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Direct observation of supramolecular binding of light hydrocarbons in vanadium(iii) and (iv) metal-organic framework materials.

ABSTRACT: Fine tuning of host-guest supramolecular interactions in porous systems enables direct control over the properties of functional materials. We report here a modification of hydrogen bonding and its effect on guest binding in a pair of redox-active metal-organic frameworks (MOFs). Oxidation of MFM-300(V^III) {[VIII2(OH)₂(L)], LH₄ = biphenyl-3,3',5,5'-tetracarboxylic acid} is accompanied by deprotonation of the bridging hydroxyl groups to afford isostructural MFM-300(V^IV), [VIV2O₂(L)]. The precise role of the hydroxyl groups, O-carboxylate centres and ?-? interactions in the supramolecular binding of C₂ hydrocarbons in these materials has been determined using neutron diffraction and inelastic neutron scattering, coupled with DFT modelling. The hydroxyl protons are observed to bind to adsorbed unsaturated hydrocarbons preferentially in MFM-300(V^III), particularly to C₂H₂, which is in a sharp contrast to MFM-300(V^IV) where interactions with O-carboxylate centres and ?-? interactions predominate. This variation in structure and redox leads to notably higher separation selectivity for C₂H₂/CH₄ and C₂H₄/CH₄ in MFM-300(V^III) than in MFM-300(V^IV). Significantly, owing to the specific host-guest interactions, MFM-300(V^III) shows a record packing density for adsorbed C₂H₂ at 303 K and 1 bar, demonstrating its potential for use in portable acetylene stores.

SUBMITTER: Lu Z

PROVIDER: S-EPMC5933292 | biostudies-literature | 2018 Apr

REPOSITORIES: biostudies-literature

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Direct observation of supramolecular binding of light hydrocarbons in vanadium(iii) and (iv) metal-organic framework materials.

Lu Zhenzhong Z Godfrey Harry G W HGW da Silva Ivan I Cheng Yongqiang Y Savage Mathew M Manuel Pascal P Rudić Svemir S Ramirez-Cuesta Anibal J AJ Yang Sihai S Schröder Martin M

Chemical science 20180221 13

Fine tuning of host-guest supramolecular interactions in porous systems enables direct control over the properties of functional materials. We report here a modification of hydrogen bonding and its effect on guest binding in a pair of redox-active metal-organic frameworks (MOFs). Oxidation of MFM-300(VIII) {[VIII2(OH)2(L)], LH4 = biphenyl-3,3',5,5'-tetracarboxylic acid} is accompanied by deprotonation of the bridging hydroxyl groups to afford isostructural MFM-30 ...[more]

PMID: 29780471

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Project description:Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in a Matrimid polymer matrix with different weight ratios (0-100 wt %) and drop-casted on planar capacitive transducer devices. These coated devices were electrically analyzed using impedance spectroscopy and investigated for their sensing properties toward the detection of a series of alcohols and water in the gas phase. The measurements indicated a reversible and reproducible response in all devices. Sensor devices containing 40 wt % NH2-MIL-53(Al) in Matrimid showed a maximum response for methanol and water. The sensor response time slowed down with increasing MOF concentration until 40 wt %. The half time of saturation response (τ0.5) increased by ∼1.75 times for the 40 wt % composition compared to devices coated with Matrimid only. This is attributed to polymer rigidification near the MOF/polymer interface. Higher MOF loadings (≥50 wt %) resulted in brittle coatings with a response similar to the 100 wt % MOF coating. Cross-sensitivity studies showed the ability to kinetically distinguish between the different alcohols with a faster response for methanol and water compared to ethanol and 2-propanol. The observed higher affinity of the pure Matrimid polymer toward methanol compared to water allows also for a higher uptake of methanol in the composite matrices. Also, as indicated by the sensing studies with a mixture of water and methanol, the methanol uptake is independent of the presence of water up to 6000 ppm of water. The NH2-MIL-53(Al) MOFs dispersed in the Matrimid matrix show a sensitive and reversible capacitive response, even in the presence of water. By tuning the precise compositions, the affinity kinetics and overall affinity can be tuned, showing the promise of this type of chemical sensors.

Dataset Information

Direct observation of supramolecular binding of light hydrocarbons in vanadium(iii) and (iv) metal-organic framework materials.

Publications

Direct observation of supramolecular binding of light hydrocarbons in vanadium(iii) and (iv) metal-organic framework materials.

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