Synthesis, characterisation and adsorption properties of microporous scandium carboxylates with rigid and flexible frameworks

Mowat, John P. S.; Miller, Stuart; Slawin, Alexandra M. Z.; Seymour, Valerie R.; Ashbrook, Sharon E.; Wright, Paul A.

doi:10.1016/j.micromeso.2010.12.016

Cited by 177 publications

(254 citation statements)

References 31 publications

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“…4, top) which is well known from the Ga-MIL-53 structure [13,31] or Ga-MIL-68 [32] and moreover was already reported as an infinite gallium acetate [33]. Two trans-positioned oxygen atoms in every octahedron are part of l-corner-sharing OH-groups while four other oxygen atoms are part of four different carboxylate groups of different linker molecules.…”

Section: Crystal Structuresmentioning

confidence: 87%

“…Thus rhombic channels are formed, which result in the microporous nature of the materials [11]. A large number of compounds is known based not only on Cr 3+ but as well on Al 3+ [12], Sc 3+ [13], In 3+ [14] or Ga 3+ [15] or incorporating extended [16] or chemically functionalised linker molecules [17,18]. Most of the reported materials show the ''breathing''-effect which means that the shape and diameter of the channels in the framework change reversibly upon adsorption of guest molecules [16].…”

Section: Introductionmentioning

confidence: 99%

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Structures and properties of gallium-MOFs with MIL-53-topology based on aliphatic linker molecules

Reinsch

Vos

2014

Microporous and Mesoporous Materials

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Section: Crystal Structuresmentioning

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Structures and properties of gallium-MOFs with MIL-53-topology based on aliphatic linker molecules

Reinsch

Vos

2014

Microporous and Mesoporous Materials

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“…Solid-state NMR (SSNMR) experiments have been shown to yield detailed shortrange structural information in a wide variety of materials, including MOFs. [14][15][16][17] Prior studies of MIL-53 (lt) using 1 H and 13 C SSNMR experiments, in conjunction with pXRD experiments, have provided valuable insights into the hydrogen-bonding network between guest H 2 O molecules and the framework. 18 Other nuclei, such as 2 H and 45 Sc, have also been used to probe the MIL-53 system.…”

Section: Introductionmentioning

confidence: 99%

Investigating adsorption of organic compounds in metal-organic framework MIL-53

Ibrahim

et al. 2015

Can. J. Chem.

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Metal-organic frameworks (MOFs) are versatile materials that incorporate metal centers along with organic linkers in highly ordered, intricate structures. MIL-53 is a MOF that exhibits a "breathing effect," where the pore size and MOF topology are profoundly influenced by the identity and binding mechanism of guest molecules. This phenomenon renders MIL-53 a promising candidate for sensing applications. In this report, the adsorption of various organic compounds within MIL-53 is investigated using a combination of complementary techniques. Thermal gravimetric analysis experiments confirm loading of the guest molecules and yield insight into adsorption interactions and strengths. Significant guest-induced changes in the crystal structure of MIL-53 are revealed by powder X-ray diffraction experiments; specific unique phases of MIL-53 are related to the identity of the guest molecule and its binding mechanism to the framework. 27 Al and 13 C solid-state NMR experiments probe the interaction between guest molecules and MIL-53. The relationship between the nature of the guest, the structure of MIL-53, and 27 Al NMR parameters is explored. 27 Al NMR parameters are sensitive to the host-guest binding mechanism (i.e., hydrogenbonding or -stacking interactions) and yield valuable information regarding the influence of the adsorbates on the local aluminum environment. This combination of physical characterization techniques is a useful probe of guest adsorption and the breathing effect within MIL-53 and should prove useful for investigation of related MOFs. Résumé: Les réseaux métallo-organiques (MOF, acronyme anglais pour Metal-Organic Frameworks) sont des matériaux polyvalents où des centres métalliques sont incorporés dans un réseau organique formant des structures complexes et hautement ordonnées. Le MIL-53 est un réseau métallo-organique présentant un « effet de respiration », dont la taille des pores et la topologie du réseau métallo-organique dépendent fortement de l'identité et du mécanisme de liaison des molécules invitées. Ce phénomène fait du MIL-53 un candidat prometteur pour des applications dans le domaine des capteurs. Dans les présents travaux, nous avons étudié l'adsorption de divers composés organiques au MIL-53 à l'aide d'un ensemble de techniques complémentaires. Des analyses thermogravimétriques confirment la charge de molécules invitées et fournissent un aperçu des interactions et des forces d'adsorption. Des expériences de diffraction des rayons X sur poudre ont permis de révéler des modifications importantes de la structure cristalline du MIL-53 induites par l'invité; des phases uniques propres au MIL-53 sont liées à l'identité de l'invité et à son mécanisme de liaison au réseau. Des expériences de RMN 27 Al et 13 C à l'état solide ont permis d'explorer les interactions entre les molécules invitées et le MIL-53. Nous avons étudié la relation entre la nature de l'invité, la structure du MIL-53 et les paramètres RMN 27 Al. Ces derniers sont sensibles au mécanisme de liaison hôte-invité (c.-à -d. les l...

