TY - JOUR
T1 - Organic linker defines the excited-state decay of photocatalytic MIL-125(Ti)-type materials
AU - Garcia Santaclara, J
AU - Nasalevich, M
AU - Castellanos Ortega, S
AU - Evers, WH
AU - Spoor, FCM
AU - Siebbeles, LDA
AU - Kapteijn, F
AU - Grozema, FC
AU - Houtepen, AJ
AU - Gascon, J
AU - van der Veen, MA
AU - More Authors, null
N1 - Green Open Access added to TU Delft Institutional Repository as part of the Taverne amendment. More information about this copyright law amendment can be found at https://www.openaccess.nl. Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.
PY - 2016
Y1 - 2016
N2 - Recently, MIL-125(Ti) and NH2-MIL-125(Ti), two titanium-based metal–organic frameworks, have attracted significant research attention in the field of photocatalysis for solar fuel generation. This work reveals that the differences between these structures are not only based on their light absorption range but also on the decay profile and topography of their excited states. In contrast to MIL-125(Ti), NH2-MIL-125(Ti) shows markedly longer lifetimes of the charge-separated state, which improves photoconversion by the suppression of competing decay mechanisms. We used spectroelectrochemistry and ultrafast spectroscopy to demonstrate that upon photoexcitation in NH2-MIL-125(Ti) the electron is located in the Ti-oxo clusters and the hole resides on the aminoterephthalate unit, specifically on the amino group. The results highlight the role of the amino group in NH2-MIL-125(Ti), the electron donation of which extends the lifetime of the photoexcited state substantially.
AB - Recently, MIL-125(Ti) and NH2-MIL-125(Ti), two titanium-based metal–organic frameworks, have attracted significant research attention in the field of photocatalysis for solar fuel generation. This work reveals that the differences between these structures are not only based on their light absorption range but also on the decay profile and topography of their excited states. In contrast to MIL-125(Ti), NH2-MIL-125(Ti) shows markedly longer lifetimes of the charge-separated state, which improves photoconversion by the suppression of competing decay mechanisms. We used spectroelectrochemistry and ultrafast spectroscopy to demonstrate that upon photoexcitation in NH2-MIL-125(Ti) the electron is located in the Ti-oxo clusters and the hole resides on the aminoterephthalate unit, specifically on the amino group. The results highlight the role of the amino group in NH2-MIL-125(Ti), the electron donation of which extends the lifetime of the photoexcited state substantially.
U2 - 10.1002/cssc.201501353
DO - 10.1002/cssc.201501353
M3 - Article
SN - 1864-564X
VL - 9
SP - 388
EP - 395
JO - ChemSusChem (online)
JF - ChemSusChem (online)
IS - 4
ER -