Tunable optical properties of isoreticular UiO-67 MOFs for photocatalysis: a theoretical study

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dc.article.numberd4dt01017e
dc.catalogadoraba
dc.contributor.authorTreto Suárez, Manuel A.
dc.contributor.authorHidalgo Rosa, Yoan
dc.contributor.authorSaavedra Torres, Mario
dc.contributor.authorKoivisto, Bryan D.
dc.contributor.authorMena Ulecia, Karel
dc.contributor.authorPáez Hernández, Dayan
dc.contributor.authorZarate, Ximena
dc.contributor.authorSchott Verdugo, Eduardo
dc.date.accessioned2024-07-18T21:31:08Z
dc.date.available2024-07-18T21:31:08Z
dc.date.issued2024
dc.description.abstractA theoretical study of the reported photocatalytic systems based on Zr-based MOF (UiO-67) with biphenyl-4,4 '-dicarboxylic acid (bpdc) and 2,2 '-bipyridine-5,5 '-dicarboxylic acid (bpydc) as linkers was performed. Quantum chemical calculations were carried out to understand the optical properties of the materials and to facilitate the rational design of new UiO-67 derivatives with potentially improved features as photocatalysts under ambient conditions. Hence, the effect of the structural modifications on the optical properties was studied considering different designs based on the nature of the linkers: in 1 only the bpdc linker was considered, or the mixture 1 : 1 between bpdc and bpydc linkers (labeled as 1A). Also, substituents R, -NH2, and -SH, were included in the 1A MOF only over the bpdc linker (labeled as 1A-bpdc-R) and on both bpdc and bpydc linkers (labeled as 1A-R). Thus a family of six isoreticular UiO-67 derivatives was theoretically characterized using Density Functional Theory (DFT) calculations on the ground singlet (S0) and first excited states (singlet and triplet) using Time-Dependent Density Functional Theory (TD-DFT), multiconfigurational post-Hartree-Fock method via Complete Active Space Self-Consistent Field (CASSCF). In addition, the use of periodic DFT calculations suggest that the energy transfer (ET) channel between bpdc and bpydc linkers might generate more luminescence quenching of 1A when compare to 1. Besides, the results suggest that the 1A-R (R: -SH and NH2) can be used under ambient conditions; however, the ET exhibited by 1A, cannot take place in the same magnitude in these systems. These ET can favor the photocatalytic reduction of a potential metal ion, that can coordinate with the bpydc ligand, via LMCT transition. Consequently, the MOF might be photocatalytically active against molecules of interest (such as H2, N2, CO2, among others) with photo-reduced metal ions. These theoretical results serve as a useful tool to guide experimental efforts in the design of new photocatalytic MOF-based systems., A theoretical computational protocol was performed to understand the optical properties, the deactivation mechanisms, and the substituent effect for a photocatalytic MOF-based system.
dc.fechaingreso.objetodigital2024-07-18
dc.fuente.origenWOS
dc.identifier.doi10.1039/d4dt01017e
dc.identifier.eissn1477-9234
dc.identifier.issn1477-9226
dc.identifier.urihttps://doi.org/10.1039/d4dt01017e
dc.identifier.urihttps://repositorio.uc.cl/handle/11534/87140
dc.identifier.wosidWOS:001251450900001
dc.information.autorucEscuela de Química; Schott Verdugo, Eduardo; 0000-0002-2546-304X; 1020229
dc.issue.numero27
dc.language.isoen
dc.nota.accesocontenido completo
dc.pagina.final11325
dc.pagina.inicio11310
dc.revistaDalton Transactions
dc.rightsacceso abierto
dc.rights.licenseATTRIBUTION-NONCOMMERCIAL 3.0 UNPORTED
dc.rights.urihttps://creativecommons.org/licenses/by-nc/3.0/
dc.subject.ddc510
dc.subject.deweyMatemática física y químicaes_ES
dc.subject.ods07 Affordable and clean energy
dc.subject.odspa07 Energía asequible y no contaminante
dc.titleTunable optical properties of isoreticular UiO-67 MOFs for photocatalysis: a theoretical study
dc.typeartículo
dc.volumen53
sipa.codpersvinculados1020229
sipa.trazabilidadWOS;2024-06-29
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