Thermodynamic Stability of Structure II Methyl Vinyl Ketone Binary Clathrate Hydrates and Effects of Secondary Guest Molecules on Large Guest Conformation

Ahn, Young‐Ho; Kang, Hyery; Cha, Minjun; Shin, Kyuchul; Lee, Huen

doi:10.1021/acsomega.7b00264

Cited by 9 publications

(5 citation statements)

References 39 publications

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“…Gauche I was the most stable conformation, and both Anti conformers (6.78 kJ/mol for Anti I and 6.83 kJ/mol for Anti II) were less stable than the three Gauche conformers (0 kJ/mol for Gauche I, 4.62 kJ/mol for Gauche II, and 3.91 kJ/mol for Gauche III). Although the Gauche conformers of CPM may be preferred in terms of potential energy, many recent reports indicate that hydrocarbon guest molecules are sometimes enclathrated as a relatively less stable conformation. − Because the energy differences among the five conformers were small, they were all considered potential candidates for enclathration in the hydrate cage if the formation of the binary CPM + CH 4 clathrate proved possible.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Therefore, it is reasonable to assign the conformation of CPM in the large cages of sII hydrate as a dynamic Anti form (Anti I or Anti II). 45,46,50,51 Figure 3 shows the Raman spectra of the binary CPM + CH 4 hydrate, which were used to investigate the guest inclusion behavior. As indicated by the 13 C NMR spectra, a weak Raman signal at 2902 cm −1 corresponded to the inclusion of CH 4 molecules in the sII-L cages, and a strong signal at 2913 cm −1 showed that CH 4 was present in the sII-S cages (Figure 3).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…As the difference in relative energies between the Anti I and Anti II conformations is very small, about 0.06 kJ/mol (Figure ), this dihedral angle is very likely dynamic and freely rotating within the time frame of the NMR experiment. Therefore, it is reasonable to assign the conformation of CPM in the large cages of sII hydrate as a dynamic Anti form (Anti I or Anti II). ,,, …”

Section: Results and Discussionmentioning

confidence: 99%

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Spectroscopic Observations of Host–Guest Hydrogen Bonding in Binary Cyclopropanemethanol + Methane Hydrate

2019

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Herein, we report a new structure II (sII) hydrate with cyclopropanemethanol (CPM) in the presence of methane (CH4) gas for the first time and investigate the host–guest hydrogen bonding in the binary CPM + CH4 hydrate via solid-state NMR, Raman spectroscopy, and synchrotron X-ray powder diffraction analysis. The crystal structure and guest distribution of the binary CPM + CH4 hydrate were characterized using solid-state 13C NMR and powder diffraction analyses, which confirmed the formation of the binary sII CPM + CH4 hydrate. The CPM in the large cages of sII hydrate was predicted to be present in the dynamic Anti (Anti I or Anti II) form based on the measured- and calculated- NMR spectra. The inclusion of CH4 molecules in both the large and small cages of the sII hydrate was observed from the 13C NMR and Raman spectra. No free OH signals of the CPM guest were observed in the Raman spectra of the binary CPM + CH4 hydrate, which indicated that the CPM guest participated in host–guest hydrogen bonding with the water framework. The powder diffraction pattern of the binary CPM + CH4 hydrate was refined using Rietveld analysis with the direct space method, and the results supported the hydrogen bonding of the hydroxyl group of the CPM guest to the host water molecules. The phase equilibrium temperature and pressure conditions of the binary CPM + CH4 hydrate were also measured, and the binary CPM + CH4 hydrate was found to be less stable than the binary tetrahydrofuran + CH4 hydrate.

