Manometric Real-Time Studies of the Mechanochemical Synthesis of Zeolitic Imidazolate Frameworks

We demonstrate a method for real-time monitoring of mechanochemical synthesis of metal-organic frameworks, by measuring changes in pressure of gas produced in the reaction. Using this manometric method to monitor the mechanosynthesis of the zeolitic imidazolate framework ZIF-8 from basic zinc carbonate reveals an intriguing feedback mechanism in which the initially formed ZIF-8 reacts with the CO2 byproduct to produce a complex metal carbonate phase, the structure of which is determined from powder X-ray diffraction data. Formation of the carbonate phase may be prevented by using excess ligand, leading to quantitative formation of ZIF-8. This reaction was performed on a 90 g scale, with the excess ligand removed by sublimation.

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Manometric real-time studies of the mechanochemical synthesis of zeolitic imidazolate frameworks

Chemical Science ◽

10.1039/c9sc05514b ◽

2020 ◽

Vol 11 (8) ◽

pp. 2141-2147 ◽

Cited By ~ 12

Author(s):

Ivana Brekalo ◽

Wenbing Yuan ◽

Cristina Mottillo ◽

Yuneng Lu ◽

Yuancheng Zhang ◽

...

Keyword(s):

Real Time ◽

Mechanochemical Synthesis ◽

Metal Organic Frameworks ◽

Zeolitic Imidazolate Frameworks ◽

Real Time Monitoring ◽

Simple Method ◽

Metal Organic

We demonstrate a simple method for real-time monitoring of mechanochemical synthesis of metal–organic frameworks, by measuring changes in pressure of gas produced in the reaction.

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Revisiting the High-Pressure Properties of the Metal-Organic Frameworks ZIF-8 and ZIF-67

10.26434/chemrxiv.13146278.v1 ◽

2020 ◽

Author(s):

Pia Vervoorts ◽

Stefan Burger ◽

Karina Hemmer ◽

Gregor Kieslich

Keyword(s):

High Pressure ◽

State Of The Art ◽

Energy Landscape ◽

Structural Flexibility ◽

Zeolitic Imidazolate Frameworks ◽

Stimuli Responsive ◽

X Ray Diffraction ◽

X Ray ◽

Open Questions ◽

Metal Organic

The zeolitic imidazolate frameworks ZIF-8 and ZIF-67 harbour a series of fascinating stimuli responsive properties. Looking at their responsitivity to hydrostatic pressure as stimulus, open questions exist regarding the isotropic compression with non-penetrating pressure transmitting media. By applying a state-of-the-art high-pressure powder X-ray diffraction setup, we revisit the high-pressure behaviour of ZIF-8 and ZIF-67 up to p = 0.4 GPa in small pressure increments. We observe a drastic, reversible change of high-pressure powder X-ray diffraction data at p = 0.3 GPa, discovering large volume structural flexibility in ZIF-8 and ZIF-67. Our results imply a shallow underlying energy landscape in ZIF-8 and ZIF-67, an observation that might point at rich polymorphism of ZIF-8 and ZIF-67, similar to ZIF-4(Zn).

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Revisiting the High-Pressure Properties of the Metal-Organic Frameworks ZIF-8 and ZIF-67

10.26434/chemrxiv.13146278 ◽

2020 ◽

Author(s):

Pia Vervoorts ◽

Stefan Burger ◽

Karina Hemmer ◽

Gregor Kieslich

Keyword(s):

High Pressure ◽

State Of The Art ◽

Energy Landscape ◽

Structural Flexibility ◽

Zeolitic Imidazolate Frameworks ◽

Stimuli Responsive ◽

X Ray Diffraction ◽

X Ray ◽

Open Questions ◽

Metal Organic

The zeolitic imidazolate frameworks ZIF-8 and ZIF-67 harbour a series of fascinating stimuli responsive properties. Looking at their responsitivity to hydrostatic pressure as stimulus, open questions exist regarding the isotropic compression with non-penetrating pressure transmitting media. By applying a state-of-the-art high-pressure powder X-ray diffraction setup, we revisit the high-pressure behaviour of ZIF-8 and ZIF-67 up to p = 0.4 GPa in small pressure increments. We observe a drastic, reversible change of high-pressure powder X-ray diffraction data at p = 0.3 GPa, discovering large volume structural flexibility in ZIF-8 and ZIF-67. Our results imply a shallow underlying energy landscape in ZIF-8 and ZIF-67, an observation that might point at rich polymorphism of ZIF-8 and ZIF-67, similar to ZIF-4(Zn).

