Comparison of Penta and Tetra-pyridyl Cobalt-based Catalysts for Water Reduction: H2 Production Cycle, Solvent Response and Reduction Free Energy

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dc.authoridGurdal, Yeliz/0000-0002-6245-891X
dc.contributor.authorGurdal, Yeliz
dc.contributor.authorIannuzzi, Marcella
dc.date.accessioned2025-01-06T17:36:04Z
dc.date.available2025-01-06T17:36:04Z
dc.date.issued2020
dc.description.abstractUnderstanding water reduction towards H-2 generation is crucial to overcome today's renewable energy obstacles. Previous studies have shown the superior H-2 production performances of Cobalt based penta-pyridyl (CoaPPy) and tetra-pyridyl (CoaTPy) complexes in solution. We investigate H-2 production cycles of CoaPPy and CoaTPy complexes immersed in water solution by means of Ab-initio Molecular Dynamics and Density Functional Theory. We monitor dynamic properties of the systems, solvent response and structural changes occurring in the catalysts, by simulating all intermediate steps of the H-2 production cycle. Reduction free energies and reorganization energies are calculated. Our results show that, following the first electron injection, H-2 production proceeds with the singlet spin state. Following the first electron insertion, we observe a significant rearrangement of the hydrogen bonding network in the first solvation shell. The cobalt center turns out to be more accessible for the surrounding water molecules in the case of CoaTPy at all the intermediate steps, which explains its higher catalytic performance over CoaPPy. Following the first reduction reaction, a larger gain in reduction free energy is estimated for CoaTPy with respect to CoaPPy, with a difference of 0.14 eV, in line with the experiments. For the second reduction, instead, CoaPPy shows more negative reduction potential, by 0.41 eV.
dc.description.sponsorshipUniversity of Zurich, the University Research Priority Program Solar Light to Chemical Energy Conversion (LightChEC), National Centres of Competence in Research-Materials Revolution: Computational Design and Discovery of Novel Materials (NCCR-MARVEL); Adana Alparslan Turkes Science and Technology University Scientific Research Project Office [19103009]
dc.description.sponsorshipWe acknowledge PRACE for awarding us access to Marconi at Cineca, Italy. We acknowledge the financial support from the University of Zurich, the University Research Priority Program Solar Light to Chemical Energy Conversion (LightChEC), National Centres of Competence in Research-Materials Revolution: Computational Design and Discovery of Novel Materials (NCCR-MARVEL). Y.G. acknowledges Adana Alparslan Turkes Science and Technology University Scientific Research Project Office (Project ID: 19103009).
dc.identifier.doi10.1002/cphc.202000600
dc.identifier.endpage2700
dc.identifier.issn1439-4235
dc.identifier.issn1439-7641
dc.identifier.issue24
dc.identifier.pmid32955784
dc.identifier.scopus2-s2.0-85097007349
dc.identifier.scopusqualityQ2
dc.identifier.startpage2692
dc.identifier.urihttps://doi.org/10.1002/cphc.202000600
dc.identifier.urihttps://hdl.handle.net/20.500.14669/1726
dc.identifier.volume21
dc.identifier.wosWOS:000591684400001
dc.identifier.wosqualityQ2
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.indekslendigikaynakPubMed
dc.language.isoen
dc.publisherWiley-V C H Verlag Gmbh
dc.relation.ispartofChemphyschem
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/closedAccess
dc.snmzKA_20241211
dc.subjectab-initio molecular dynamics
dc.subjectcobalt-bipyridine-pyridine based catalysts
dc.subjectdensity functional theory
dc.subjectreduction free energy
dc.subjectwater reduction
dc.titleComparison of Penta and Tetra-pyridyl Cobalt-based Catalysts for Water Reduction: H2 Production Cycle, Solvent Response and Reduction Free Energy
dc.typeArticle

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