Supercritical CO2 utilization for the crystallization of 2D metal-organic frameworks using tert-butylpyridine additive

Portolés‐Gil, Núria; Gowing, Sarah; Vallcorba, Oriol; Domingo, Concepción; López‐Periago, Ana M.; Ayllón, José A.

doi:10.1016/j.jcou.2018.02.004

Cited by 15 publications

(9 citation statements)

References 25 publications

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“…Note that these MOF syntheses were investigated at supercritical conditions of CO 2 (160 bar, 80 °C) and for extended reaction times (48 h) which differ from conditions chosen in Peng's research introduced previously. The extreme reaction conditions in CO 2 have also been employed in the synthesis of 1D, 2D, and 3D MOFs by reactive crystallisation in the absence of or using lower volumes of solvents [117][118][119].…”

Section: Compressed or Supercritical Carbon Dioxide Methodsmentioning

confidence: 99%

Hierarchical Metal–Organic Frameworks with Macroporosity: Synthesis, Achievements, and Challenges

et al. 2019

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HIGHLIGHTS• The advantages of macroporous metal-organic frameworks (MOFs) in comparison with micro-and mesoporous MOFs are discussed.• A range of synthetic methods for the fabrication and characterisation of hierarchical MOFs with macroporosity are reviewed.• The applications, advancements, and challenges of each method are compared and assessed in detail.ABSTRACT Introduction of multiple pore size regimes into metalorganic frameworks (MOFs) to form hierarchical porous structures can lead to improved performance of the material in various applications.In many cases, where interactions with bulky molecules are involved, enlarging the pore size of typically microporous MOF adsorbents or MOF catalysts is crucial for enhancing both mass transfer and molecular accessibility. In this review, we examine the range of synthetic strategies which have been reported thus far to prepare hierarchical MOFs or MOF composites with added macroporosity. These fabrication techniques can be either pre-or post-synthetic and include using hard or soft structural template agents, defect formation, routes involving supercritical CO 2 , and 3D printing. We also discuss potential applications and some of the challenges involved with current techniques, which must be addressed if any of these approaches are to be taken forward for industrial applications.

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Section: Compressed or Supercritical Carbon Dioxide Methodsmentioning

confidence: 99%

Hierarchical Metal–Organic Frameworks with Macroporosity: Synthesis, Achievements, and Challenges

et al. 2019

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“…MOF syntheses in scCO 2 are normally carried out in the presence of organic liquids such as DMF and DMSO to increase the solubility of both polar and nonpolar compounds in the reaction. It has been shown that using ligands such as tert-butylpyridine (t-bpy) and 4,4 -bipyridine can increase the solubility of the reagents in the reaction media, resulting in more efficient use of scCO 2 [41,42,55]. Here, we employ the flexible reduced Schiff-base compound 4-carboxy-phenylene-methyleneamino-4-benzoic acid as a linker; we note that the biphenyl-4,4 -dicarboxylate linkers have been used with great success in MOF synthesis [56][57][58][59].…”

Section: Methodsmentioning

confidence: 99%

“…Due to the high interest in these materials, various synthetic methods have been developed beyond the conventional solvothermal approaches which, though a straightforward way to achieve highly crystalline materials, have the potential to use large amounts of organic solvents. In addition, there has been a recent trend towards the creation of multiple porosities (so-called hierarchical pore structures) in these materials [23,24], leading to the development of a number of innovative synthetic strategies including macrostructural templating [25][26][27][28][29], gelation [30][31][32][33], acid etching [34][35][36][37], use of scCO 2 [38][39][40][41][42], and three-dimensional (3D) printing [43][44][45][46].…”