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High-Throughput Electron Diffraction Reveals a Hidden Novel Metal-Organic Framework for Electrocatalysis

10.26434/chemrxiv.13725817.v2 ◽

2021 ◽

Author(s):

Meng Ge ◽

Yanzhi Wang ◽

Francesco Carraro ◽

Weibin Liang ◽

Morteza Roostaeinia ◽

...

Keyword(s):

Electron Diffraction ◽

High Throughput ◽

Metal Organic Framework ◽

Three Dimensional ◽

Reduction Reaction ◽

New Materials ◽

X Ray Diffraction ◽

Zeolitic Imidazolate Framework ◽

Wide Range ◽

Metal Organic

Metal-organic frameworks (MOFs) are known for their versatile combination of inorganic building units and organic linkers, which offers immense opportunities in a wide range of applications. However, many MOFs are typically synthesized as multiphasic polycrystalline powders, which are challenging for studies by X-ray diffraction. Therefore, developing new structural characterization techniques is highly desired in order to accelerate discoveries of new materials. Here, we report a high-throughput approach for structural analysis of MOF nano- and sub-microcrystals by three-dimensional electron diffraction (3DED). A new zeolitic-imidazolate framework (ZIF), denoted ZIF-EC1<a>, </a>was first discovered in a trace amount during the study of a known ZIF-CO3-1 material by 3DED. The structures of both ZIFs were solved and refined using 3DED data. ZIF-EC1 has a dense 3D framework structure, which is built by linking mono- and bi-nuclear Zn clusters and 2-methylimidazolates (mIm-). With a composition of Zn3(mIm)5(OH), ZIF-EC1 exhibits high N and Zn densities. We show that the N-doped carbon material derived from ZIF-EC1 is a promising electrocatalysis for oxygen reduction reaction (ORR). The discovery of this new MOF and its conversion to an efficient electrocatalyst highlights the power of 3DED in developing new materials and their applications.

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Inside Back Cover: Real-Time In Situ Powder X-ray Diffraction Monitoring of Mechanochemical Synthesis of Pharmaceutical Cocrystals (Angew. Chem. Int. Ed. 44/2013)

Angewandte Chemie International Edition ◽

10.1002/anie.201308380 ◽

2013 ◽

Vol 52 (44) ◽

pp. 11665-11665

Author(s):

Ivan Halasz ◽

Andreas Puškarić ◽

Simon A. J. Kimber ◽

Patrick J. Beldon ◽

Ana M. Belenguer ◽

...

Keyword(s):

Real Time ◽

Mechanochemical Synthesis ◽

X Ray Diffraction ◽

Pharmaceutical Cocrystals ◽

X Ray ◽

Back Cover

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Real-Time In Situ Powder X-ray Diffraction Monitoring of Mechanochemical Synthesis of Pharmaceutical Cocrystals

Angewandte Chemie ◽

10.1002/ange.201305928 ◽

2013 ◽

Vol 125 (44) ◽

pp. 11752-11755 ◽

Cited By ~ 23

Author(s):

Ivan Halasz ◽

Andreas Puškarić ◽

Simon A. J. Kimber ◽

Patrick J. Beldon ◽

Ana M. Belenguer ◽

...

Keyword(s):

Real Time ◽

Mechanochemical Synthesis ◽

X Ray Diffraction ◽

Pharmaceutical Cocrystals ◽

X Ray

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Innenrücktitelbild: Real-Time In Situ Powder X-ray Diffraction Monitoring of Mechanochemical Synthesis of Pharmaceutical Cocrystals (Angew. Chem. 44/2013)

Angewandte Chemie ◽

10.1002/ange.201308380 ◽

2013 ◽

Vol 125 (44) ◽

pp. 11881-11881

Author(s):

Ivan Halasz ◽

Andreas Puškarić ◽

Simon A. J. Kimber ◽

Patrick J. Beldon ◽

Ana M. Belenguer ◽

...

