Defect engineering of UiO-66 for CO<sub>2</sub> and H<sub>2</sub>O uptake – a combined experimental and simulation study

Liang, Weibin; Coghlan, Campbell J.; Ragon, Florence; Rubio-Martínez, Marta; D’Alessandro, Deanna M.; Babarao, Ravichandar

doi:10.1039/c6dt00189k

Cited by 191 publications

(196 citation statements)

References 44 publications

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“…Pore size distribution analysis clearly shows disappearance of pores having half width of 7.4 ,a ssociated with missing cluster defects and well visible in FA_mod (Figure 3b). [17] 1 HNMR analysis of hydrolysed FA_mod-PSE-50 confirms that no exchange of BDC has occurred and all the exchanged PyDC has replaced FA at missing-cluster defective sites,inline with the result of the in situ experiment. This is good evidence that no significant diffusion limitations exist and exchange occurs homogeneously throughout the crystallites (see at the Supporting Information for ad etailed discussion of microstructural aspects of PSE).…”

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confidence: 63%

Post‐Synthetic Ligand Exchange in Zirconium‐Based Metal–Organic Frameworks: Beware of The Defects!

et al. 2018

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Post-synthetic ligand exchange in the prototypical zirconium-based metal-organic framework (MOF) UiO-66 was investigated by in situ solution H NMR spectroscopy. Samples of UiO-66 having different degrees of defectivity were exchanged using solutions of several terephthalic acid analogues in a range of conditions. Linker exchange only occurred in defect-free UiO-66, whereas monocarboxylates grafted at defect sites were found to be preferentially exchanged with respect to terephthalic acid over the whole range of conditions investigated. A 1:1 exchange ratio between the terephthalic acid analogue and modulator was observed, providing evidence that the defects had missing-cluster nature. Ex situ characterisation of the MOF powders after exchange corroborated these findings and showed that the physical-chemical properties of the MOF depend on whether the functionalisation occurs at defective sites or on the framework.

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confidence: 63%

Post‐Synthetic Ligand Exchange in Zirconium‐Based Metal–Organic Frameworks: Beware of The Defects!

et al. 2018

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“…The low separation factor might be caused by the missing linkers generated by the addition of acetic acid in the solvothermal synthesis. Indeed, the water adsorption increased as the number of missing linkers increased , . Thus, the ethanol selectivity of UiO‐66 could be improved by preparing the membrane with less missing linkers.…”

Section: Resultsmentioning

confidence: 99%

An Organoselective Zirconium‐Based Metal–Organic‐Framework UiO‐66 Membrane for Pervaporation

et al. 2017

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A UiO‐66 membrane was synthesized on an Al2O3 support by an in situ solvothermal method with a coordination modulation technique. We first confirmed the organic selectivity of the UiO‐66 membrane for methanol, ethanol, and acetone in mixtures with water. The membrane displayed highly stable pervaporation performance during the test and exhibited a separation factor of approximately 4.3 and a flux of 1.28 kg m–2 h–1 in ethanol/water. From the water and ethanol vapor adsorption measurement, the water uptake was lower in a binary system than that in a single system, although the ethanol uptake was similar for the binary and single systems. Therefore, the ethanol selectivity of the UiO‐66 membrane can be attributed to the preferential adsorption of the organic compound rather than water, as confirmed by a binary‐vapor adsorption measurement.

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“…44,45 Recently, Goodwin and co-workers showed that correlations between defects can be introduced and controlled, yielding nanoscale defect structures. 46 The presence of these defects may alter the catalytic properties, 47,48 thermal stability, 49 proton conductivity, 50,51 and adsorption behavior 43,52−55 of the host material. While recent work also indicates a decrease in bulk modulus and hence robustness upon the introduction of defects, 54,56 it remains to be investigated how the precise molecular nature of these defects alters the pressure-induced disorder in UiO-66-type materials.…”

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confidence: 99%

Thermodynamic Insight in the High-Pressure Behavior of UiO-66: Effect of Linker Defects and Linker Expansion

et al. 2016

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In this Article, we present a molecular-level understanding of the experimentally observed loss of crystallinity in UiO-66-type metal–organic frameworks, including the pristine UiO-66 to -68 as well as defect-containing UiO-66 materials, under the influence of external pressure. This goal is achieved by constructing pressure-versus-volume profiles at finite temperatures using a thermodynamic approach relying on ab initio derived force fields. On the atomic level, the phenomenon is reflected in a sudden drop in the number of symmetry operators for the crystallographic unit cell because of the disordered displacement of the organic linkers with respect to the inorganic bricks. For the defect-containing samples, a reduced mechanical stability is observed, however, critically depending on the distribution of these defects throughout the material, hence demonstrating the importance of judiciously characterizing defects in these materials.

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Defect engineering of UiO-66 for CO₂ and H₂O uptake – a combined experimental and simulation study

Abstract: Defect concentrations and their compensating groups have been systematically tuned within UiO-66 frameworks by using modified microwave-assisted solvothermal methods. Both of these factors have a pronounced effect on CO2 and H2O adsorption at low and high pressure.

Cited by 191 publications

References 44 publications

Post‐Synthetic Ligand Exchange in Zirconium‐Based Metal–Organic Frameworks: Beware of The Defects!

Post‐Synthetic Ligand Exchange in Zirconium‐Based Metal–Organic Frameworks: Beware of The Defects!

An Organoselective Zirconium‐Based Metal–Organic‐Framework UiO‐66 Membrane for Pervaporation

Thermodynamic Insight in the High-Pressure Behavior of UiO-66: Effect of Linker Defects and Linker Expansion

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Defect engineering of UiO-66 for CO2 and H2O uptake – a combined experimental and simulation study

Abstract: Defect concentrations and their compensating groups have been systematically tuned within UiO-66 frameworks by using modified microwave-assisted solvothermal methods. Both of these factors have a pronounced effect on CO2 and H2O adsorption at low and high pressure.

Cited by 191 publications

References 44 publications

Post‐Synthetic Ligand Exchange in Zirconium‐Based Metal–Organic Frameworks: Beware of The Defects!

Post‐Synthetic Ligand Exchange in Zirconium‐Based Metal–Organic Frameworks: Beware of The Defects!

An Organoselective Zirconium‐Based Metal–Organic‐Framework UiO‐66 Membrane for Pervaporation

Thermodynamic Insight in the High-Pressure Behavior of UiO-66: Effect of Linker Defects and Linker Expansion

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Defect engineering of UiO-66 for CO₂ and H₂O uptake – a combined experimental and simulation study