TY - JOUR
T1 - Electronic origins of photocatalytic activity in d 0 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
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.
UR - http://www.scopus.com/inward/record.url?scp=84962348619&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1038/srep23676
UR - http://dx.doi.org/10.1038/srep23676
U2 - 10.1038/srep23676
DO - 10.1038/srep23676
M3 - Article
AN - SCOPUS:84962348619
SN - 2045-2322
VL - 6
JO - Scientific Reports
JF - Scientific Reports
M1 - 23676
ER -