). The calculations reported in this paper were performed at the TUBITAK ULAKBIM, High Performance and Grid Computing Center (TRUBA), based in Turkiye.
dc.identifier.doi10.1021/acs.jpcc.4c04733
dc.identifier.endpage20548
dc.identifier.issn1932-7447
dc.identifier.issn1932-7455
dc.identifier.issue48
dc.identifier.scopus2-s2.0-85210273167
dc.identifier.scopusqualityQ1
dc.identifier.startpage20537
dc.identifier.urihttps://doi.org/10.1021/acs.jpcc.4c04733
dc.identifier.urihttps://hdl.handle.net/20.500.14669/3251
dc.identifier.volume128
dc.identifier.wosWOS:001362815700001
dc.identifier.wosqualityN/A
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.language.isoen
dc.publisherAmer Chemical Soc
dc.relation.ispartofJournal of Physical Chemistry C
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/closedAccess
dc.snmzKA_20241211
dc.subjectElectrocatalytıc Hydrogen Evolutıon
dc.subjectWater
dc.subjectGeneratıon
dc.subjectComplexes
dc.subjectMechanısm
dc.titleH2 Evolution Reaction Pathway of a Cobalt Bis-bipyridyl Planar Catalyst Revealed by Ab Initio Simulations
dc.typeArticle

Dosyalar

Koleksiyon

WoS İndeksli Yayınlar Koleksiyonu
Scopus İndeksli Yayınlar Koleksiyonu