Interplay of linker functionalization and hydrogen adsorption in the metal-organic framework MIL-101

Functionalization of metal–organic frameworks results in higher hydrogen uptakes owing to stronger hydrogen–host interactions. However, it has not been studied whether a given functional group acts on existing adsorption sites (linker or metal) or introduces new ones. In this work, the effect of two types of functional groups on MIL-101 (Cr) is analyzed. Thermal-desorption spectroscopy reveals that the −Br ligand increases the secondary building unit’s hydrogen affinity, while the −NH2 functional group introduces new hydrogen adsorption sites. In addition, a subsequent introduction of −Br and −NH2 ligands on the linker results in the highest hydrogen-store interaction energy on the cationic nodes. The latter is attributed to a push-and-pull effect of the linkers.

[1]  J. Gascón,et al.  Post-synthetic cation exchange in the robust metal–organic framework MIL-101(Cr) , 2013 .

[2]  Freek Kapteijn,et al.  MOF@MOF core–shell vs. Janus particles and the effect of strain: potential for guest sorption, separation and sequestration , 2013 .

[3]  Yunqi Liu,et al.  Host-guest synthesis and encapsulation of phosphotungstic acid in MIL-101 via "bottle around ship": An effective catalyst for oxidative desulfurization , 2013 .

[4]  Dongmei Jiang,et al.  Synthesis and post-synthetic modification of MIL-101(Cr)-NH2 via a tandem diazotisation process. , 2012, Chemical communications.

[5]  Li Wang,et al.  Hydrogen Storage in Metal-Organic Frameworks , 2012, Journal of Inorganic and Organometallic Polymers and Materials.

[6]  Seth M. Cohen,et al.  Postsynthetic ligand and cation exchange in robust metal-organic frameworks. , 2012, Journal of the American Chemical Society.

[7]  Yichao Lin,et al.  Direct synthesis of amine-functionalized MIL-101(Cr) nanoparticles and application for CO2 capture , 2012 .

[8]  M. Vandichel,et al.  Electronic effects of linker substitution on Lewis acid catalysis with metal-organic frameworks. , 2012, Angewandte Chemie.

[9]  Daqiang Yuan,et al.  The current status of hydrogen storage in metal–organic frameworks—updated , 2011 .

[10]  Carlos Palomino Cabello,et al.  Enthalpy-Entropy Correlation for Hydrogen Adsorption on MOFs: Variable- Temperature FTIR Study of Hydrogen Adsorption on MIL-100(Cr) and MIL- 101(Cr) , 2011 .

[11]  C. Serre,et al.  Direct covalent post-synthetic chemical modification of Cr-MIL-101 using nitrating acid. , 2011, Chemical communications.

[12]  Randall Q. Snurr,et al.  Optimal isosteric heat of adsorption for hydrogen storage and delivery using metal-organic frameworks , 2010 .

[13]  M. Hirscher,et al.  Influence of [Mo6Br8F6]2- cluster unit inclusion within the mesoporous solid MIL-101 on hydrogen storage performance. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[14]  Jeff Tollefson,et al.  Hydrogen vehicles: Fuel of the future? , 2010, Nature.

[15]  J. Botas,et al.  Cobalt doping of the MOF-5 framework and its effect on gas-adsorption properties. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[16]  C. Knobler,et al.  Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks , 2010, Science.

[17]  Mircea Dincă,et al.  Hydrogen storage in metal-organic frameworks. , 2009, Chemical Society reviews.

[18]  Gerard P M van Klink,et al.  Isoreticular MOFs as efficient photocatalysts with tunable band gap: an operando FTIR study of the photoinduced oxidation of propylene. , 2008, ChemSusChem.

[19]  C. Serre,et al.  High-throughput assisted rationalization of the formation of metal organic frameworks in the Iron(III) aminoterephthalate solvothermal system. , 2008, Inorganic chemistry.

[20]  Dan Zhao,et al.  The current status of hydrogen storage in metal–organic frameworks , 2008 .

[21]  Michael Hirscher,et al.  Low-temperature thermal-desorption mass spectroscopy applied to investigate the hydrogen adsorption on porous materials , 2007 .

[22]  Gérard Férey,et al.  Hydrogen storage in the giant-pore metal-organic frameworks MIL-100 and MIL-101. , 2006, Angewandte Chemie.

[23]  Ulrich Müller,et al.  Hydrogen Adsorption in Metal–Organic Frameworks: Cu‐MOFs and Zn‐MOFs Compared , 2006 .

[24]  Omar M Yaghi,et al.  Exceptional H2 saturation uptake in microporous metal-organic frameworks. , 2006, Journal of the American Chemical Society.

[25]  S. Bhatia,et al.  Optimum conditions for adsorptive storage. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[26]  Omar M Yaghi,et al.  Effects of functionalization, catenation, and variation of the metal oxide and organic linking units on the low-pressure hydrogen adsorption properties of metal-organic frameworks. , 2006, Journal of the American Chemical Society.

[27]  C. Serre,et al.  A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area , 2005, Science.

[28]  Richard I. Cooper,et al.  CRYSTALS version 12: software for guided crystal structure analysis , 2003 .

[29]  Miroslav Haluska,et al.  Thermal desorption spectroscopy as a quantitative tool to determine the hydrogen content in solids , 2003 .

[30]  Andreas K. Freund,et al.  Nine-crystal multianalyzer stage for high-resolution powder diffraction between 6 keV and 40 keV , 1998, Optics & Photonics.