Supercooling suppression in the tetrahydrofuran clathrate hydrate formation

Machida, Haruhiko; Sugahara, Takeshi; Hirasawa, Izumi

doi:10.1039/d2ce00645f

Cited by 2 publications

(6 citation statements)

References 40 publications

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“…Here, we applied various size-uniform nanoparticles (involving graphene oxide nanosheets with size about 31 nm, 38 nm and 46 nm, gold or silver nanocubes with the size about 45 nm and 70 nm, respectively) and achieve highly-consistent results on the supercooling (Δ T ) - dependent of the critical nucleus size of THF hydrates. We experimentally proved the formation of a critical nucleus as the key step of the phase transition of THF clathrate hydrate; and it is further showed that the spherical radius of the critical nucleus of the THF hydrates in nm is about , which is about a few times larger than that of ice in experiment 29 and that of gas clathrate hydrates in simulations 19 , but seems to be consistent with a recent (relevant) cryo-SEM experimental measurement, which reported the formation of about 10–30 nm nanoclusters in diameter of THF clathrate hydrates before the appearance of THF clathrate crystals at the supercooling Δ T = 20 °C 33 . The results indicate that the microscopic properties of the formed critical nuclei of THF hydrates and their surrounding solution differ from their macroscopic counterparts.…”

Section: Introductionsupporting

confidence: 89%

“…With an approximate constant Δ S for not large Δ T , thus we have with the approximated constant coefficient . It is worth mentioning that the inverse-proportional relationship between the radius of critical nucleus and the supercooling is more general than the CNT although it was usually derived via the CNT in literature 18 , 19 , 33 .…”

Section: Resultsmentioning

confidence: 99%

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Probing the critical nucleus size in tetrahydrofuran clathrate hydrate formation using surface-anchored nanoparticles

Xue,

Li,

Wang

et al. 2024

Nat Commun

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Controlling the formation of clathrate hydrates is crucial for advancing hydrate-based technologies. However, the microscopic mechanism underlying clathrate hydrate formation through nucleation remains poorly elucidated. Specifically, the critical nucleus, theorized as a pivotal step in nucleation, lacks empirical validation. Here, we report uniform nanoparticles, e.g., graphene oxide (GO) nanosheets and gold or silver nanocubes with controlled sizes, as nanoprobes to experimentally measure the size of the critical nucleus of tetrahydrofuran (THF) clathrate hydrate formation. The capability of the nanoparticles in facilitating THF clathrate hydrate nucleation displays generally an abrupt change at a nanoparticle-size-determined specific supercooling. It is revealed that the free-energy barrier shows an abrupt change when the nanoparticles have an approximately the same size as that of the critical nucleus. Thus, it is inferred that THF clathrate hydrate nucleation involves the creation of a critical nucleus with its size being inversely proportional to the supercooling. By proving the existence and determining the supercooling-dependent size of the critical nucleus of the THF clathrate hydrates, this work brings insights in the microscopic pictures of the clathrate hydrate nucleation.

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Section: Introductionsupporting

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Probing the critical nucleus size in tetrahydrofuran clathrate hydrate formation using surface-anchored nanoparticles

Xue,

Li,

Wang

et al. 2024

Nat Commun

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“…The interruption of the hydrogen bond promotes water molecules to form a hydration shell around THF, increasing the chances of hydrate formation. Machida et al also suggested that the bonding of THF with AgO and Ag 3 PO 4 through coordination bond helps in the suppression of the supercooling requirement (Δ T ) for the hydrate formation. Machida et al reported proof of an AgO coordination bond with THF.…”

Section: Resultsmentioning

confidence: 99%

“…Machida et al also suggested that the bonding of THF with AgO and Ag 3 PO 4 through coordination bond helps in the suppression of the supercooling requirement (Δ T ) for the hydrate formation. Machida et al reported proof of an AgO coordination bond with THF. However, no substantial spectral change occurred for Ag 3 PO 4 , despite the promotion of nucleation of THF hydrate.…”

Section: Resultsmentioning

confidence: 99%

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Can Aluminum Cations Promote Nucleation for THF Hydrate Growth?

Ravesh,

Ansari,

Panigrahi

et al. 2024

Langmuir

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Rapid nucleation of tetrahydrofuran (THF) hydrate is essential for developing a THF hydrate-based cold storage technology. Earlier works have hypothesized the role of aluminum complexes in initiating the nucleation of clathrate hydrates using aluminum metal electrodes and substrates. This study investigates if the nucleation promotional effect of hydrate can be achieved using the aluminum salt, AlCl3, due to the formation of aluminum aqua complexes in water. Metal chlorides NaCl and MgCl2 are also utilized to evaluate the effect of cation type in initiating nucleation, i.e., the effect of charge/radius ratio. The induction time is measured in a stirred reactor at various subcoolings and concentrations of 0.05, 0.1, 0.5, 1, and 2 wt %. The nucleation time is studied in two reactor configurations based on the nature of salt introduction in the THF solution, i.e., salt premixed in solution and salt injected inside the solution. The sudden rise in the reactor temperature due to hydrate formation is used as an indicator of hydrate formation. Results indicate that AlCl3 promotes hydrate nucleation as AlCl3 reduces induction time by 92.2% at 0.05 wt % concentration compared with water. Nearly instantaneous nucleation is also achieved by directly injecting AlCl3. MgCl2 and NaCl do not show a similar effect on induction time as AlCl3. The pH and Raman spectra measurements with and without salts are carried out to explain the effect of cations on the THF–water solution.

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Supercooling suppression in the tetrahydrofuran clathrate hydrate formation

Abstract: Generally, supercooling as large as about 25 K is necessary to form the tetrahydrofuran clathrate hydrate (THF hydrate). In the present study, we have investigated how the existence of various...

Cited by 2 publications

References 40 publications

Probing the critical nucleus size in tetrahydrofuran clathrate hydrate formation using surface-anchored nanoparticles

Probing the critical nucleus size in tetrahydrofuran clathrate hydrate formation using surface-anchored nanoparticles

Can Aluminum Cations Promote Nucleation for THF Hydrate Growth?

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