Keyword(s):

Real Time ◽

Mechanochemical Synthesis ◽

X Ray Diffraction ◽

Pharmaceutical Cocrystals ◽

X Ray

Download Full-text

High-Throughput Electron Diffraction Reveals a Hidden Novel Metal-Organic Framework for Electrocatalysis

10.26434/chemrxiv.13725817.v3 ◽

2021 ◽

Author(s):

Meng Ge ◽

Yanzhi Wang ◽

Francesco Carraro ◽

Weibin Liang ◽

Morteza Roostaeinia ◽

...

Keyword(s):

Electron Diffraction ◽

High Throughput ◽

Metal Organic Framework ◽

Three Dimensional ◽

Reduction Reaction ◽

New Materials ◽

X Ray Diffraction ◽

Zeolitic Imidazolate Framework ◽

Wide Range ◽

Metal Organic

Metal-organic frameworks (MOFs) are known for their versatile combination of inorganic building units and organic linkers, which offers immense opportunities in a wide range of applications. However, many MOFs are typically synthesized as multiphasic polycrystalline powders, which are challenging for studies by X-ray diffraction. Therefore, developing new structural characterization techniques is highly desired in order to accelerate discoveries of new materials. Here, we report a high-throughput approach for structural analysis of MOF nano- and sub-microcrystals by three-dimensional electron diffraction (3DED). A new zeolitic-imidazolate framework (ZIF), denoted ZIF-EC1<a>, </a>was first discovered in a trace amount during the study of a known ZIF-CO3-1 material by 3DED. The structures of both ZIFs were solved and refined using 3DED data. ZIF-EC1 has a dense 3D framework structure, which is built by linking mono- and bi-nuclear Zn clusters and 2-methylimidazolates (mIm-). With a composition of Zn3(mIm)5(OH), ZIF-EC1 exhibits high N and Zn densities. We show that the N-doped carbon material derived from ZIF-EC1 is a promising electrocatalysis for oxygen reduction reaction (ORR). The discovery of this new MOF and its conversion to an efficient electrocatalyst highlights the power of 3DED in developing new materials and their applications.

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High-Throughput Electron Diffraction Reveals a Hidden Novel Metal-Organic Framework for Electrocatalysis

10.26434/chemrxiv.13725817.v1 ◽

2021 ◽

Author(s):

Meng Ge ◽

Yanzhi Wang ◽

Francesco Carraro ◽

Weibin Liang ◽

Morteza Roostaeinia ◽

...

Keyword(s):

Electron Diffraction ◽

High Throughput ◽

Metal Organic Framework ◽

Three Dimensional ◽

Reduction Reaction ◽

New Materials ◽

X Ray Diffraction ◽

Zeolitic Imidazolate Framework ◽

Wide Range ◽

Metal Organic

Metal-organic frameworks (MOFs) are known for their versatile combination of inorganic building units and organic linkers, which offers immense opportunities in a wide range of applications. However, many MOFs are typically synthesized as multiphasic polycrystalline powders, which are challenging for studies by X-ray diffraction. Therefore, developing new structural characterization techniques is highly desired in order to accelerate discoveries of new materials. Here, we report a high-throughput approach for structural analysis of MOF nano- and sub-microcrystals by three-dimensional electron diffraction (3DED). A new zeolitic-imidazolate framework (ZIF), denoted ZIF-EC1<a>, </a>was first discovered in a trace amount during the study of a known ZIF-CO3-1 material by 3DED. The structures of both ZIFs were solved and refined using 3DED data. ZIF-EC1 has a dense 3D framework structure, which is built by linking mono- and bi-nuclear Zn clusters and 2-methylimidazolates (mIm-). With a composition of Zn3(mIm)5(OH), ZIF-EC1 exhibits high N and Zn densities. We show that the N-doped carbon material derived from ZIF-EC1 is a promising electrocatalysis for oxygen reduction reaction (ORR). The discovery of this new MOF and its conversion to an efficient electrocatalyst highlights the power of 3DED in developing new materials and their applications.

Download Full-text