In SituStudies of the Crystallization of Metal-Organic Frameworks

Walton, Richard I.; Millange, Franck

doi:10.1002/9783527693078.ch24

Cited by 16 publications

(28 citation statements)

References 99 publications

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“…The Gualtieri model was employed to extract kinetic information about the crystallisation process from the plots of the extent of crystallisation as a function of time. 2,6,37 The Gualtieri model is a physically derived model which stemmed from experimental studies of the hydrothermal crystallisation of zeolites. 37 This makes it an attractive model for crystallisation of MOFs under hydro-or solvothermal conditions.…”

Section: Kinetic Analysismentioning

confidence: 99%

“…Investigating the influence of reaction conditions on the thermodynamics and kinetics of crystallisation of metalorganic frameworks (MOFs) is extremely beneficial to gather information on the relationship between crystal structure and synthetic parameters, to optimise the reaction conditions for up-scaling of synthetic protocols and to aid the design of new materials. [1][2][3] Since the majority of MOF syntheses is carried out starting from liquid reaction mixtures, the formation of the solid product can be followed in situ employing scattering techniquessuch as X-ray diffraction (XRD), [4][5][6][7][8] small angle X-ray scattering (SAXS), [9][10][11] static/dynamic light scattering (SLS/DLS), [12][13] -or turbidity measurements. [14][15] SAXS, SLS/DLS and turbidity are especially suited to study the earliest stages of crystallisation because they can detect particles with subnanometric size, but they provide no information about the crystal structure of the scattering objects.…”

Section: Introductionmentioning

confidence: 99%

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In situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)-based Metal-Organic Frameworks with UiO-66 and MIL-140 architectures

Shearan¹,

Jacobsen²,

Costantino³

et al. 2021

Preprint

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We report on the results of a thorough in situ synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce(IV)-based metal-organic frameworks (MOFs), analogues of the already well investigated Zr(IV)-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as building blocks, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds in situ in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO3) and amount of the coordination modulator acetic acid (AcOH). When only HNO3 is present in the reaction environment, F4_MIL-140A(Ce) is obtained as a pure phase. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C, whereas the modulator influences nucleation and crystal growth to a similar extent. Upon addition of AcOH to the system, alongside HNO3, mixed-phased products, consisting of F4_MIL-140A(Ce) and F4_UiO-66(Ce), are obtained. In these conditions, F4_UiO-66(Ce) is always formed faster and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate determining step. An increase in the amount of HNO3 slows down both nucleation and growth rates for F4_MIL-140A(Ce), whereas nucleation is mainly affected for F4_UiO-66(Ce). In addition, a higher amount HNO3 favours the formation of F4_MIL-140A(Ce). Similarly, increasing the amount of AcOH leads to slowing down of the nucleation and growth rate, but favours the formation of F4_UiO-66(Ce). The pure F4_UiO-66(Ce) phase could also be obtained when using larger amounts of AcOH in the presence of minimal HNO3. Based on these in situ results, a new optimised route to achieving a pure, high quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.

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Section: Kinetic Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

In situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)-based Metal-Organic Frameworks with UiO-66 and MIL-140 architectures

Shearan¹,

Jacobsen²,

Costantino³

et al. 2021

Preprint

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“…In situ investigations have been widely used in materials chemistry to monitor synthetic processes, especially those involving the self-assembly of well-defined building blocks into crystalline compounds [92]. Besides simply following the products' formation, this approach is powerful in identifying the different phases and intermediates that form over the course of a reaction [93].…”

Section: In Situ Characterisationmentioning

confidence: 99%

New Directions in Metal Phosphonate and Phosphinate Chemistry

et al. 2019

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In September 2018, the First European Workshop on Metal Phosphonates Chemistry brought together some prominent researchers in the field of metal phosphonates and phosphinates with the aim of discussing past and current research efforts and identifying future directions. The scope of this perspective article is to provide a critical overview of the topics discussed during the workshop, which are divided into two main areas: synthesis and characterisation, and applications. In terms of synthetic methods, there has been a push towards cleaner and more efficient approaches. This has led to the introduction of high-throughput synthesis and mechanochemical synthesis. The recent success of metal–organic frameworks has also promoted renewed interest in the synthesis of porous metal phosphonates and phosphinates. Regarding characterisation, the main advances are the development of electron diffraction as a tool for crystal structure determination and the deployment of in situ characterisation techniques, which have allowed for a better understanding of reaction pathways. In terms of applications, metal phosphonates have been found to be suitable materials for several purposes: they have been employed as heterogeneous catalysts for the synthesis of fine chemicals, as solid sorbents for gas separation, notably CO2 capture, as materials for electrochemical devices, such as fuel cells and rechargeable batteries, and as matrices for drug delivery.

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“…In situ techniques, which very often necessitate the use of synchrotron radiation, allow the non-invasive observation of chemical processes within a sealed reaction vessel without the need for quenching and ex situ characterization [155,155,177]. Crystalline intermediate phases may be observed and crystallization kinetics can be deduced by applying physical models.…”

Section: In Situ Characterization During Synthesismentioning

confidence: 99%

“…Crystalline intermediate phases may be observed and crystallization kinetics can be deduced by applying physical models. An overview on in situ monitoring of the formation of crystalline solids in general and in situ studies on MOF syntheses have been summarized by N. Pienack and W. Bensch [178], N. Stock and S. Biswas [155], R. Walton and F. Millange [179] and I. Senkovska and V. Bon [177]. In situ studies carried out by the groups of R. A. Fischer and C. Wöll on layer-by-layer growth of SURMOFs [180] will be covered in Section 5.8.…”

Section: In Situ Characterization During Synthesismentioning

confidence: 99%

Metal–organic frameworks in Germany: From synthesis to function

Evans

Garai

Reinsch

et al. 2019

Coordination Chemistry Reviews

107

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Metal-organic frameworks (MOFs) are constructed from a combination of inorganic and organic units to produce materials which display high porosity, among other unique and exciting properties. MOFs have shown promise in many wide ranging applications, such as catalysis and gas separations. In this review, we highlight MOF research conducted by Germany-based research groups. Specifically, we feature approaches for the synthesis of new MOFs, high-throughput MOF production, advanced characterization methods and examples of advanced functions and properties.

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In SituStudies of the Crystallization of Metal-Organic Frameworks

Cited by 16 publications

References 99 publications

In situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)-based Metal-Organic Frameworks with UiO-66 and MIL-140 architectures

In situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)-based Metal-Organic Frameworks with UiO-66 and MIL-140 architectures

New Directions in Metal Phosphonate and Phosphinate Chemistry

Metal–organic frameworks in Germany: From synthesis to function

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