Print Email Facebook Twitter Electronic origins of photocatalytic activity in d0 metal organic frameworks Title Electronic origins of photocatalytic activity in d0 metal organic frameworks Author Nasalevich, M. (TU Delft ChemE/Catalysis Engineering) Hendon, Christopher H. (University of Bath) Garcia Santaclara, J. (TU Delft ChemE/Catalysis Engineering) Svane, Katrine (University of Bath) van der Linden, B. (TU Delft ChemE/Catalysis Engineering) Veber, Sergey L. (Novosibirsk State University) Fedin, Matvey V. (Novosibirsk State University) Houtepen, A.J. (TU Delft ChemE/Opto-electronic Materials) van der Veen, M.A. (TU Delft ChemE/Catalysis Engineering) Kapteijn, F. (TU Delft ChemE/Catalysis Engineering) Walsh, Aron (Yonsei University) Gascon, Jorge (TU Delft ChemE/Catalysis Engineering) Date 2016-03-29 Abstract Metal-organic frameworks (MOFs) containing d0 metals such as NH2-MIL-125(Ti), NH2-UiO-66(Zr) and NH2-UiO-66(Hf) are among the most studied MOFs for photocatalytic applications. Despite structural similarities, we demonstrate that the electronic properties of these MOFs are markedly different. As revealed by quantum chemistry, EPR measurements and transient absorption spectroscopy, the highest occupied and lowest unoccupied orbitals of NH2-MIL-125(Ti) promote a long lived ligandto-metal charge transfer upon photoexcitation, making this material suitable for photocatalytic applications. In contrast, in case of UiO materials, the d-orbitals of Zr and Hf, are too low in binding energy and thus cannot overlap with the π orbital of the ligand, making both frontier orbitals localized at the organic linker. This electronic reconfiguration results in short exciton lifetimes and diminishes photocatalytic performance. These results highlight the importance of orbital contributions at the band edges and delineate future directions in the development of photo-active hybrid solids. To reference this document use: http://resolver.tudelft.nl/uuid:0283aa21-1863-4e7f-a7eb-90b8c49aa3bf DOI https://doi.org/10.1038/srep23676 ISSN 2045-2322 Source Scientific Reports, 6, 1-9 Part of collection Institutional Repository Document type journal article Rights © 2016 M. Nasalevich, Christopher H. Hendon, J. Garcia Santaclara, Katrine Svane, B. van der Linden, Sergey L. Veber, Matvey V. Fedin, A.J. Houtepen, M.A. van der Veen, F. Kapteijn, Aron Walsh, Jorge Gascon Files PDF srep23676.pdf 1.3 MB Close viewer /islandora/object/uuid:0283aa21-1863-4e7f-a7eb-90b8c49aa3bf/datastream/OBJ/view