Organic Linker Defines the Excited-State Decay of Photocatalytic MIL-125(Ti)-Type Materials

Jara G. Santaclara, Maxim A. Nasalevich, Sonia Castellanos, Wiel H. Evers, Frank C.M. Spoor, Kamila Rock, Laurens D.A. Siebbeles, Freek Kapteijn, Ferdinand Grozema, Arjan Houtepen, Jorge Gascon, Johannes Hunger, Monique A. Van Der Veen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

86 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)388-395
Number of pages8
Issue number4
StatePublished - Feb 19 2016
Externally publishedYes


  • amines
  • metal-organic frameworks
  • photochemistry
  • titanium
  • water splitting

ASJC Scopus subject areas

  • General Chemical Engineering
  • General Energy
  • General Materials Science
  • Environmental Chemistry


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