Show simple item record

dc.contributorVirginia Tech
dc.contributor.authorWhite, Travis A.
dc.contributor.authorKnoll, Jessica D.
dc.contributor.authorArachchige, Shamindri M.
dc.contributor.authorBrewer, Karen J.
dc.date.accessioned2014-01-15T14:16:36Z
dc.date.available2014-01-15T14:16:36Z
dc.date.issued2011-12-27
dc.identifier.citationWhite, Travis A.; Knoll, Jessica D.; Arachchige, Shamindri M.; Brewer, Karen J. 2012. "A Series of Supramolecular Complexes for Solar Energy Conversion via Water Reduction to Produce Hydrogen: An Excited State Kinetic Analysis of Ru(II),Rh(III),Ru(II) Photoinitiated Electron Collectors." Materials 2012, 5(1), 27-46; doi:10.3390/ma5010027.
dc.identifier.issn1996-1944
dc.identifier.urihttp://hdl.handle.net/10919/24850
dc.description.abstractMixed-metal supramolecular complexes have been designed that photochemically absorb solar light, undergo photoinitiated electron collection and reduce water to produce hydrogen fuel using low energy visible light. This manuscript describes these systems with an analysis of the photophysics of a series of six supramolecular complexes, [{(TL)2Ru(dpp)}2RhX2](PF6)5 with TL = bpy, phen or Ph2phen with X = Cl or Br. The process of light conversion to a fuel requires a system to perform a number of complicated steps including the absorption of light, the generation of charge separation on a molecular level, the reduction by one and then two electrons and the interaction with the water substrate to produce hydrogen. The manuscript explores the rate of intramolecular electron transfer, rate of quenching of the supramolecules by the DMA electron donor, rate of reduction of the complex by DMA from the 3MLCT excited state, as well as overall rate of reduction of the complex via visible light excitation. Probing a series of complexes in detail exploring the variation of rates of important reactions as a function of sub-unit modification provides insight into the role of each process in the overall efficiency of water reduction to produce hydrogen. The kinetic analysis shows that the complexes display different rates of excited state reactions that vary with TL and halide. The role of the MLCT excited state is elucidated by this kinetic study which shows that the 3MLCT state and not the 3MMCT is likely that key contributor to the photoreduction of these complexes. The kinetic analysis of the excited state dynamics and reactions of the complexes are important as this class of supramolecules behaves as photoinitiated electron collectors and photocatalysts for the reduction of water to hydrogen.
dc.format.mimetypeapplication/pdf
dc.language.isoen_US
dc.publisherMDPI
dc.rightsCreative Commons Attribution 4.0 International
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectintramolecular electron transfer
dc.subjectphotoinitiated electron collection
dc.subjectsupramolecular photocatalysis
dc.subjectexcited state quenching;
dc.subjecthydrogen production
dc.titleA Series of Supramolecular Complexes for Solar Energy Conversion via Water Reduction to Produce Hydrogen: An Excited State Kinetic Analysis of Ru(II),Rh(III),Ru(II) Photoinitiated Electron Collectorsen_US
dc.typeArticle - Refereed
dc.identifier.urlhttp://www.mdpi.com/1996-1944/5/1/27
dc.date.accessed2014-01-06
dc.title.serialMaterials
dc.identifier.doihttps://doi.org/10.3390/ma5010027
dc.type.dcmitypeText


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record

Creative Commons Attribution 4.0 International
License: Creative Commons Attribution 4.0 International