Synthesis of<scp>MOFs</scp>at the Industrial Scale

Firmino, Ana D. G.; Mendes, Ricardo F.; Tomé, João P. C.; Paz, Filipe A. Almeida

doi:10.1002/9783527809097.ch3

Cited by 10 publications

(10 citation statements)

References 58 publications

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“…Herein, we proposed that the employment of a small-scale solvothermal reaction in the synthesis of M-MOF-184 will be a potential strategy for achieving the pure phase of the crystalline framework endowed with optimal surface areas and accessible pore apertures. 45,46 As expected, our activated M-MOF-184 (M = Mg, Co, Ni, Zn) materials had high surface areas (S BET > 3200 m 2 g −1 ), and Mg-MOF-184 represented one of the highest BET surface area values reported for isoreticular MOF-74 structures (>4000 m 2 g −1 ). Specifically, Co-MOF-184 had the highest CO 2 uptake at 298 K, and Zn-MOF-184 revealed the best catalytic activity upon cycloaddition of CO 2 among the series.…”

Section: ■ Introductionsupporting

confidence: 76%

Series of M-MOF-184 (M = Mg, Co, Ni, Zn, Cu, Fe) Metal–Organic Frameworks for Catalysis Cycloaddition of CO₂

et al. 2020

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In light of the chemical exploitation of CO 2 , new reusable materials for efficiently catalyzing the cycloaddition of CO 2 and epoxides under moderate conditions are needed. Herein, a new series of isostructural metal−organic frameworks (MOFs) M 2 (EDOB) [EDOB 4− = 4,4′-(ethyne-1,2-diyl)bis(2-oxidobenzoate), M = Mg, Ni, Co, Zn, Cu, Fe], known as M-MOF-184, analogous to a well-studied MOF-74 structure, were synthesized and fully characterized. The M-MOF-184 (M = Mg, Co, Ni, Zn) frameworks exhibit accessible mesopore channels (24 Å) and high porosity. Among them, Mg-MOF-184 demonstrated the most upper surface area (>4000 m 2 g −1 ) in any reported MOF-74-type frameworks. Furthermore, Co-MOF-184 revealed the highest CO 2 uptake (73 cm 3 g −1 , at 298 K), and Zn-MOF-184 showed the highest catalytic activity upon the cycloaddition of CO 2 (96% conversion, 86% selectivity, and 82% yield) under mild conditions (1 atm CO 2 , 80 °C, 6 h, and solvent-free). Notably, the catalytic performance of Zn-MOF-184 outperformed that of the original M-MOF-74 (M = Mg, Co, Zn) materials and various Zn-based MOFs. To evaluate the acidity and basicity of a series of M-MOF-184 (M = Mg, Co, Ni, Zn) frameworks, the interaction of these MOFs with acetonitrile vapor was investigated by vapor adsorption and ATR-FTIR spectroscopy measurements. As such, Zn-MOF-184 showed the strongest Lewis acidity derived by Zn cations, which was correlated to the highest catalytic activity upon the cycloaddition of CO 2 . Interestingly, the 2-oxidobenzoate anions from Co-MOF-184 showed the strongest basicity among the series, which was associated with the highest saturated acetonitrile uptake (544 cm 3 g −1 at 298 K). Our findings suggest that the integration of Lewis acidic and basic sites, high surface area, and large accessible pores into the framework can facilitate the CO 2 fixation reaction.

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Section: ■ Introductionsupporting

confidence: 76%

Series of M-MOF-184 (M = Mg, Co, Ni, Zn, Cu, Fe) Metal–Organic Frameworks for Catalysis Cycloaddition of CO₂

et al. 2020

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“…For real synthesis, cracks and/or defects may occur at the interface which can affect the flux of gas molecules through the pores of MOF membranes. Additionally, industrial-scale synthesis of these MOFs requires large-scale production in which the cost and rapid availability of reactants, a high-yield synthesis procedure, and purity of the compounds should be considered . Among the top candidates, RAVWOC, RAVXAP, and RAVXIX are isoreticular series of MOF-74, which is commercially produced .…”

Section: Results and Discussionmentioning

confidence: 99%

“…Additionally, industrial-scale synthesis of these MOFs requires large-scale production in which the cost and rapid availability of reactants, a high-yield synthesis procedure, and purity of the compounds should be considered . Among the top candidates, RAVWOC, RAVXAP, and RAVXIX are isoreticular series of MOF-74, which is commercially produced . Nontoxic metal sources and/or biocompatible linkers offer an advantage for environmentally friendly MOF synthesis .…”

Section: Results and Discussionmentioning

confidence: 99%

Biocompatible MOFs for Storage and Separation of O₂: A Molecular Simulation Study

Gülçay

Eruçar

2019

Ind. Eng. Chem. Res.

