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

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

10.26434/chemrxiv.13252544.v2 ◽

2021 ◽

Author(s):

Stephen Shearan ◽

Jannick Jacobsen ◽

Ferdinando Costantino ◽

Roberto D’Amato ◽

Dmitri Novikov ◽

...

Keyword(s):

Crystal Growth ◽

Metal Organic Frameworks ◽

Nucleation And Growth ◽

X Ray Diffraction ◽

X Ray ◽

Rate Determining Step ◽

Wide Range ◽

Metal Organic ◽

Two Phases

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

Chemistry - A European Journal ◽

10.1002/chem.202005085 ◽

2021 ◽

Author(s):

Stephen J. I. Shearan ◽

Jannick Jacobsen ◽

Ferdinando Costantino ◽

Roberto D’Amato ◽

Dmitri Novikov ◽

...

Keyword(s):

Metal Organic Frameworks ◽

X Ray Diffraction ◽

X Ray ◽

Metal Organic

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In situ identification and absolute separation of small molecules by single crystal X-ray diffraction in metal–organic frameworks

CrystEngComm ◽

10.1039/c6ce01085g ◽

2016 ◽

Vol 18 (29) ◽

pp. 5429-5433 ◽

Cited By ~ 2

Author(s):

Heng Ya Gao ◽

Le Zhang ◽

Chang Sheng Yan ◽

Li Na Meng ◽

Jian Qiang Li ◽

...

Keyword(s):

Single Crystal ◽

Small Molecules ◽

Metal Organic Frameworks ◽

X Ray Diffraction ◽

X Ray ◽

Metal Organic

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Probing open metal sites in high-valence metal–organic frameworks by in situ single-crystal X-ray diffraction

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s0108767319098805 ◽

2019 ◽

Vol 75 (a1) ◽

pp. a119-a119

Author(s):

Qi Wang ◽

Shuai Yuan ◽

Junsheng Qin ◽

Wenmiao Chen ◽

Hongcai Zhou

Keyword(s):

Single Crystal ◽

Metal Organic Frameworks ◽

X Ray Diffraction ◽

X Ray ◽

Open Metal Sites ◽

Metal Organic

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Correlated defects in group 4 metal-organic frameworks

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314088755 ◽

2014 ◽

Vol 70 (a1) ◽

pp. C1124-C1124

Author(s):

Matthew Cliffe ◽

Wei Wan ◽

Xiaodong Zou ◽

François-Xavier Coudert ◽

Andrew Goodwin

Keyword(s):

Acid Catalysis ◽

Catalytic Properties ◽

Metal Organic Frameworks ◽

X Ray Diffraction ◽

X Ray ◽

Framework Materials ◽

Group 4 ◽

Wide Range ◽

Metal Organic ◽

Group 4 Metal

The importance of defects for inorganic functional framework materials is well established, being crucial for properties from relaxor ferroelectricity to superconductivity. The corresponding study of defects in metal-organic frameworks (MOFs) is still however in its infancy. Recent studies have established that ligand-absence defects can be controllably introduced into frameworks and that these defects can drastically improve the material properties, but have so far shown no evidence of correlation between defects. Much of this research has focussed on UiO-66, a zirconium dicarboxylate MOF that was amongst the first very stable MOFs to be discovered.[1] As a result of its stability, it and its derivatives have been investigated for a wide range of properties including photo- and Brønsted acid catalysis, sensing and gas sorption properties. The ability to introduce defects has been demonstrated to substantially enhance both the sorption and catalytic properties of UiO-66.[2][3] We have demonstrated, using a combination of powder X-ray diffraction, total scattering and electron diffraction measurements, that UiO-66 can be engineered, under the appropriate synthetic conditions, to accommodate correlated defect nanodomains. These correlations offer exciting opportunities for manipulating the physical properties, including mass transport, chemical activity and mechanical flexibility.

