Tuning the breathing behaviour of MIL-53 by cation mixing

Nouar, Farid; Devic, Thomas; Chevreau, Hubert; Guillou, Nathalie; Gibson, Emma K.; Clet, Guillaume; Daturi, Marco; Vimont, Alexandré; Grenèche, Jean‐Marc; Breeze, Matthew I.; Walton, Richard I.; Llewellyn, Philip L.; Serre, Christian

doi:10.1039/c2cc35348b

Cited by 135 publications

(110 citation statements)

References 35 publications

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“…Overall, the flexibility of the reported MC‐MOFs is strongly defined by the (V IV O) content in mixed Al/V chains with rather gradual trends: (1) in the 1 – 5 sequence, with increasing V content, the induction of the initial lp–np transition upon CO 2 adsorption or cooling of the samples becomes more difficult, and the np contribution considerably diminishes (Figure 8, b); (2) as a consequence, the p (CO 2 ) required for the subsequent np–lp transitions in 1 – 5 decreases (from 600 to 0 mbar). In parallel to our studies, a Cr/Fe (60:40) MIL‐53 has been obtained 9e. The combination of two flexible MIL‐53(Cr) and MIL‐53(Fe) materials also provided a flexible material with breathing behaviour different to either of the parent monometallic analogues.…”

Section: Resultsmentioning

confidence: 99%

A Solid‐Solution Approach to Mixed‐Metal Metal–Organic Frameworks – Detailed Characterization of Local Structures, Defects and Breathing Behaviour of Al/V Frameworks

et al. 2013

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The doping of [Al(OH)L]n [L = 1,4‐benzenedicarboxylate (bdc) or 1,4‐naphthalenedicarboxylate (ndc)] with vanadium ions yields crystalline porous mixed‐metal solid‐solution metal–organic frameworks (MOFs) of general formula [(AlOH)1–x(VO)xL]n (x can be varied in the whole range from 0 to 1). Several characterization methods, including powder X‐ray diffraction (PXRD), electron paramagnetic resonance (EPR), solid‐state NMR and FTIR spectroscopy, strongly support the effective incorporation of vanadium cations. The Al/V‐doped MOFs are isostructural to the parent monometallic MOFs and show a characteristic uniform dependence of the cell parameters on the metal ratios. Detailed spectroscopic investigation provided evidence that the introduced species are fairly well ordered. Interestingly, for low amounts of doped vanadium for both activated and as‐synthesized Al/V phases, the EPR results revealed the presence of vanadyl units as local defects in pseudo‐octahedral or square‐pyramidal environments, which are different from those in the parent MIL‐47(V). This observation matches the nonlinear response of the adsorption properties on variation of the composition. Remarkably, the presence of such mixed Al/V chains strongly affects the breathing behaviour of the materials. Both CO2 sorption and in situ PXRD studies validated a gradual change from highly flexible (with easily induced phase transitions) to totally rigid structures upon increasing vanadium content.

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Section: Resultsmentioning

confidence: 99%

A Solid‐Solution Approach to Mixed‐Metal Metal–Organic Frameworks – Detailed Characterization of Local Structures, Defects and Breathing Behaviour of Al/V Frameworks

et al. 2013

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“…a material with a band gap of ~3.0 eV, or the difference in band gaps between np and lp forms being as small as possible. We also note that partial substitutions of the metal cations, 34,[68][69][70] i.e. a single MIL-53 material with a mixture of different types of metal cations in the same valence, or mixed MIL-53/47 material with different inorganic linkers (i.e.…”