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Metal organic frameworks (MOFs) are great candidates for capturing O2 due to their highly porous structures and tunable physical and chemical properties. In this study, we assessed the performance of 1525 biocompatible MOFs which have endogenous linkers and nontoxic metal centers for adsorption-based and membrane-based O2 separation and also for high-pressure O2 storage. We initially computed Henry’s constants of O2 and N2 at zero coverage and 298 K by performing Grand Canonical Monte Carlo (GCMC) simulations and estimated infinite dilution adsorption selectivities for O2/N2 mixture. We performed binary mixture GCMC simulations for the top 15 candidates at various pressures and 298 K and compared mixture adsorption selectivities with those obtained from infinite dilution. We then estimated O2 working capacities of 315 biocompatible MOFs obtained at 298 K and 140 bar for storage and 5 bar for release pressures. Our results showed that 15 biocompatible MOFs outperform gravimetric O2 working capacities of the traditional adsorbent materials such as activated carbon and NaX and some common MOFs such as NU-125 and UMCM-152 at 298 K. We finally calculated O2 and N2 permeabilities and membrane selectivities of 45 promising MOF candidates for O2/N2 separation. Seventeen biocompatible MOF membranes were identified to exceed the Robeson’s upper bound established for polymers. This computational study will be useful to identify the promising biocompatible MOFs for storage and separation of O2. The bio-MOF library constructed in this study will also guide both experimental and computational studies for design and development of biocompatible MOFs for various medical applications.

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“…Please do not adjust margins Please do not adjust margins scale synthesis at ambient pressure using green solvent. 9,10 Furthermore, the type of solvent employed is of great importance to the process, in regards to safety, legal and economic limitations. The use of so called "green" solvents (i.e.…”

Section: Introductionmentioning

confidence: 99%

“…8 Sulphates, carbonates, oxides and acetates are considered as a safer alternative, however, their use is challenged by poor solubility or hydrolysis. 7,10 In addition, the presence of such salts in the effluents can sometimes be restricted by environmental regulations leading, in turn, to higher manufacture costs. 6 With all safety and environmental requirements carefully addressed, an economical assessment can be initiated after a process synthesis (i.e.…”

Section: Introductionmentioning

confidence: 99%

MOFs industrialization: a complete assessment of production costs

et al. 2021

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Synthesis ofMOFsat the Industrial Scale

Cited by 10 publications

References 58 publications

Series of M-MOF-184 (M = Mg, Co, Ni, Zn, Cu, Fe) Metal–Organic Frameworks for Catalysis Cycloaddition of CO₂

Series of M-MOF-184 (M = Mg, Co, Ni, Zn, Cu, Fe) Metal–Organic Frameworks for Catalysis Cycloaddition of CO₂

Biocompatible MOFs for Storage and Separation of O₂: A Molecular Simulation Study

MOFs industrialization: a complete assessment of production costs

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Synthesis ofMOFsat the Industrial Scale

Cited by 10 publications

References 58 publications

Series of M-MOF-184 (M = Mg, Co, Ni, Zn, Cu, Fe) Metal–Organic Frameworks for Catalysis Cycloaddition of CO2

Series of M-MOF-184 (M = Mg, Co, Ni, Zn, Cu, Fe) Metal–Organic Frameworks for Catalysis Cycloaddition of CO2

Biocompatible MOFs for Storage and Separation of O2: A Molecular Simulation Study

MOFs industrialization: a complete assessment of production costs

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Product

Resources

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Series of M-MOF-184 (M = Mg, Co, Ni, Zn, Cu, Fe) Metal–Organic Frameworks for Catalysis Cycloaddition of CO₂

Series of M-MOF-184 (M = Mg, Co, Ni, Zn, Cu, Fe) Metal–Organic Frameworks for Catalysis Cycloaddition of CO₂

Biocompatible MOFs for Storage and Separation of O₂: A Molecular Simulation Study