Methane is considered to be a cubic structure I (CS-I) clathrate hydrate former, although in a number of instances, small amounts of structure II (CS-II) clathrate hydrate have been transiently observed as well. In this work, solid-state magic angle spinning 13C NMR spectra of methane hydrate formed at low temperatures inside silica-based nanoporous materials with pores in the range of 3.8–20.0 nm (CPG-20, Vycor, and MCM-41) show methane in several different environments. In addition to methane encapsulated in the dodecahedral 512 (D) and tetrakaidecahedral 51262 (T) cages typical of the CS-I clathrate hydrate phase, methane guests in pentakaidecahedral 51263 (P) and hexakaidecahedral 51264 (H) cages are also identified, and these appear to be stabilized for extended periods of time. The ratio of methane guests among the D and T cages determined from the line intensities is significantly different from that of bulk CS-I samples and indicates that both CS-I and CS-II are present as the dominant species. This is the first observation of methane in P cages, and the possible structures in which they could be present are discussed. Broad and relatively strong methane peaks, which are also observed in the spectra, can be related to methane dissolved in an amorphous component of water adjacent to the pore walls. Nanoconfinement and interaction with the pore walls clearly have a strong influence on the hydrate formed and may reflect species present in the early stages of hydrate growth.
REFERENCES
1.
J. A.
Ripmeester
and S.
Alavi
, Clathrate Hydrates: Molecular Science and Characterization
(Wiley
, Weinheim, Germany
, 2022
).2.
J. A.
Ripmeester
, S.
Takeya
, and S.
Alavi
, “Classification of clathrate hydrates
,” in Clathrate Hydrates: Molecular Science and Characterization
, edited by J. A.
Ripmeester
and S.
Alavi
(Wiley
, Weinheim, Germany
, 2022
), p. 78
, Table 3.5.3.
A.
Vysniauskas
and P. R.
Bishnoi
, “A kinetic study of methane hydrate formation
,” Chem. Eng. Sci.
38
, 1061
–1072
(1983
).4.
B.
Li
, X.-S.
Li
, and G.
Li
, “Kinetic studies of methane hydrate formation in porous media based on experiments in a pilot-scale hydrate simulator and a new model
,” Chem. Eng. Sci.
105
, 220
–230
(2014
).5.
J. M.
Schicks
and J. A.
Ripmeester
, “The coexistence of two different methane hydrate phases under moderate pressure and temperature conditions: Kinetic versus thermodynamic products
,” Angew. Chem., Int. Ed.
43
, 3310
–3313
(2004
).6.
M.
Choukroun
, Y.
Morizet
, and O.
Grasset
, “Raman study of methane clathrate hydrates under pressure: New evidence for the metastability of structure II
,” J. Raman Spectrosc.
38
, 440
–451
(2007
).7.
A. K.
Sum
, R. C.
Burruss
, and E. D.
Sloan
, “Measurement of clathrate hydrates via Raman spectroscopy
,” J. Phys. Chem. B
101
(38
), 7371
–7377
(1997
).8.
S.
Subramanian
and E. D.
Sloan
, “Trends in vibrational frequencies of guests trapped in clathrate hydrate cages
,” J. Phys. Chem. B
106
, 4348
–4355
(2002
).9.
H.
Ohno
, I. L.
Moudrakovski
, R.
Gordienko
, J. A.
Ripmeester
, and V. K.
Walker
, “Structures of hydrocarbon hydrates during formation with and without inhibitors
,” J. Phys. Chem. A
116
, 1337
–1343
(2012
).10.
T.
Pietrass
, H. C.
Gaede
, A.
Bifone
, A.
Pines
, and J. A.
Ripmeester
, “Monitoring xenon clathrate hydrate formation on ice surfaces with optically enhanced 129Xe NMR
,” J. Am. Chem. Soc.
117
, 7520
–7525
(1995
).11.
I. L.
Moudrakovski
, A. A.
Sanchez
, C. I.
Ratcliffe
, and J. A.
Ripmeester
, “Nucleation and growth of hydrates on ice surfaces: New insights from 129Xe NMR experiments with hyperpolarized xenon
,” J. Phys. Chem. B
105
, 12338
–12347
(2001
).12.
L.
del Rosso
, M.
Celli
, and L.
Ulivi
, “Raman measurements of pure hydrogen Clathrate formation from a supercooled hydrogen–water solution
,” J. Phys. Chem. Lett.
6
, 4309
–4313
(2015
).13.
D. K.
Staykova
, W. F.
Kuhs
, A. N.
Salamatin
, and T.
Hansen
, “Formation of porous gas hydrates from ice powders: Diffraction experiments and multistage model
,” J. Phys. Chem. B
107
, 10299
–10311
(2003
).14.
A.
Falenty
, A. N.
Salamatin
, and W. F.
Kuhs
, “Kinetics of CO2-hydrate formation from ice powders: Data summary and modeling extended to low temperatures
,” J. Phys. Chem. C
117
, 8443
–8457
(2013
).15.
S. F.
Dec
. “Clathrate hydrate formation: Dependence on aqueous hydration number
,” J. Phys. Chem. C
113
, 12355
–12361
(2009
);Correction:
S. F.
Dec
. J. Phys. Chem.
