Electronic origins of photocatalytic activity in d0 metal organic frameworks

Maxim A. Nasalevich, Christopher H. Hendon, Jara G. Santaclara, Katrine Svane, Bart Van Der Linden, Sergey L. Veber, Matvey V. Fedin, Arjan J. Houtepen, Monique A. Van Der Veen, Freek Kapteijn, Aron Walsh, Jorge Gascon

Research output: Contribution to journalArticle

72 Citations (Scopus)

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.

Original languageEnglish
Article number23676
JournalScientific reports
Volume6
DOIs
Publication statusPublished - 2016 Mar 29

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Metals
Quantum chemistry
Photoexcitation
Binding energy
Absorption spectroscopy
Electronic properties
Paramagnetic resonance
Charge transfer
Ligands
N(1)-methyl-2-lysergic acid diethylamide

All Science Journal Classification (ASJC) codes

  • General

Cite this

Nasalevich, M. A., Hendon, C. H., Santaclara, J. G., Svane, K., Van Der Linden, B., Veber, S. L., ... Gascon, J. (2016). Electronic origins of photocatalytic activity in d0 metal organic frameworks. Scientific reports, 6, [23676]. https://doi.org/10.1038/srep23676
Nasalevich, Maxim A. ; Hendon, Christopher H. ; Santaclara, Jara G. ; Svane, Katrine ; Van Der Linden, Bart ; Veber, Sergey L. ; Fedin, Matvey V. ; Houtepen, Arjan J. ; Van Der Veen, Monique A. ; Kapteijn, Freek ; Walsh, Aron ; Gascon, Jorge. / Electronic origins of photocatalytic activity in d0 metal organic frameworks. In: Scientific reports. 2016 ; Vol. 6.
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Nasalevich, MA, Hendon, CH, Santaclara, JG, Svane, K, Van Der Linden, B, Veber, SL, Fedin, MV, Houtepen, AJ, Van Der Veen, MA, Kapteijn, F, Walsh, A & Gascon, J 2016, 'Electronic origins of photocatalytic activity in d0 metal organic frameworks', Scientific reports, vol. 6, 23676. https://doi.org/10.1038/srep23676

Electronic origins of photocatalytic activity in d0 metal organic frameworks. / Nasalevich, Maxim A.; Hendon, Christopher H.; Santaclara, Jara G.; Svane, Katrine; Van Der Linden, Bart; Veber, Sergey L.; Fedin, Matvey V.; Houtepen, Arjan J.; Van Der Veen, Monique A.; Kapteijn, Freek; Walsh, Aron; Gascon, Jorge.

In: Scientific reports, Vol. 6, 23676, 29.03.2016.

Research output: Contribution to journalArticle

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AU - Nasalevich, Maxim A.

AU - Hendon, Christopher H.

AU - Santaclara, Jara G.

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AU - Van Der Linden, Bart

AU - Veber, Sergey L.

AU - Fedin, Matvey V.

AU - Houtepen, Arjan J.

AU - Van Der Veen, Monique A.

AU - Kapteijn, Freek

AU - Walsh, Aron

AU - Gascon, Jorge

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N2 - 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.

AB - 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.

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Nasalevich MA, Hendon CH, Santaclara JG, Svane K, Van Der Linden B, Veber SL et al. Electronic origins of photocatalytic activity in d0 metal organic frameworks. Scientific reports. 2016 Mar 29;6. 23676. https://doi.org/10.1038/srep23676