Why the Perfectly Symmetric Cobalt-Pentapyridyl Loses the H2 Production Challenge: Theoretical Insight into Reaction Mechanism and Reduction Free Energies

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dc.authoridGurdal, Yeliz/0000-0002-6245-891X
dc.contributor.authorKiser, Ayas
dc.contributor.authorGurdal, Yeliz
dc.date.accessioned2025-01-06T17:44:49Z
dc.date.available2025-01-06T17:44:49Z
dc.date.issued2024
dc.description.abstractResearchers have extensively investigated photo-catalytic water reduction utilizing Cobalt-based catalysts with polypyridyl ligands. While catalysts exhibiting distorted polypyridyl ligand demonstrate higher H-2 production yields, those with ideal octahedral coordination display poor performance. This outcome suggests the crucial role of ligand framework in catalytic activity, yet reasons behind the disparity in H-2 production rates for catalysts with octahedral geometries remain unclear. We theoretically examined the water reduction mechanism of Co-based poly-pyridyl catalyst, CoPy5, having perfect octahedral coordination. We clarified the effect of octahedral coordination by utilizing each intermediate step of ECEC mechanism. We determined spin states, solvent response, electronic structures, and reduction free energies. CoPy5 with perfect octahedral coordination, alongside its distorted counterparts, exhibit similar spin states as the reaction progresses through each intermediate step. However, the first reduction free energy obtained for the CoPy5 is slightly higher than that of its distorted counterparts. Following the second protonation, resulting H-2 molecule experiences limited diffusion from the Co center due to the compact structure of the CoPy5, which blocks the Co center for the next H-2 production cycle. Catalysts having distorted octahedral geometries facilitate fast removal of H-2 into the solvent. Thus, the reaction center becomes immediately available for subsequent H-2 production.
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 p; 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.doi10.1002/cctc.202300901
dc.identifier.issn1867-3880
dc.identifier.issn1867-3899
dc.identifier.issue1
dc.identifier.scopus2-s2.0-85174578872
dc.identifier.scopusqualityQ1
dc.identifier.urihttps://doi.org/10.1002/cctc.202300901
dc.identifier.urihttps://hdl.handle.net/20.500.14669/3191
dc.identifier.volume16
dc.identifier.wosWOS:001089491500001
dc.identifier.wosqualityQ2
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.language.isoen
dc.publisherWiley-V C H Verlag Gmbh
dc.relation.ispartofChemcatchem
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/openAccess
dc.snmzKA_20241211
dc.subjectwater splitting
dc.subjectab initio molecular dynamics
dc.subjectdensity functional theory
dc.subjectfree energy perturbation theory
dc.titleWhy the Perfectly Symmetric Cobalt-Pentapyridyl Loses the H2 Production Challenge: Theoretical Insight into Reaction Mechanism and Reduction Free Energies
dc.typeArticle

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