Functionalization in Flexible Porous Solids: Effects on the Pore Opening and the Host-Guest Interactions

被引：437

作者：

Devic, Thomas ^{[1
]}

Horcajada, Patricia ^{[1
]}

Serre, Christian ^{[1
]}

Salles, Fabrice ^{[2
]}

Maurin, Guillaume ^{[2
]}

Moulin, Beatrice ^{[3
]}

Heurtaux, Daniela ^{[1
]}

Clet, Guillaume ^{[3
]}

Vimont, Alexandre ^{[3
]}

Greneche, Jean-Marc ^{[4
]}

Le Ouay, Benjamin ^{[1
]}

Moreau, Florian ^{[1
]}

Magnier, Emmanuel ^{[1
]}

Filinchuk, Yaroslav ^{[5
]}

Marrot, Jerome ^{[1
]}

Lavalley, Jean-Claude ^{[3
]}

Daturi, Marco ^{[3
]}

Ferey, Gerard ^{[1
]}

机构：

[1] Univ Versailles St Quentin en Yvelines, CNRS, Inst Lavoisier, UMR 8180, F-78035 Versailles, France

[2] Univ Montpellier 2, ENSCM, CNRS, Inst Charles Gerhardt Montpellier,UMR 5253, F-34095 Montpellier 05, France

[3] Univ Caen, ENSICAEN, CNRS, Catalyse & Spectrochim Lab, F-14050 Caen, France

[4] Univ Maine, CNRS, Lab Phys Etat Condense, UMR 6087, F-72085 Le Mans, France

[5] ESRF, Swiss Norwegian Beamlines, F-38043 Grenoble, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 03期

关键词：

METAL-ORGANIC-FRAMEWORK; HYDROGEN-ADSORPTION PROPERTIES; POSTSYNTHETIC MODIFICATION; COVALENT MODIFICATION; COORDINATION POLYMER; GAS-ADSORPTION; MIL-53; BENZENEDICARBOXYLATE; SEPARATION; DESIGN;

D O I：

10.1021/ja9092715

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The synthesis on the gram scale and characterization of a series of flexible functionalized iron terephthalate MIL-53(Fe) type solids are reported. Chemical groups of various polarities, hydrophilicities, and acidities (-Cl, -Br, -CF3, -CH3, -NH2, -OH, -CO2H) were introduced through the aromatic linker, to systematically modify the pore surface. X-ray powder diffraction (XRPD), molecular simulations, thermogravimetric analyses, and in situ IR and Fe-57 Mossbauer spectrometries indicate some similarities with the pristine MIL-53(Fe) solid, with the adoption of the narrow pore form for all solids in both the hydrated and dry forms. Combined XRPD and computational structure determinations allow concluding that the geometry of the pore opening is predominantly correlated with the intraframework interactions rather than the steric hindrance of the substituent. Only (MIL-53(Fe)-(CF3)(2)) exhibits a nitrogen accessible porosity (S-BET approximate to 100 m(2) g(-1)). The adsorption of some liquids leads to pore openings showing some very specific behaviors depending on the guest-MIL-53(Fe) framework interactions, which can be related to the energy difference between the narrow and large pore forms evaluated by molecular simulation.

引用

页码：1127 / 1136

页数：10

共 66 条

[1] Selective Adsorption and Separation of ortho-Substituted Alkylaromatics with the Microporous Aluminum Terephthalate MIL-53 [J].