In-situ IR monitoring of the formation of Zr-fumarate MOF

Ren, Jianwei; Musyoka, Nicholas M.; Langmi, Henrietta W.; North, Brian C; Mathe, Mkhulu; Pang, Wan; Wang, Mingjie; Walker, J.F.

doi:10.1016/j.apsusc.2017.01.271

Cited by 28 publications

(21 citation statements)

References 54 publications

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“…These weight loss differences could originate from the drying stage of the materials; however, they have been placed in the same climatic oven for the same duration. These weight losses are consistent with former studies, which supports our suggestion [28,40,48,49].…”

Section: Characterization Of Mofssupporting

confidence: 93%

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Zirconium-Based Metal Organic Frameworks for the Capture of Carbon Dioxide and Ethanol Vapour. A Comparative Study

Saidi

Yadav

et al. 2021

Molecules

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This paper reports on the comparison of three zirconium-based metal organic frameworks (MOFs) for the capture of carbon dioxide and ethanol vapour at ambient conditions. In terms of efficiency, two parameters were evaluated by experimental and modeling means, namely the nature of the ligands and the size of the cavities. We demonstrated that amongst three Zr-based MOFs, MIP-202 has the highest affinity for CO2 (−50 kJ·mol−1 at low coverage against around −20 kJ·mol−1 for MOF-801 and Muc Zr MOF), which could be related to the presence of amino functions borne by its aspartic acid ligands as well as the presence of extra-framework anions. On the other side, regardless of the ligand size, these three materials were able to adsorb similar amounts of carbon dioxide at 1 atm (between 2 and 2.5 µmol·m−2 at 298 K). These experimental findings were consistent with modeling studies, despite chemisorption effects, which could not be taken into consideration by classical Monte Carlo simulations. Ethanol adsorption confirmed these results, higher enthalpies being found at low coverage for the three materials because of stronger van der Waals interactions. Two distinct sorption processes were proposed in the case of MIP-202 to explain the shape of the enthalpic profiles.

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Section: Characterization Of Mofssupporting

confidence: 93%

“…This is likely due to the presence of physisorbed water in the mesopores of this material (see below). As confinement effects are directly related to the size of the pores, it can be deduced that water desorption can take place faster in mesopores compared to that observed for the microporous muc-Zr MOF and MIP-202 [48,49].…”

Section: Characterization Of Mofsmentioning

confidence: 96%

Zirconium-Based Metal Organic Frameworks for the Capture of Carbon Dioxide and Ethanol Vapour. A Comparative Study

Saidi

Yadav

et al. 2021

Molecules

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“…Synthesis can only take place under modulation/coordination conditions, using considerable amounts of competing monotopic acids as the modulator, resulting in higher crystallinity and yield of the material. Indeed, when not using this approach, the resulting material is nearly amorphous 38 . Zr-fumarate-MOF has recently been the subject of scientific interest due to its high water stability 39 , as well as its potential for green synthesis 40 and facile shaping through direct monolith formation by a gel approach 41 .…”

Section: Introductionmentioning

confidence: 99%

Role of Structural Defects in the Adsorption and Separation of C3 Hydrocarbons in Zr-Fumarate-MOF (MOF-801)

et al. 2019

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An effective separation of propylene/propane mixtures is one of the most important processes in the petrochemical industry. Incidentally this separation is challenging due to the extensive similarities between both gases in terms of physicochemical properties such as, but not only limited to, boiling point, kinetic diameter and molecular weight. A drive to switch to less energy consuming processes, like adsorption or membrane separation, has highlighted several microporous metal organic frameworks as promising materials. In this work, we present a combined numerical and experimental investigation on propane and propylene adsorption in Zr-fumarate-MOF (also known as MOF-801), a small pore isoreticular analogue of UiO-66. Here, we demonstrate how the presence of structural defects can completely change the sorptive properties and separation performance of the Zr-fumarate-MOF, with enhanced capacity and gas diffusion rates for C3-sized hydrocarbons at the cost of kinetic selectivity. Extensive GCMC simulations performed on mixed defective supercells show that a percentage of missing cluster defects of around 1/8 th can best account for the experimental results. Furthermore, analysis of low-frequency phonon spectra is used to explain gaseous diffusion in the original pristine material. A slight preference for propane over propylene is highlighted in the defective sample, and confirmed through column breakthrough experiments, suggesting the potential applicability of the Zr-fumarate-MOF in this challenging separation. File list (3) download file view on ChemRxiv manuscript.pdf (3.98 MiB) download file view on ChemRxiv manuscript-SI.pdf (3.63 MiB) download file view on ChemRxiv structures.zip (60.21 KiB)

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“…To shed light on the early stages of MOF formation and gain knowledge about the short-range atomic order of MOFs, NMR, IR, and Raman spectroscopy are suitable techniques, as they provide information on interactions between functional groups. However, to the best of our knowledge, only Ren et al have used in situ IR spectroscopy to monitor the formation of Zr-fumarate MOF [57]. Thus, MIL-53(Al), one of the most-studied MOFs with interesting breathing behavior and high thermal stability, was used as a model system to study MOF formation by ATR-FTIR and Raman spectroscopy [58,59].…”

Section: Metal-organic Framework Mil-53(al)mentioning

confidence: 99%

In Situ Monitoring of Particle Formation with Spectroscopic and Analytical Techniques Under Solvothermal Conditions

et al. 2020

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The formation of multifunctional materials involves various simultaneous and closely entangled physicochemical processes including nucleation, growth, aggregation, and in some cases also growth by oriented aggregation. These elementary particle formation processes occur in broad size ranges from the molecular to micrometer level and time scales ranging from seconds to hours. This contribution demonstrates that the in situ monitoring of reaction mixtures and dispersions with several simultaneous analytical and spectroscopic techniques is an effective and widely applicable strategy to achieve an in-depth understanding of the formation of complex particulate structures and to move towards the rational design of materials.

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In-situ IR monitoring of the formation of Zr-fumarate MOF

Cited by 28 publications

References 54 publications

Zirconium-Based Metal Organic Frameworks for the Capture of Carbon Dioxide and Ethanol Vapour. A Comparative Study

Zirconium-Based Metal Organic Frameworks for the Capture of Carbon Dioxide and Ethanol Vapour. A Comparative Study

Role of Structural Defects in the Adsorption and Separation of C3 Hydrocarbons in Zr-Fumarate-MOF (MOF-801)

In Situ Monitoring of Particle Formation with Spectroscopic and Analytical Techniques Under Solvothermal Conditions

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