Section: Figurementioning

confidence: 98%

Unusually Large Band Gap Changes in Breathing Metal–Organic Framework Materials

Ling

Slater

2015

J. Phys. Chem. C

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Many of the potential applications for metal organic frameworks (MOFs) focus on exploiting their porosity for molecular storage, release and separation where the functional behaviour is controlled by a subtle balance of host-guest interactions. Typically the host structure is relatively unperturbed by the presence of guests, however, a subset of metal organic frameworks exhibit dramatic phase change behaviour triggered by the adsorption of guests or other stimuli, for which the MIL-53 material is an archetype. In this work, we use density functional approaches to examine the electronic structure changes associated with changes of phase and density and find the associated change in band gaps can be larger than 1 eV for known MIL-53 type materials and hypothecated structures. Moreover, we show that internal pressure (via guest molecules) and external pressure can exert a major influence on the band gap size and gap states. The large response in electronic properties to breathing transitions in MOFs could be exploitable in future applications in resistive switching, phase change memory, piezoresistor, gas sensor, and thermochromic materials.structure of non-conducting MOFs, although the more widespread parlance of band gap terminology is still de facto and we will refer to both band gaps and HOMO-LUMO nomenclature in this work.The MOF literature is dominated by synthesis and characterisation reports of new materials and input from theory typically focuses on rationalising observation through classical simulations of host-guest interactions. Nevertheless, there are an increasing number of electronic studies of MOFs which date back more than decade: early work of Dovesi reported a high-level ab initio study of the electronic properties of MOF-5, 10 through tight-binding calculations, Kuc et al. found the band gaps of a series of Zn-based isoreticular MOFs (IRMOFs) are determined by the carbon sp 2 states of the organic linkers and longer linkers yield smaller band gaps. 9 In a recent density functional theory (DFT) study by Pham et al., halogen functionalization of the organic linkers of IRMOFs was found to modify the band gaps and also affect the absolute positions of the valence band maxima. 11 The nature of the metal centres also affects electronic properties; using DFT, Fuentes-Cabrera et al. studied IRMOF1 with different metal centres, including Be, Mg, Ca, Zn and Cd, and found all these materials possess similar band gaps but distinct conduction band splitting, and that the metallicity can be influenced by selective metal doping. 12 Tunable electronic properties of IRMOFs have been verified in different experiments. For example, in a recent UV/Vis spectroscopy experiment by Gascon et al., it was reported the band gaps of IRMOFs are conditioned by the organic linkers of IRMOFs, and that 1,4-or 2,6-naphthalenedicarboxylic acid organic linkers yielded the smallest band gaps (~ 3.3 eV) . 13 In another experiment by Lin et al., it was shown that the band gaps of Zn-based MOFs can be tuned by changing the cluster size...

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“…3 Likewise, partial replacement of one trivalent metal by another can adjust the response of the framework to stimuli. 4 The potentially most versatile method of modification of MIL-53 materials, however, is the addition of functional groups to the aromatic ring of the terephthalate linker: this has been widely studied for a range of substituents and a common strategy is to premake substituted 1,4-benzenedicarboxylic acid that is then used as a reagent for the crystallisation of MIL-53. 5,6 This has been used with great effect to modify the response of the MIL-53 towards guest molecules and their thermally induced breathing behaviour, 7,8,9 or to introduce reactive functionalities that can be used for further chemical modification.…”

Section: Introductionmentioning

confidence: 99%

Iodine sequestration by thiol-modified MIL-53(Al)

et al. 2016

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A thiol-modified version of the porous metal organic framework MIL-53 is synthesised in a single step using the functionalised ligand precursor 2,5-dithiol-1,4-benzenedicarboxylic acid and aluminium as the framework metal. Careful washing is needed to remove unreacted and dimerised linker from the material after synthesis, but once performed profile fitting of powder Xray diffraction shows that thiol-modified MIL-53(Al) presents a closed, narrow-pore, structure with unit cell volume ~1103 Å 3 (space group C2/c). The presence of intact thiol groups is confirmed using sulfur K-edge XANES spectroscopy and IR spectroscopy, while nitrogen BET surface area analysis and krypton and xenon adsorption isotherms reveal the porosity of the material. The thiol-modified solid is capable of iodine adsorption from the vapour phase and from solution and 2 an equilibrium uptake of ~325 mg per g is reached, which is higher than other reported modified forms of MIL-53. Infrared spectroscopy shows the disappearance of the S-H stretch after iodine adsorption, while sulfur K-edge XANES shows a complex spectrum, consistent with the formation of sulfenyl iodide but also oxidation of some sulfur to disulfide having occurred. We therefore propose that formation of covalent S-I bonds allows the sequestration of iodine by the porous solid, but that a proportion of the thiol groups are also in close enough proximity for the formation of disulfide links.

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Tuning the breathing behaviour of MIL-53 by cation mixing

Abstract: A mixed cation MIL-53(Cr-Fe) MOF has been obtained by direct synthesis. Multiple experimental techniques have demonstrated the presence of a genuine mixed phase, leading to a breathing behaviour different from either of the single cation analogues.

Cited by 135 publications

References 35 publications

A Solid‐Solution Approach to Mixed‐Metal Metal–Organic Frameworks – Detailed Characterization of Local Structures, Defects and Breathing Behaviour of Al/V Frameworks

A Solid‐Solution Approach to Mixed‐Metal Metal–Organic Frameworks – Detailed Characterization of Local Structures, Defects and Breathing Behaviour of Al/V Frameworks

Unusually Large Band Gap Changes in Breathing Metal–Organic Framework Materials

Iodine sequestration by thiol-modified MIL-53(Al)

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