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

doi:10.1038/srep23676

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

Department of Physics

Research output: Contribution to journal › Article › peer-review

208 Scopus citations

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 language	English
Article number	23676
Journal	Scientific Reports
Volume	6
DOIs	https://doi.org/10.1038/srep23676
State	Published - 29 Mar 2016

Bibliographical note

Funding Information:
Dr. Sonia Castellanos Ortega is gratefully acknowledged for scanning electron microscopy. The Dutch National Research School Combination Catalysis Controlled by Chemical Design (NRSC-Catalysis) is acknowledged for funding the work at Delft. The work at Bath was supported by the European Research Council (Starting Grant 277757), and access to ARCHER through membership in the UK's HPC Materials Chemistry Consortium, which is funded by EPSRC (Grant No. EP/L00202). S.L.V. and M.V.F. thank the Russian Science Foundation (no. 14-13-00826).

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10.1038/srep23676

Cite this

@article{c66c5c5eaed04704a351917ca490f1fa,

title = "Electronic origins of photocatalytic activity in d0 metal organic frameworks",

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.",

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

note = "Funding Information: Dr. Sonia Castellanos Ortega is gratefully acknowledged for scanning electron microscopy. The Dutch National Research School Combination Catalysis Controlled by Chemical Design (NRSC-Catalysis) is acknowledged for funding the work at Delft. The work at Bath was supported by the European Research Council (Starting Grant 277757), and access to ARCHER through membership in the UK's HPC Materials Chemistry Consortium, which is funded by EPSRC (Grant No. EP/L00202). S.L.V. and M.V.F. thank the Russian Science Foundation (no. 14-13-00826).",

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month = mar,

day = "29",

doi = "10.1038/srep23676",

language = "English",

volume = "6",

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T1 - Electronic origins of photocatalytic activity in d0 metal organic frameworks

AU - Nasalevich, Maxim A.

AU - Hendon, Christopher H.

AU - Santaclara, Jara G.

AU - Svane, Katrine

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

N1 - Funding Information: Dr. Sonia Castellanos Ortega is gratefully acknowledged for scanning electron microscopy. The Dutch National Research School Combination Catalysis Controlled by Chemical Design (NRSC-Catalysis) is acknowledged for funding the work at Delft. The work at Bath was supported by the European Research Council (Starting Grant 277757), and access to ARCHER through membership in the UK's HPC Materials Chemistry Consortium, which is funded by EPSRC (Grant No. EP/L00202). S.L.V. and M.V.F. thank the Russian Science Foundation (no. 14-13-00826).

PY - 2016/3/29

Y1 - 2016/3/29

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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