Photoelectrochemical water oxidation by a MOF/semiconductor composite

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dc.contributor.authorGibbons, Bradleyen
dc.contributor.authorCairnie, Daniel R.en
dc.contributor.authorThomas, Benjaminen
dc.contributor.authorYang, Xiaozhouen
dc.contributor.authorIlic, Stefanen
dc.contributor.authorMorris, Amanda J.en
dc.date.accessioned2023-10-06T12:49:34Zen
dc.date.available2023-10-06T12:49:34Zen
dc.date.issued2023-05en
dc.description.abstractArtificial photosynthesis is one of the most promising forms of renewable fuel production, due to the abundance of water, carbon dioxide, and sunlight. However, the water oxidation reaction remains a significant bottleneck due to the high thermodynamic and kinetic requirements of the four-electron process. While significant work has been done on the development of catalysts for water splitting, many of the catalysts reported to date operate at high overpotentials or with the use of sacrificial oxidants to drive the reaction. Here, we present a catalyst embedded metal-organic framework (MOF)/ semiconductor composite that performs photoelectrochemical oxidation of water at a formal underpotential. Ru-UiO-67 (where Ru stands for the water oxidation catalyst [Ru(tpy)(dcbpy)OH2](2+) (tpy = 2,2':6',2''-terpyridine, dcbpy = 5,5-dicarboxy-2,2'-bipyridine)) has been previously shown to be active for water oxidation under both chemical and electrochemical conditions, but here we demonstrate, for the first time, incorporation of a light harvesting n-type semiconductor as a base photoelectrode. RuUiO-67/WO3 is active for photoelectrochemical water oxidation at a thermodynamic underpotential ( h approximate to 200 mV; E-onset = 600 mV vs. NHE), and incorporation of a molecular catalyst onto the oxide layer increases efficiency of charge transport and separation over bare WO3. The charge-separation process was evaluated with ultrafast transient absorption spectroscopy (ufTA) and photocurrent density measurements. These studies suggest that a key contributor to the photocatalytic process involves a hole transfer from excited WO* (3) to Ru-UiO-67. To our knowledge, this is the first report of a MOFbased catalyst active for water oxidation at a thermodynamic underpotential, a key step towards lightdriven water oxidation.en
dc.description.notesThis work was supported by the Department of Energy under Grant DE-SC0012445. This work used shared facilities at the Nanoscale Characterization and Fabrication Laboratory, which is funded and managed by Virginia Tech's Institute for Critical Technology and Applied Science. Additional support for these facilities is provided by the Virginia Tech National Center for Earth and Environmental Nanotechnology Infrastructure (NanoEarth), a member of the National Nanotechnology Coordinated Infrastructure (NNCI), supported by NSF (ECCS 1542100 and ECCS 2025151).en
dc.description.sponsorshipDepartment of Energy [DE-SC0012445]; NSF [ECCS 1542100, ECCS 2025151]en
dc.description.versionPublished versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.doihttps://doi.org/10.1039/d2sc06361aen
dc.identifier.eissn2041-6539en
dc.identifier.issn2041-6520en
dc.identifier.issue18en
dc.identifier.pmid37181771en
dc.identifier.urihttp://hdl.handle.net/10919/116421en
dc.identifier.volume14en
dc.language.isoenen
dc.publisherRoyal Society of Chemistryen
dc.rightsCreative Commons Attribution-NonCommercial 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by-nc/4.0/en
dc.subjectmetal-organic frameworken
dc.subjectcharge-carrier dynamicsen
dc.subjectthin-filmsen
dc.subjectruthenium(ii) complexesen
dc.subjectabsorption-spectraen
dc.subjectsolaren
dc.subjectcatalysten
dc.subjectphotoanodeen
dc.subjectstateen
dc.subjectidentificationen
dc.titlePhotoelectrochemical water oxidation by a MOF/semiconductor compositeen
dc.title.serialChemical Scienceen
dc.typeArticle - Refereeden
dc.type.dcmitypeTexten

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