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“…Furthermore, CO 2 adsorption studies suggest that motion of -NO 2 groups can occur, even at low temperatures, and that the heat of CO 2 adsorption can be increased by incorporating NH 2 groups. Hydrothermal crystallization using scandium oxide, reported to produce the Sc 2 BDC 3 framework, 11 was successful for the preparation of the functionalized forms of the Sc 2 BDC 3 material using the 2-nitroterephthalic acid (Alfa Aesar, 99%) and 2-aminoterephthalic acid (Aldrich, 99%). Subsequently, hydrothermal synthesis using scandium nitrate was also successful in attempts to prepare the -NO 2 form of Sc 2 BDC 3 ( Table 1).…”

Section: Introductionmentioning

confidence: 99%

Structural Chemistry, Monoclinic-to-Orthorhombic Phase Transition, and CO₂ Adsorption Behavior of the Small Pore Scandium Terephthalate, Sc₂(O₂CC₆H₄CO₂)₃, and Its Nitro- And Amino-Functionalized Derivatives

et al. 2011

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The crystal structure of the small pore scandium terephthalate Sc(2)(O(2)CC(6)H(4)CO(2))(3) (hereafter Sc(2)BDC(3), BDC = 1,4-benzenedicarboxylate) has been investigated as a function of temperature and of functionalization, and its performance as an adsorbent for CO(2) has been examined. The structure of Sc(2)BDC(3) has been followed in vacuo over the temperature range 140 to 523 K by high resolution synchrotron X-ray powder diffraction, revealing a phase change at 225 K from monoclinic C2/c (low temperature) to Fddd (high temperature). The orthorhombic form shows negative thermal expansivity of 2.4 × 10(-5) K(-1): Rietveld analysis shows that this results largely from a decrease in the c axis, which is caused by carboxylate group rotation. (2)H wide-line and MAS NMR of deuterated Sc(2)BDC(3) indicates reorientation of phenyl groups via π flips at temperatures above 298 K. The same framework solid has also been prepared using monofunctionalized terephthalate linkers containing -NH(2) and -NO(2) groups. The structure of Sc(2)(NH(2)-BDC)(3) has been determined by Rietveld analysis of synchrotron powder diffraction at 100 and 298 K and found to be orthorhombic at both temperatures, whereas the structure of Sc(2)(NO(2)-BDC)(3) has been determined by single crystal diffraction at 298 K and Rietveld analysis of synchrotron powder diffraction at 100, 298, 373, and 473 K and is found to be monoclinic at all temperatures. Partial ordering of functional groups is observed in each structure. CO(2) adsorption at 196 and 273 K indicates that whereas Sc(2)BDC(3) has the largest capacity, Sc(2)(NH(2)-BDC)(3) shows the highest uptake at low partial pressure because of strong -NH(2)···CO(2) interactions. Remarkably, Sc(2)(NO(2)-BDC)(3) adsorbs 2.6 mmol CO(2) g(-1) at 196 K (P/P(0) = 0.5), suggesting that the -NO(2) groups are able to rotate to allow CO(2) molecules to diffuse along the narrow channels.

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Synthesis, characterisation and adsorption properties of microporous scandium carboxylates with rigid and flexible frameworks

Cited by 177 publications

References 31 publications

Structures and properties of gallium-MOFs with MIL-53-topology based on aliphatic linker molecules

Structures and properties of gallium-MOFs with MIL-53-topology based on aliphatic linker molecules

Investigating adsorption of organic compounds in metal-organic framework MIL-53

Structural Chemistry, Monoclinic-to-Orthorhombic Phase Transition, and CO₂ Adsorption Behavior of the Small Pore Scandium Terephthalate, Sc₂(O₂CC₆H₄CO₂)₃, and Its Nitro- And Amino-Functionalized Derivatives

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Synthesis, characterisation and adsorption properties of microporous scandium carboxylates with rigid and flexible frameworks

Cited by 177 publications

References 31 publications

Structures and properties of gallium-MOFs with MIL-53-topology based on aliphatic linker molecules

Structures and properties of gallium-MOFs with MIL-53-topology based on aliphatic linker molecules

Investigating adsorption of organic compounds in metal-organic framework MIL-53

Structural Chemistry, Monoclinic-to-Orthorhombic Phase Transition, and CO2 Adsorption Behavior of the Small Pore Scandium Terephthalate, Sc2(O2CC6H4CO2)3, and Its Nitro- And Amino-Functionalized Derivatives

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Structural Chemistry, Monoclinic-to-Orthorhombic Phase Transition, and CO₂ Adsorption Behavior of the Small Pore Scandium Terephthalate, Sc₂(O₂CC₆H₄CO₂)₃, and Its Nitro- And Amino-Functionalized Derivatives