Host–guest selectivity in a series of isoreticular metal–organic frameworks: observation of acetylene-to-alkyne and carbon dioxide-to-amide interactions

Humby, Jack D.; Benson, Oguarabau; Smith, Gemma L.; Argent, Stephen P.; Silva, Iván da; Cheng, Yongqiang; Rudić, Svemir; Manuel, Pascal; Frogley, Mark D.; Cinque, Gianfelice; Saunders, Lucy K.; Vitórica-Yrezábal, Iñigo J.; Whitehead, George F. S.; Easun, Timothy L.; Lewis, William; Blake, Alexander J.; Ramirez‐Cuesta, Anibal J.; Yang, Sihai; Schröder, Martin

doi:10.1039/c8sc03622e

Cited by 51 publications

(38 citation statements)

References 36 publications

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“…As illustrated in Figure 2 the uptake capacity of C 2 H 2 molecules in all Ni‐MOF structures is approximately twice of the adsorption amount of CO 2 molecules being indicative of high selectivity towards C 2 H 2 gas molecules (see below). This result can be attributed to the presence of the alkyne functional group within the framework, resulting in much more effective interaction with C 2 H 2 [14,15] . Proper pore size match is another key factor that provides effective interactions with guest molecules within the structures.…”

Section: Resultsmentioning

confidence: 99%

“…Among them, functionalization of pore surfaces along with post‐modification treatments can result in a high gas adsorption capacity and selectivity to a gas molecule [13] . A few systematic investigations have revealed that alkyne‐functionalized MOFs demonstrate higher adsorption capacity along with desired selectivity for acetylene gas molecules in comparison to their non‐functionalized analogues [14,15] . Along with these observations, as demonstrated by previous work of some of us, the exploitation of pyrazolate‐based spacers can afford remarkable chemical and thermal stability to MOFs, often exceeding 400 °C in air [16,17] .…”

Section: Introductionmentioning

confidence: 87%

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Impact of Pore Size and Defects on the Selective Adsorption of Acetylene in Alkyne‐Functionalized Nickel(II)‐Pyrazolate‐Based MOFs

Afshariazar

Morsali

Sorbara

et al. 2021

Chemistry A European J

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C2H2/CO2 separation is a highly challenging process as a consequence of their similar physicochemical properties. In this work we have explored, by static and dynamic gas sorption techniques and computational modelling, the suitability of a series of two isoreticular robust Ni(II)pyrazolate‐based MOFs, bearing alkyne moieties on the ligand backbones, for C2H2/CO2 separation. The results are consistent with high adsorption capacity and selectivity of the essayed systems towards C2H2 molecules. Furthermore, a post‐synthetic treatment with KOH ethanolic solution gives rise to linker vacancy defects and incorporation of extraframework potassium ions. Creation of defects is responsible for increased adsorption capacity for both gases, however, strong interactions of the cluster basic sites and extraframework potassium cations with CO2 molecules are responsible for a lowering of C2H2 over CO2 selectivity.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 87%

Impact of Pore Size and Defects on the Selective Adsorption of Acetylene in Alkyne‐Functionalized Nickel(II)‐Pyrazolate‐Based MOFs

Afshariazar

Morsali

Sorbara

et al. 2021

Chemistry A European J

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“…Developments in gas-handling systems have also paved the way to probe gate-opening and related network-breathing phenomena arising from the unique elastic properties of MOFs—see entries in Table 1 and Refs. [ 151 , 266 , 267 , 268 , 269 , 270 , 271 , 272 , 273 , 274 , 275 , 276 , 277 , 278 , 279 , 280 , 281 , 282 , 283 , 284 , 285 , 286 , 287 , 288 , 289 , 290 ].…”

Section: From Confined Polymers To Soft Supramolecular Frameworkmentioning

confidence: 99%

Dynamics & Spectroscopy with Neutrons—Recent Developments & Emerging Opportunities

2021

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This work provides an up-to-date overview of recent developments in neutron spectroscopic techniques and associated computational tools to interrogate the structural properties and dynamical behavior of complex and disordered materials, with a focus on those of a soft and polymeric nature. These have and continue to pave the way for new scientific opportunities simply thought unthinkable not so long ago, and have particularly benefited from advances in high-resolution, broadband techniques spanning energy transfers from the meV to the eV. Topical areas include the identification and robust assignment of low-energy modes underpinning functionality in soft solids and supramolecular frameworks, or the quantification in the laboratory of hitherto unexplored nuclear quantum effects dictating thermodynamic properties. In addition to novel classes of materials, we also discuss recent discoveries around water and its phase diagram, which continue to surprise us. All throughout, emphasis is placed on linking these ongoing and exciting experimental and computational developments to specific scientific questions in the context of the discovery of new materials for sustainable technologies.

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“…These organic/inorganic three-dimensional hybrid networks often have well-defined structures, are commonly highly crystalline and can have very high surface areas. MOF materials with tunable physical and chemical properties have a wide range of applications in gas sorption and separations [6][7][8][9][10][11][12], catalysis [13][14][15] and contaminant removal [16,17]. Substantial research efforts have been made on CO 2 gas adsorption applications.…”

Section: Introductionmentioning

confidence: 99%

Ethylenediamine loading into a manganese-based metal–organic framework enhances water stability and carbon dioxide uptake of the framework

et al. 2020

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Metal–organic frameworks (MOFs) based on 2,5-dihydroxyterepthalic acid (DOBDC) as the linker show very high CO 2 uptake capacities at low to moderate CO 2 pressures; however, these MOFs often require expensive solvent for synthesis and are difficult to regenerate. We have synthesized a Mn-DOBDC MOF and modified it to introduce amine groups into the structure by functionalizing its metal coordination sites with ethylenediamine (EDA). Repeat framework synthesis was then also successfully performed using recycled dimethylformamide (DMF) solvent. Characterization by elemental analysis, FTIR and thermogravimetric studies suggest that EDA molecules are successfully substituting the original metal-bound DMF. This modification not only enhances the material's carbon dioxide sorption capacity, increasing stability to repeated CO 2 sorption cycles, but also improves the framework's stability to moisture. Moreover, this is one of the first amine-modified MOFs that can demonstrably be synthesized using recycled solvent, potentially reducing the future costs of production at larger scales.

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Host–guest selectivity in a series of isoreticular metal–organic frameworks: observation of acetylene-to-alkyne and carbon dioxide-to-amide interactions

Abstract: We report a series of six isoreticular metal–organic frameworks (MOFs) for selective gas adsorption, specifically for selective adsorption of CO2 and C2H2.

Cited by 51 publications

References 36 publications

Impact of Pore Size and Defects on the Selective Adsorption of Acetylene in Alkyne‐Functionalized Nickel(II)‐Pyrazolate‐Based MOFs

Impact of Pore Size and Defects on the Selective Adsorption of Acetylene in Alkyne‐Functionalized Nickel(II)‐Pyrazolate‐Based MOFs

Dynamics & Spectroscopy with Neutrons—Recent Developments & Emerging Opportunities

Ethylenediamine loading into a manganese-based metal–organic framework enhances water stability and carbon dioxide uptake of the framework

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