On the Electronic and Optical Properties of Metal-Organic Frameworks: Case Study of MIL-125 and MIL-125-NH2

被引：61

作者：

Capano, Gloria ^{[1
]}

Ambrosio, Francesco ^{[2
,3
,4
]}

Kampouri, Stavroula ^{[1
]}

Stylianou, Kyriakos C. ^{[1
]}

Pasquarello, Alfredo ^{[2
]}

Smit, Berend ^{[1
]}

机构：

[1] EPFL, Inst Sci & Ingn Chim, Lab Mol Simulat LSMO, CH-1951 Sion, Switzerland

[2] Ecole Polytech Fed Lausanne, CSEA, CH-1015 Lausanne, Switzerland

[3] Ist CNR Sci & Tecnol Mol ISTM CNR, Computat Lab Hybrid Organ Photovolta CLHYO, I-06123 Perugia, Italy

[4] Ist Italiano Tecnol, CompuNet, I-16163 Genoa, Italy

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2020年 / 124卷 / 07期

基金：

瑞士国家科学基金会;

关键词：

HYDROGEN-PRODUCTION; BAND-GAPS; WATER; OXIDATION; ALIGNMENT; ZN;

D O I：

10.1021/acs.jpcc.9b09453

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The photo-active MIL-125 and MIL-125-NH2 metal-organic frameworks (MOFs), despite having a very similar crystalline structure, exhibit different optical behaviors. Luminescence in MIL-125 decays in about 1 ns, while for its amino counterpart, the lifetime of charge carriers is at least 1 order of magnitude larger. The origin of this difference is the key element for understanding the photocatalytic behavior of MIL-125-NH2 when associated with active nanoparticles, a behavior that is completely absent in MIL-125. By performing advanced ab initio electronic structure calculations, we find that charge carriers interact differently in the two MOFs with subsequent effects on the luminescence lifetimes and their catalytic performances. To confirm the predictions of our model, we synthesized a novel material in the MIL-125 family, MIL-125-NH2-[10%](OH)(2), and confirm that our theory correctly predicts a faster decay compared to MIL-125-NH2.

引用

页码：4065 / 4072

页数：8

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