On the Spontaneous Formation of Clathrate Hydrates at Water–Guest Interfaces

Boewer, Lars; Nase, Julia; Paulus, Michael; Lehmkühler, Felix; Tiemeyer, Sebastian; Hölz, Sebastian; Pontoni, Diego; Tolan, Metin

doi:10.1021/jp211784w

Cited by 27 publications

(25 citation statements)

References 33 publications

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“…It rather implies an enrichment of guest molecules in the water phase. While there is clear evidence from reflectometry that gases can be enriched in water at the molecular‐scale gas‐water interface [ Boewer et al ., ; Lehmkühler et al ., ], unequivocal experimental evidence for a metastable enrichment of gases in thicker interfaces or bulk water was not available.…”

Section: Metastable Enrichment Of Gases In Liquid Watermentioning

confidence: 99%

Microstructural evolution of gas hydrates in sedimentary matrices observed with synchrotron X‐ray computed tomographic microscopy

Chaouachi

Falenty

Sell

et al. 2015

Geochem Geophys Geosyst

224

210

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The formation process of gas hydrates in sedimentary matrices is of crucial importance for the physical and transport properties of the resulting aggregates. This process has never been observed in situ at submicron resolution. Here we report on synchrotron-based microtomographic studies by which the nucleation and growth processes of gas hydrate were observed at 276 K in various sedimentary matrices such as natural quartz (with and without admixtures of montmorillonite type clay) or glass beads with different surface properties, at varying water saturation. Both juvenile water and metastably gas-enriched water obtained from gas hydrate decomposition was used. Xenon gas was employed to enhance the density contrast between gas hydrate and the fluid phases involved. The nucleation sites can be easily identified and the various growth patterns are clearly established. In sediments under-saturated with juvenile water, nucleation starts at the water-gas interface resulting in an initially several micrometer thick gas hydrate film; further growth proceeds to form isometric single crystals of 10-20 mm size. The growth of gas hydrate from gas-enriched water follows a different pattern, via the nucleation in the bulk of liquid producing polyhedral single crystals. A striking feature in both cases is the systematic appearance of a fluid phase film of up to several micron thickness between gas hydrates and the surface of the quartz grains. These microstructural findings are relevant for future efforts of quantitative rock physics modeling of gas hydrates in sedimentary matrices and explain the anomalous attenuation of seismic/sonic waves.

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Section: Metastable Enrichment Of Gases In Liquid Watermentioning

confidence: 99%

Microstructural evolution of gas hydrates in sedimentary matrices observed with synchrotron X‐ray computed tomographic microscopy

Chaouachi

Falenty

Sell

et al. 2015

Geochem Geophys Geosyst

224

210

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“…This could be the scenario for the formation of naturally deposited methane clathrate at the bottom of oceans originating from methane gas released from the ocean floor in the form of gas bubbles in water. Indeed, clathrate growth initiated from the gaswater interface could be observed visually (21) and by laser (26), Xray (27), and neutron scattering (26,(28)(29)(30). Unfortunately, very limited microscopic information about the nucleation process could be extracted from these experiments as well as other experiments using Raman scattering (31,32) and NMR (33,34).…”

Section: Significancementioning

confidence: 99%

Nucleation and dissociation of methane clathrate embryo at the gas–water interface

Liang

Sun

et al. 2019

Proc. Natl. Acad. Sci. U.S.A.

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Among natural energy resources, methane clathrate has attracted tremendous attention because of its strong relevance to current energy and environment issues. Yet little is known about how the clathrate starts to nucleate and disintegrate at the molecular level, because such microscopic processes are difficult to probe experimentally. Using surface-specific sum-frequency vibrational spectroscopy, we have studied in situ the nucleation and disintegration of methane clathrate embryos at the methane-gas–water interface under high pressure and different temperatures. Before appearance of macroscopic methane clathrate, the interfacial structure undergoes 3 stages as temperature varies, namely, dissolution of methane molecules into water interface, formation of cage-like methane–water complexes, and appearance of microscopic methane clathrate, while the bulk water structure remains unchanged. We find spectral features associated with methane–water complexes emerging in the induction time. The complexes are present over a wide temperature window and act as nuclei for clathrate growth. Their existence in the melt of clathrates explains why melted clathrates can be more readily recrystallized at higher temperature, the so-called “memory effect.” Our findings here on the nucleation mechanism of clathrates could provide guidance for rational control of formation and disintegration of clathrates.

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“…In recent years, several high-pressure cells for neutron reflectivity were developed and pressures up to 2.5 kbar were achieved (Kreuzer et al, 2011;Jeworrek et al, 2011;Wang et al, 2012;Carmichael et al, 2012). However, X-ray reflectivity studies at the solid/gas, liquid/gas and liquid/liquid interfaces have been limited to pressures below 0.1 kbar in large-volume gas cells (Paulus et al, 2008;Lehmkü hler et al, 2009;Venturini et al, 2011;Boewer et al, 2012) so far.…”

Section: Introductionmentioning

confidence: 99%

X-ray reflectivity measurements of liquid/solid interfaces under high hydrostatic pressure conditions

et al. 2013

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A high-pressure cell for in situ X-ray reflectivity measurements of liquid/solid interfaces at hydrostatic pressures up to 500 MPa (5 kbar), a pressure regime that is particularly important for the study of protein unfolding, is presented. The original set-up of this hydrostatic high-pressure cell is discussed and its unique properties are demonstrated by the investigation of pressure-induced adsorption of the protein lysozyme onto hydrophobic silicon wafers. The presented results emphasize the enormous potential of X-ray reflectivity studies under high hydrostatic pressure conditions for the in situ investigation of adsorption phenomena in biological systems.

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On the Spontaneous Formation of Clathrate Hydrates at Water–Guest Interfaces

Cited by 27 publications

References 33 publications

Microstructural evolution of gas hydrates in sedimentary matrices observed with synchrotron X‐ray computed tomographic microscopy

Microstructural evolution of gas hydrates in sedimentary matrices observed with synchrotron X‐ray computed tomographic microscopy

Nucleation and dissociation of methane clathrate embryo at the gas–water interface

X-ray reflectivity measurements of liquid/solid interfaces under high hydrostatic pressure conditions

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