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

被引：102

作者：

Santaclara, Jara G. ^{[1
]}

Nasalevich, Maxim A. ^{[1
]}

Castellanos, Sonia ^{[1
]}

Evers, Wiel H. ^{[2
,3
]}

Spoor, Frank C. M. ^{[2
]}

Rock, Kamila ^{[4
]}

Siebbeles, Laurens D. A. ^{[2
]}

Kapteijn, Freek ^{[1
]}

Grozema, Ferdinand ^{[2
]}

Houtepen, Arjan ^{[2
]}

Gascon, Jorge ^{[1
]}

Hunger, Johannes ^{[4
]}

van der Veen, Monique A. ^{[1
]}

机构：

[1] Delft Univ Technol, Dept Chem Engn, Catalysis Engn, Julianalaan 136, NL-2628 BL Delft, Netherlands

[2] Delft Univ Technol, Dept Chem Engn, Optoelect Mat, Julianalaan 136, NL-2628 BL Delft, Netherlands

[3] Delft Univ Technol, Kavli Inst Nanosci, Lorentzweg 1, NL-2628 CJ Delft, Netherlands

[4] Max Planck Inst Polymer Res, Ackermannweg 10, D-55128 Mainz, Germany

来源：

CHEMSUSCHEM | 2016年 / 9卷 / 04期

关键词：

amines; metal-organic frameworks; photochemistry; titanium; water splitting; ELECTRON-TRANSFER; RADICAL CATIONS; AROMATIC-AMINES; WATER OXIDATION; PHOTOSYSTEM-II; TRIPLET-STATES; CO2; REDUCTION; FRAMEWORKS; ANILINE; TITANIUM(IV);

D O I：

10.1002/cssc.201501353

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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.

引用

页码：388 / 395

页数：8

共 56 条

[1] Impact assessment and efficiency evaluation of hydrogen production methods [J].

Acar, Canan ;

Dincer, Ibrahim .

INTERNATIONAL JOURNAL OF ENERGY RESEARCH, 2015, 39 (13) :1757-1768

[2] Semiconductor behavior of a metal-organic framework (MOF) [J].

Alvaro, Mercedes ;

Carbonell, Esther ;

Ferrer, Belen ;

Llabres i Xamena, Francesc X. ;

Garcia, Hermenegildo .

CHEMISTRY-A EUROPEAN JOURNAL, 2007, 13 (18) :5106-5112

[3] Ultrafast electron transfer dynamics from molecular adsorbates to semiconductor nanocrystalline thin films [J].

Asbury, JB ;

Hao, E ;

Wang, YQ ;

Ghosh, HN ;

Lian, TQ .

JOURNAL OF PHYSICAL CHEMISTRY B, 2001, 105 (20) :4545-4557

[4] Ultrafast transient absorption spectroscopy: principles and application to photosynthetic systems [J].

Berera, Rudi ;

van Grondelle, Rienk ;

Kennis, John T. M. .

PHOTOSYNTHESIS RESEARCH, 2009, 101 (2-3) :105-118

[5] Multistep π Dimerization of Tetrakis(n-decyl) heptathienoacene Radical Cations: A Combined Experimental and Theoretical Study [J].

Capel Ferron, Cristina ;

Capdevila-Cortada, Marcal ;

Balster, Russell ;

Hartl, Frantisek ;

Niu, Weijun ;

He, Mingqian ;

Novoa, Juan J. ;

Lopez Navarrete, Juan T. ;

Hernandez, Victor ;

Ruiz Delgado, M. Carmen .

CHEMISTRY-A EUROPEAN JOURNAL, 2014, 20 (33) :10351-10359

[6] Semiconductor-based Photocatalytic Hydrogen Generation [J].

Chen, Xiaobo ;

Shen, Shaohua ;

Guo, Liejin ;

Mao, Samuel S. .

CHEMICAL REVIEWS, 2010, 110 (11) :6503-6570

[7] Binding of catechols to mononuclear titanium(IV) and to 1-and 5-nm TiO2 nanoparticles [J].

Creutz, Carol ;

Chou, Mei H. .

INORGANIC CHEMISTRY, 2008, 47 (09) :3509-3514

[8] A New Photoactive Crystalline Highly Porous Titanium(IV) Dicarboxylate [J].

Dan-Hardi, Meenakshi ;

Serre, Christian ;

Frot, Theo ;

Rozes, Laurence ;

Maurin, Guillaume ;

Sanchez, Clement ;

Ferey, Gerard .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (31) :10857-+

[9] Adsorptive characterization of porous solids: Error analysis guides the way [J].

De Lange, Martijn F. ;

Vlugt, Thijs J. H. ;

Gascon, Jorge ;

Kapteijn, Freek .

MICROPOROUS AND MESOPOROUS MATERIALS, 2014, 200 :199-215

[10] Evidence of Photoinduced Charge Separation in the Metal-Organic Framework MIL-125(Ti)-NH2 [J].

de Miguel, Maykel ;

Ragon, Florence ;

Devic, Thomas ;

Serre, Christian ;

Horcajada, Patricia ;

Garcia, Hermenegildo .

CHEMPHYSCHEM, 2012, 13 (16) :3651-3654

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