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
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
收藏
页码:388 / 395
页数:8
相关论文
共 45 条
[21]   Visible-light-driven photocatalytic degradation of pollutants over Cu-doped NH2 -MIL-125(Ti) [J].
Ao, Dan ;
Zhang, Jiang ;
Liu, Hong .
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 2018, 364 :524-533
[22]   Inhibiting photocatalytic electron-hole recombination by coupling MIL-125 (Ti) with chemically reduced, nitrogen-containing graphene oxide [J].
Fatima, Rida ;
Kim, Jong-Oh .
APPLIED SURFACE SCIENCE, 2021, 541
[23]   First-Principles Calculations of Excited-State Decay Rate Constants in Organic Fluorophores [J].
do Casal, Mariana T. ;
Veys, Koen ;
Bousquet, Manon H. E. ;
Escudero, Daniel ;
Jacquemin, Denis .
JOURNAL OF PHYSICAL CHEMISTRY A, 2023, 127 (48) :10033-10053
[24]   In-Situ generation of nano TiO2 from MIL-125(Ti) and its role in boosting the photocatalytic degradation of tetracycline hydrochloride [J].
Lu, Chuyu ;
Yi, Futao ;
Ma, Jianqing ;
Sillanpaa, Mika Erik Tapio ;
Zhou, Minghua ;
Ye, Qing ;
Jin, Huixia ;
Zhang, Kefeng .
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 2025, 459
[25]   Zn-free MOFs like MIL-53(Al) and MIL-125(Ti) for the preparation of defect-rich, ultrafine ZnO nanosheets with high photocatalytic performance [J].
Xiao, He ;
Zhang, Wenyao ;
Yao, Qiushi ;
Huang, Liulian ;
Chen, Lihui ;
Boury, Bruno ;
Chen, Zhongwei .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2019, 244 :719-731
[26]   Plasma-Induced Defects Enhance the Visible-Light Photocatalytic Activity of MIL-125(Ti)-NH2 for Overall Water Splitting [J].
Cabrero-Antonino, Maria ;
Albero, Josep ;
Garcia-Valles, Cristina ;
alvaro, Mercedes ;
Navalon, Sergio ;
Garcia, Hermenegildo .
CHEMISTRY-A EUROPEAN JOURNAL, 2020, 26 (67) :15682-15689
[27]   Cyclohexene Oxidation with H2O2 over Metal-Organic Framework MIL-125(Ti): The Effect of Protons on Reactivity [J].
Maksimchuk, Nataliya ;
Lee, Ji Sun ;
Ayupov, Artem ;
Chang, Jong-San ;
Kholdeeva, Oxana .
CATALYSTS, 2019, 9 (04)
[28]   Separation properties of the MIL-125(Ti) Metal-Organic Framework in high-performance liquid chromatography revealing cis/trans selectivity [J].
Van der Perre, Stijn ;
Liekens, Anuschka ;
Bueken, Bart ;
De Vos, Dirk E. ;
Baron, Gino V. ;
Denayer, Joeri F. M. .
JOURNAL OF CHROMATOGRAPHY A, 2016, 1469 :68-76
[29]   A novel solar-triggered MIL-125(Ti)/g-C3N4/SA composite aerogel with high catalytic activity for degradation of organic contaminants [J].
Zhao, Jie ;
Li, Bingzhang ;
Liu, Zongyang ;
Dai, Danling ;
Li, Yuqi ;
Shi, Ronghui ;
Zhang, Hui .
SEPARATION AND PURIFICATION TECHNOLOGY, 2021, 279
[30]   Effective elimination of As(III) via simultaneous photocatalytic oxidation and adsorption by a bifunctional cake-like TiO2 derived from MIL-125(Ti) [J].
Liu, Zhongmin ;
Wu, Yongchuan ;
Chen, Jitao ;
Li, Yaru ;
Zhao, Jingyu ;
Gao, Kaihua ;
Na, Ping .
CATALYSIS SCIENCE & TECHNOLOGY, 2018, 8 (07) :1936-1944