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dc.contributor.authorSchmitt, Wolfgang
dc.date.accessioned2022-06-23T08:58:46Z
dc.date.available2022-06-23T08:58:46Z
dc.date.issued2021
dc.date.submitted2021en
dc.identifier.citationSoriano-López, J.; Elliott, R.; Kathalikkattil, A.C.; Ako, A.M.; Schmitt, W. Tuning the Catalytic Water Oxidation Activity through Structural Modifications of High-Nuclearity Mn-oxo Clusters [Mn18M] (M = Sr2+, Mn2+). Water 2021, 13, 2042en
dc.identifier.otherY
dc.identifier.urihttp://hdl.handle.net/2262/99587
dc.description.abstractThe water oxidation half-reaction is considered the bottleneck in the development of technological advances to replace fossil fuels with sustainable and economically affordable energy sources. In natural photosynthesis, water oxidation occurs in the oxygen evolving complex (OEC), a manganese-oxo cluster {Mn4CaO5} with a cubane-like topology that is embedded within a redox-active protein environment located in photosystem II (PS II). Therefore, the preparation of biomimetic manganese-based compounds is appealing for the development of efficient and inexpensive water oxidation catalysts. Here, we present the water oxidation catalytic activity of a high-nuclearity mixed-metal manganese-strontium cluster, [MnIII12MnII6Sr(μ4-O8)(μ3-Cl)8(HLMe)12(MeCN)6]Cl2∙15MeOH (Mn18Sr) (HLMe = 2,6-bis(hydroxymethyl)-p-cresol), in neutral media. This biomimetic mixed-valence cluster features different cubane-like motifs and it is stabilized by redox-active, quinone-like organic ligands. The complex displays a low onset overpotential of 192 mV and overpotentials of 284 and 550 mV at current densities of 1 mA cm−2 and 10 mA cm−2, respectively. Direct O2 evolution measurements under visible light-driven water oxidation conditions demonstrate the catalytic capabilities of this cluster, which exhibits a turnover frequency of 0.48 s−1 and a turnover number of 21.6. This result allows for a direct comparison to be made with the structurally analogous Mn-oxo cluster [MnIII12MnII7(µ4-O)8(µ3-OCH3)2(µ3-Br)6(HLMe)12(MeOH)5(MeCN)]Br2·9MeCN·MeOH (Mn19), the water oxidation catalytic activity of which was recently reported by us. This work highlights the potential of this series of compounds towards the water oxidation reaction and their amenability to induce structural changes that modify their reactivity. View Full-Texten
dc.language.isoenen
dc.relation.ispartofseriesWater (Switzerland);
dc.relation.ispartofseries13;
dc.relation.ispartofseries15;
dc.rightsYen
dc.subjectImmobilized molecular catalysten
dc.subjectBiomimetic catalysten
dc.subjectCubane-type structureen
dc.subjectRedox-active ligandsen
dc.subjectManganeseen
dc.subjectWater oxidation catalysisen
dc.subjectOxygen evolution reactionen
dc.titleTuning the Catalytic Water Oxidation Activity through Structural Modifications of High-Nuclearity Mn-oxo Clusters [Mn18M] (M = Sr2+, Mn2+)en
dc.typeJournal Articleen
dc.type.supercollectionscholarly_publicationsen
dc.type.supercollectionrefereed_publicationsen
dc.identifier.peoplefinderurlhttp://people.tcd.ie/schmittw
dc.identifier.rssinternalid243678
dc.identifier.doihttp://dx.doi.org/10.3390/w13152042
dc.rights.ecaccessrightsopenAccess


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