Section: Introductionmentioning

confidence: 99%

Using Supercritical CO2 in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation

et al. 2019

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In this report, we explore the use of supercritical CO2 (scCO2) in the synthesis of well-known metal-organic frameworks (MOFs) including Zn-MOF-74 and UiO-66, as well as on the preparation of [Cu24(OH-mBDC)24]n metal-organic polyhedra (MOPs) and two new MOF structures {[Zn2(L1)(DPE)]∙4H2O}n and {[Zn3(L1)3(4,4′-azopy)]∙7.5H2O}n, where BTC = benzene-1,3,5-tricarboxylate, BDC = benzene-1,4-dicarboxylate, L1 = 4-carboxy-phenylene-methyleneamino-4-benzoate, DPE = 1,2-di(4-pyridyl)ethylene, 4.4′-azopy = 4,4′- azopyridine, and compare the results versus traditional solvothermal preparations at low temperatures (i.e., 40 °C). The objective of the work was to see if the same or different products would result from the scCO2 route versus the solvothermal method. We were interested to see which method produced the highest yield, the cleanest product and what types of morphology resulted. While there was no evidence of additional meso- or macroporosity in these MOFs/MOPs nor any significant improvements in product yields through the addition of scCO2 to these systems, it was shown that the use of scCO2 can have an effect on crystallinity, crystal size and morphology.

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“…Historically, continuous-flow scCO 2 processes focused on applications involving botanical extraction, coal gasification, and turbomachinery power cycles − – not on the synthesis of complex materials such as MOFs. Recently in a batch process, scCO 2 was used to synthesize MOFs, but in addition to being noncontinuous, the method also had long reaction times, ranging between 3 and 90 h . In contrast to the batch method, a continuous-flow process requires the management of phase changes occurring in the reactor. , Additionally, because thermodynamic properties vary significantly near the critical point, design decisions must consider these nonlinearities.…”

Section: Introductionmentioning

confidence: 99%

Scalable Continuous Flow Metal–Organic Framework (MOF) Synthesis Using Supercritical CO₂

Rasmussen

Kramlich

Novosselov

2020

ACS Sustainable Chem. Eng.

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The high surface areas and tunable porous structures of Metal−Organic Framework (MOF) materials offer desirable capabilities in a wide range of applications. One challenge to the widespread use of MOFs is a lack of large-scale manufacturing synthesis processes. This paper presents a novel method of continuous synthesis of MOF using supercritical carbon dioxide (scCO 2 ), introduced through a custom counter-current mixer, to provide enhanced heat and mass transfer to MOF precursor materials. The method was used to synthesize the zirconium-based MOF UiO-66 at a production rate of 104 g/h. Synthesis of UiO-66 was confirmed via SEM images, powder X-ray diffraction (PXRD) spectra, and physisorption analysis. Additionally, testing showed that this method could be used to activate as well as continuously synthesize MOF materials. Our method results in rapid reaction time (<3s), can be easily scaled, and it allows for recovery of effluent and unreacted material, which is challenging in hydrothermal and supercritical water-based systems.

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Supercritical CO2 utilization for the crystallization of 2D metal-organic frameworks using tert-butylpyridine additive

Cited by 15 publications

References 25 publications

Hierarchical Metal–Organic Frameworks with Macroporosity: Synthesis, Achievements, and Challenges

Hierarchical Metal–Organic Frameworks with Macroporosity: Synthesis, Achievements, and Challenges

Using Supercritical CO2 in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation

Scalable Continuous Flow Metal–Organic Framework (MOF) Synthesis Using Supercritical CO₂

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Supercritical CO2 utilization for the crystallization of 2D metal-organic frameworks using tert-butylpyridine additive

Cited by 15 publications

References 25 publications

Hierarchical Metal–Organic Frameworks with Macroporosity: Synthesis, Achievements, and Challenges

Hierarchical Metal–Organic Frameworks with Macroporosity: Synthesis, Achievements, and Challenges

Using Supercritical CO2 in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation

Scalable Continuous Flow Metal–Organic Framework (MOF) Synthesis Using Supercritical CO2

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Product

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Scalable Continuous Flow Metal–Organic Framework (MOF) Synthesis Using Supercritical CO₂