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In Situ MOF-Templating of Rh Nanocatalysts under Reducing Conditions

Australian Journal of Chemistry ◽

10.1071/ch20193 ◽

2020 ◽

Vol 73 (12) ◽

pp. 1271

Author(s):

Renata Lippi ◽

Campbell J. Coghlan ◽

Shaun C. Howard ◽

Christopher D. Easton ◽

Qinfen Gu ◽

...

Keyword(s):

Photoelectron Spectroscopy ◽

Main Product ◽

Metal Organic Frameworks ◽

Co2 Hydrogenation ◽

X Ray Diffraction ◽

X Ray ◽

Reducing Atmosphere ◽

Reducing Conditions ◽

Metal Organic

Manganese-based metal–organic frameworks (MOFs) metalated with Rh were used as pre-catalysts for CO2 hydrogenation. Activated insitu (80% H2, 20% CO2, 350°C), the resulting templated catalysts displayed CO2 conversion of up to 20%, with CH4 as the main product. Used catalysts were compared with samples templated in 5% H2/Ar at 350°C using powder X-ray diffraction, electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy. It was found that under reducing atmosphere Rh0 nanoparticles formed and organic MOF components decomposed, which allowed growth of MnO or MnCO3 and the formation of a mesh of catalytic Rh0 nanoparticles.

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Phase Transitions in Metal–Organic Frameworks Directly Monitored through In Situ Variable Temperature Liquid-Cell Transmission Electron Microscopy and In Situ X-ray Diffraction

Journal of the American Chemical Society ◽

10.1021/jacs.0c00542 ◽

2020 ◽

Vol 142 (10) ◽

pp. 4609-4615 ◽

Cited By ~ 11

Author(s):

Jiafei Lyu ◽

Xinyi Gong ◽

Seung-Joon Lee ◽

Karthikeyan Gnanasekaran ◽

Xuan Zhang ◽

...

Keyword(s):

Electron Microscopy ◽

Variable Temperature ◽

Metal Organic Frameworks ◽

X Ray Diffraction ◽

X Ray ◽

Transmission Electron ◽

Metal Organic ◽

Liquid Cell ◽

Temperature Liquid

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Insights into Microscopic Crystal Growth Dynamics of CH3NH3PbI3 under a Laser Deposition Process Revealed by In Situ X-ray Diffraction

ACS Applied Materials & Interfaces ◽

10.1021/acsami.1c04488 ◽

2021 ◽

Author(s):

Tetsuhiko Miyadera ◽

Yuto Auchi ◽

Kohei Yamamoto ◽

Noboru Ohashi ◽

Tomoyuki Koganezawa ◽

...

Keyword(s):

Crystal Growth ◽

Growth Dynamics ◽

Deposition Process ◽

Laser Deposition ◽

X Ray Diffraction ◽

X Ray

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Synthesis, crystal structure, luminescence, and photocatalytic properties of a 2D Cu(II) metal-organic frameworks based on 3,5-di(1H-benzimidazol-1-yl)pyridine and 4,4′-oxybis(benzoate) ligands

Zeitschrift für Naturforschung B ◽

10.1515/znb-2020-0041 ◽

2020 ◽

Vol 75 (8) ◽

pp. 727-732

Author(s):

Chen Zhang ◽

Jian-Qing Tao

Keyword(s):

Crystal Structure ◽

Thermal Analysis ◽

Uv Light ◽

Metal Organic Framework ◽

Metal Organic Frameworks ◽

X Ray Diffraction ◽

X Ray ◽

Uv Light Irradiation ◽

Photocatalytic Activities ◽

Metal Organic

AbstractA new Cu(II) metal-organic framework, [Cu(L)(OBA)·H2O]n (1) [H2OBA = 4,4′-oxybis(benzoic acid), L = 3,5-di(1H-benzimidazol-1-yl)pyridine] was hydrothermally synthesized and characterized through IR spectroscopy, elemental and thermal analysis and single-crystal X-ray diffraction. Complex 1 is a four-connected uni-nodal 2D net with a (44·62) topology which shows an emission centered at λ ∼393 nm upon excitation at λ = 245 nm. Moreover, complex 1 possesses high photocatalytic activities for the decomposition of Rhodamine B (RhB) under UV light irradiation.

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