title: Organic Linker Defines the Excited-State Decay of Photocatalytic MIL-125(Ti)-Type Materials.
abstract: 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.
authors: Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands.
authors: Jara G
authors: JG
authors: Santaclara
authors: Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands.
authors: Maxim A
authors: MA
authors: Nasalevich
authors: Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands.
authors: Sonia
authors: S
authors: Castellanos
authors: Optoelectronic Materials, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands.|Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ, Delft, The Netherlands.
authors: Wiel H
authors: WH
authors: Evers
authors: Optoelectronic Materials, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands.
authors: Frank C M
authors: FC
authors: Spoor
authors: Max Planck Institute for Polymer Research, Ackermannweg 10, 55128, Mainz, Germany.
authors: Kamila
authors: K
authors: Rock
authors: Optoelectronic Materials, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands.
authors: Laurens D A
authors: LD
authors: Siebbeles
authors: Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands.
authors: Freek
authors: F
authors: Kapteijn
authors: Optoelectronic Materials, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands.
authors: Ferdinand
authors: F
authors: Grozema
authors: Optoelectronic Materials, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands.
authors: Arjan
authors: A
authors: Houtepen
authors: Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands.
authors: Jorge
authors: J
authors: Gascon
authors: Max Planck Institute for Polymer Research, Ackermannweg 10, 55128, Mainz, Germany.
authors: Johannes
authors: J
authors: Hunger
authors: Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands. M.A.vanderVeen@tudelft.nl.
authors: Monique A
authors: MA
authors: van der Veen
mesh_terms: D002384:Catalysis; D009930:Organic Chemicals / Q000737:chemistry*; D010777:Photochemistry; D014025:Titanium / Q000737:chemistry*
chemical_list: D009930:Organic Chemicals; D014025:Titanium
keywords: amines; metal-organic frameworks; photochemistry; titanium; water splitting