Scale‐up of the Synthesis of Zeolitic Imidazolate Framework ZIF‐4

Hovestadt, Maximilian; Schmitz, Jürgen Vargas; Weissenberger, Tobias; Reif, Florian; Kaspereit, Malte; Schwieger, Wilhelm; Hartmann, Martin

doi:10.1002/cite.201700105

Cited by 11 publications

(11 citation statements)

References 18 publications

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“…Additionally, identifying MOF thermal stability through TGA measurements must be considered because the mass loss maybe not inevitably correlated to structural changes [84]. Therefore, nitrogen has been used as the carrier gas to implement TGA on ZIFs and the heating rate has been fixed to 2 K min −1 in ranges between 30 • C and 700 • C [92].…”

Section: Thermogravimetric Analysis (Tga)mentioning

confidence: 99%

Green Synthesis of Zeolitic Imidazolate Frameworks: A Review of Their Characterization and Industrial and Medical Applications

et al. 2022

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Metal organic frameworks (MOF) are a class of hybrid networks of supramolecular solid materials comprising a large number of inorganic and organic linkers, all bound to metal ions in a well-organized fashion. Zeolitic imidazolate frameworks (ZIFs) are a sub-group of MOFs with imidazole as an organic linker to metals; it is rich in carbon, nitrogen, and transition metals. ZIFs combine the classical zeolite characteristics of thermal and chemical stability with pore-size tunability and the rich topological diversity of MOFs. Due to the energy crisis and the existence of organic solvents that lead to environmental hazards, considerable research efforts have been devoted to devising clean and sustainable synthesis routes for ZIFs to reduce the environmental impact of their preparation. Green chemistry is the key to sustainable development, as it will lead to new solutions to existing problems. Moreover, it will present opportunities for new processes and products and, at its heart, is scientific and technological innovation. The green chemistry approach seeks to redesign the materials that make up the basis of our society and our economy, including the materials that generate, store, and transport our energy, in ways that are benign for humans and the environment and that possess intrinsic sustainability. This study covers the principles of green chemistry as used in designing strategies for synthesizing greener, less toxic ZIFs the consume less energy to produce. First, the necessity of green methods in today’s society, their replacement of the usual non-green methods and their benefits are discussed; then, various methods for the green synthesis of ZIF compounds, such as hydrothermally, ionothermally, and by the electrospray technique, are considered. These methods use the least harmful and toxic substances, especially concerning organic solvents, and are also more economical. When a compound is synthesized by a green method, a question arises as to whether these compounds can replace the same compounds as synthesized by non-green methods. For example, is the thermal stability of these compounds (which is one of the most important features of ZIFs) preserved? Therefore, after studying the methods of identifying these compounds, in the last part, there is an in-depth discussion on the various applications of these green-synthesized compounds.

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Section: Thermogravimetric Analysis (Tga)mentioning

confidence: 99%

Green Synthesis of Zeolitic Imidazolate Frameworks: A Review of Their Characterization and Industrial and Medical Applications

et al. 2022

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“…These materials show stronger interaction with olefin, and the loading is based on the effect described by Dewar, Chatt, and Duncanson [ 9 , 10 ]. A selectivity analogous to ZIF-4 has in principle been reported for similar adsorbents namely ZIF-7 [ 11 ], ZIF-8 [ 7 ], ZIF-71 [ 2 ] FIR-51 [ 12 ], UTSA-10 [ 13 ], and PCN-250 [ 14 ] and several activated carbons [ 15 , 16 , 17 ]. However, these materials are more expensive in preparation, exhibit an unfavorable separation potential, or are not well studied.…”

Section: Introductionmentioning

confidence: 85%

Continuous Separation of Light Olefin/Paraffin Mixtures on ZIF-4 by Pressure Swing Adsorption and Membrane Permeation

et al. 2018

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In this study, two zeolitic imidazolate frameworks (ZIFs) called ZIF-4 and ZIF-zni (zni is the network topology) were characterized by sorption studies regarding their paraffin/olefin separation potential. In particular, equilibrated pure and mixed gas adsorption isotherms of ethane and ethene were recorded at 293 K up to 3 MPa. ZIF-4 exhibits selectivities for ethane in the range of 1.5–3, which is promising for continuous pressure swing adsorption (PSA). ZIF-4 shows high cycle stability with promising separation potential regarding ethane, which results in purification of the more industrial desired olefin. Furthermore, both ZIF materials were implemented in Matrimid to prepare a mixed matrix membrane (MMM) and were used in the continuous separation of a propane/propene mixture. The separation performance of the neat polymer is drastically increased after embedding porous ZIF-4 crystals in the Matrimid matrix, especially at higher feed pressures (3–5 barg). Due to the smaller kinetic diameter of the olefin, the permeability is higher compared to the paraffin.

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“…Among all those polymorphs, ZIF-4 is relatively the most energetically stable and most studied phase among the microporous Zn(Im) 2 compounds. ZIF-4 has a remarkable performance in separation of olefin/paraffin mixtures compared to other promising MOFs such as CPO-27 and MIL-53, the capability of adsorbing and retaining radioactive iodine, and ability to be shaped. , The synthetic route to ZIF-4 is scalable, which demonstrates a potential for its industrial applications. Meanwhile, ZIF- zni and ZIF- coi compete as the most stable dense polymorphs …”

Section: Introductionmentioning

confidence: 99%

Rich Polymorphism of a Metal–Organic Framework in Pressure–Temperature Space

et al. 2019

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We present an in situ powder X-ray diffraction study on the phase stability and polymorphism of the metal− organic framework ZIF-4, Zn(imidazolate) 2 , at simultaneous high pressure and high temperature, up to 8 GPa and 600 °C. The resulting pressure−temperature phase diagram reveals four, previously unknown, high-pressure−high-temperature ZIF phases. The crystal structures of two new phasesZIF-4cp-II and ZIF-hPT-IIwere solved by powder diffraction methods. The total energy of ZIF-4-cp-II was evaluated using density functional theory calculations and was found to lie in between that of ZIF-4 and the most thermodynamically stable polymorph, ZIF-zni. ZIF-hPT-II was found to possess a doubly interpenetrated diamondoid topology and is isostructural with previously reported Cd(Imidazolate) 2 and Hg(Imidazolate) 2 phases. This phase exhibited extreme resistance to both temperature and pressure. The other two new phases could be assigned with a unit cell and space group, although their structures remain unknown. The pressure−temperature phase diagram of ZIF-4 is strikingly complicated when compared with that of the previously investigated, closely related ZIF-62 and demonstrates the ability to traverse complex energy landscapes of metal−organic systems using the combined application of pressure and temperature.

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Scale‐up of the Synthesis of Zeolitic Imidazolate Framework ZIF‐4

Cited by 11 publications

References 18 publications

Green Synthesis of Zeolitic Imidazolate Frameworks: A Review of Their Characterization and Industrial and Medical Applications

Green Synthesis of Zeolitic Imidazolate Frameworks: A Review of Their Characterization and Industrial and Medical Applications

Continuous Separation of Light Olefin/Paraffin Mixtures on ZIF-4 by Pressure Swing Adsorption and Membrane Permeation

Rich Polymorphism of a Metal–Organic Framework in Pressure–Temperature Space

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