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

doi:10.1002/cssc.201501353

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 journal › Article › peer-review

94 Scopus citations

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.

Original language	English (US)
Pages (from-to)	388-395
Number of pages	8
Journal	CHEMSUSCHEM
Volume	9
Issue number	4
DOIs	https://doi.org/10.1002/cssc.201501353
State	Published - Feb 19 2016
Externally published	Yes

Keywords

amines
metal-organic frameworks
photochemistry
titanium
water splitting

ASJC Scopus subject areas

General Chemical Engineering
General Energy
General Materials Science
Environmental Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/cssc.201501353

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Santaclara, J. G., Nasalevich, M. A., Castellanos, S., Evers, W. H., Spoor, F. C. M., Rock, K., Siebbeles, L. D. A., Kapteijn, F., Grozema, F., Houtepen, A., Gascon, J., Hunger, J., & Van Der Veen, M. A. (2016). Organic Linker Defines the Excited-State Decay of Photocatalytic MIL-125(Ti)-Type Materials. CHEMSUSCHEM, 9(4), 388-395. https://doi.org/10.1002/cssc.201501353

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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.",

keywords = "amines, metal-organic frameworks, photochemistry, titanium, water splitting",

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

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doi = "10.1002/cssc.201501353",

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T1 - Organic Linker Defines the Excited-State Decay of Photocatalytic MIL-125(Ti)-Type Materials

AU - Santaclara, Jara G.

AU - Nasalevich, Maxim A.

AU - Castellanos, Sonia

AU - Evers, Wiel H.

AU - Spoor, Frank C.M.

AU - Rock, Kamila

AU - Siebbeles, Laurens D.A.

AU - Kapteijn, Freek

AU - Grozema, Ferdinand

AU - Houtepen, Arjan

AU - Gascon, Jorge

AU - Hunger, Johannes

AU - Van Der Veen, Monique A.

PY - 2016/2/19

Y1 - 2016/2/19

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.

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KW - metal-organic frameworks

KW - photochemistry

KW - titanium

KW - water splitting

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

Abstract

Keywords

ASJC Scopus subject areas

UN SDGs

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