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Section: Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

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Spectroscopic Observations of Host–Guest Hydrogen Bonding in Binary Cyclopropanemethanol + Methane Hydrate

2019

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“…Numerous organic compounds can act as hydrate formers and are not limited to hydrocarbons. Diverse sII and sH formers contain various functional groups have been reported thus far, including hydroxyl, − ether, − ketone, ,,− amine, − nitro, , and others. − The ability of a compound to act as a hydrate former and the specific hydrate structure it forms primarily depends on its size, although other factors also influence it. For example, diisopropyl amine is an sH former, whereas 2,4-dimethylpentane and diisopropyl ether are not, despite being isoelectric and exhibiting similar structures and size.…”

Section: Introductionmentioning

confidence: 99%

Geometric and Hydrophilic Effects of Oxirane Compounds with a Four-Carbon Backbone on Clathrate Hydrate Formation

Seol

2023

ACS Omega

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The physicochemical properties of clathrate hydrates are influenced by the chemical nature and three-dimensional (3D) geometry of the added molecules. This study investigates the effects of five oxirane compounds: cis-2,3-epoxybutane (c23EB), trans-2,3-epoxybutane (t23EB), 1,2-epoxybutane (12EB), 1,2,3,4-diepoxybutane (DEB), and 3,3-dimethylepoxybutane (33DMEB) on CH4 hydrate formation. Despite having a four-carbon backbone, these compounds differ in their 3D geometries. The structures and stabilities of CH4 hydrates containing each compound were analyzed using high-resolution powder diffraction, solid-state 13C NMR, and phase equilibrium measurements. The experimental results revealed that c23EB, 12EB, and 33DMEB act as sII/sH hydrate formers and thermodynamic promoters, whereas t23EB and DEB have opposite roles. These results were analyzed in relation to the 3D geometries and relative stabilities of various rotational isomers using DFT calculations. Hydrate structure was influenced by both the length and thickness of the added compounds. Moreover, an appropriate level of (not excessive) hydrophilicity induced by an oxirane group appeared to enhance the thermodynamic stability of the hydrates. This study provides insights into how the chemical nature of additives influences the structure and stability of clathrate hydrates.

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“…Irradiating solid crystalline materials with high-energy protons or electrons has emerged as a novel approach to lattice engineering because it often creates unexpected beneficial effects in the physicochemical properties of the nanosystem . Various nanostructured materials, including carbons, − magnetics, , silicon clusters, and host–guest inclusion compounds, − have been explored by irradiation with energetic particles, and have produced breakthroughs in their inherent properties. Recently, energetic particle irradiated clathrate hydrates have been intensively examined to shed light on functionalized icy materials.…”

Section: Introductionmentioning

confidence: 99%

Enhancing Hydrogen Cluster Storage in Clathrate Hydrates via Defect-Mediated Lattice Engineering

et al. 2021

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Can we create even more “plenty of room at the bottom” of the confined nanospaces in clathrate hydrates by tuning the complex interactions between the host water frameworks and guest molecules? Because the lattice of the clathrate hydrate is stabilized by van der Waals forces between the host and guest, irradiating the lattice of the clathrate hydrate with energetic particles is anticipated to introduce artificial defects on the host water molecules, resulting in creating a better occupation of guest molecules. Here, we explored the effects of proton irradiation on the intermolecular hydrogen and intramolecular polar covalent bonds in the host frameworks of THF hydrates. The distinct roles of the secondary guest molecules in the lattice elongation of the proton irradiated THF hydrates were examined experimentally. Conclusively, multiple occupations of H2 in small cages was observed at moderate pressure and temperature conditions following H2 reloading of the lattice elongated THF hydrate.

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Thermodynamic Stability of Structure II Methyl Vinyl Ketone Binary Clathrate Hydrates and Effects of Secondary Guest Molecules on Large Guest Conformation

Cited by 9 publications

References 39 publications

Spectroscopic Observations of Host–Guest Hydrogen Bonding in Binary Cyclopropanemethanol + Methane Hydrate

Spectroscopic Observations of Host–Guest Hydrogen Bonding in Binary Cyclopropanemethanol + Methane Hydrate

Geometric and Hydrophilic Effects of Oxirane Compounds with a Four-Carbon Backbone on Clathrate Hydrate Formation

Enhancing Hydrogen Cluster Storage in Clathrate Hydrates via Defect-Mediated Lattice Engineering

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