116
, 6504
(2012
).16.
M. R.
Walsh
, C. A.
Koh
, E. D.
Sloan
, A. K.
Sum
, and D. T.
Wu
, “Microsecond simulations of spontaneous methane hydrate nucleation and growth
,” Science
326
, 1095
–1098
(2009
).17.
J.
Vatamanu
and P. G.
Kusalik
, “Observation of two-step nucleation in methane hydrates
,” Phys. Chem. Chem. Phys.
12
, 15065
–15072
(2010
).18.
S.
Sarupria
and P. G.
Debenedetti
, “Homogeneous nucleation of methane hydrate in microsecond molecular dynamics simulations
,” J. Phys. Chem. Lett.
3
, 2942
–2947
(2012
).19.
L. C.
Jacobson
, W.
Hujo
, and V.
Molinero
, “Amorphous precursors in the nucleation of clathrate hydrates
,” J. Am. Chem. Soc.
132
, 11806
–11811
(2010
).20.
M.
Lauricella
, G.
Ciccotti
, N. J.
English
, B.
Peters
, and S.
Meloni
, “Mechanisms and nucleation rate of methane hydrate by dynamical nonequilibrium molecular dynamics
,” J. Phys. Chem. C
121
, 24223
–24234
(2017
).21.
C.
Moon
, P. C.
Taylor
, and P. M.
Rodger
, “Molecular dynamics study of gas hydrate formation
,” J. Am. Chem. Soc.
125
, 4706
–4707
(2003
).22.
M. R.
Walsh
, G. T.
Beckham
, C. A.
Koh
, E. D.
Sloan
, D. T.
Wu
, and A. K.
Sum
, “Methane hydrate nucleation rates from molecular dynamics simulations: Effects of aqueous methane concentration, interfacial curvature, and system size
,” J. Phys. Chem. C
115
, 21241
–21248
(2011
).23.
R. V.
Belosludov
, K. V.
Gets
, R. K.
Zhdanov
, Y. Y.
Bozhko
, V. R.
Belosludov
, L.-J.
Chen
, and Y.
Kawazoe
, “Molecular dynamics study of clathrate-like ordering of water in supersaturated methane solution at low pressure
,” Molecules
28
, 2960
(2023
).24.
L.
Li
, J.
Zhong
, Y.
Yan
, J.
Zhang
, J.
Xu
, J. S.
Francisco
, and X. C.
Zeng
, “Unraveling nucleation pathway in methane clathrate formation
,” Proc. Natl. Acad. Sci. U. S. A.
117
, 24701
–24708
(2020
).25.
G.-J.
Guo
, M.
Li
, Y.-G.
Zhang
, and C.-H.
Wu
, “Why can water adsorb aqueous methane? A potential of mean force calculation on hydrate nucleation mechanisms
,” Phys. Chem. Chem. Phys.
11
, 10427
–10437
(2009
).26.
M. R.
Walsh
, J. D.
Rainey
, P. G.
Lafond
, D.-H.
Park
, G. T.
Beckham
, M. D.
Jones
, K.-H.
Lee
, C. A.
Koh
, E. D.
Sloan
, D. T.
Wu
, and A. K.
Sum
, “The cages, dynamics, and structuring of incipient methane clathrate hydrates
,” Phys. Chem. Chem. Phys.
13
, 19951
–15959
(2011
).27.
Z.
Zhang
, M. R.
Walsh
, and G.-J.
Guo
, “Microcanonical molecular simulations of methane hydrate nucleation and growth: Evidence that direct nucleation to sI hydrate is among the multiple nucleation pathways
,” Phys. Chem. Chem. Phys.
17
, 8870
–8876
(2015
).28.
T.
Yagasaki
, M.
Matsumoto
, and H.
Tanaka
, “Formation of clathrate hydrates of water-soluble guest molecules
,” J. Phys. Chem. C
120
, 21512
–21521
(2016
).29.
D.
Bai
, G.
Chen
, X.
Zhang
, and W.
Wang
, “Microsecond molecular dynamics simulations of the kinetic pathways of gas hydrate formation from solid surfaces
,” Langmuir
27
, 5961
–5967
(2011
).30.
D.
Bai
, G.
Chen
, X.
Zhang
, and W.
Wang
, “Nucleation of the CO2 hydrate from three-phase contact lines
,” Langmuir
28
, 7730
–7736
(2012
).31.
D.
Bai
, G.
Chen
, X.
Zhang
, A. K.
Sum
, and W.
Wang
, “How properties of solid surfaces modulate the nucleation of gas hydrate
,” Sci. Rep.
5
(1
), 12747
(2015
).32.
S.
Jahnert
, F.
Vaca Chavez
, G. E.
Schaumann
, A.
Schreiber
, M.
Schonhoff
, and G. H.
Findenegg
, “Melting and freezing of water in cylindrical silica nanopores
,” Phys. Chem. Chem. Phys.
10
, 6039
–6051
(2008
).33.
G. H.
Findenegg
, S.
Jahnert
, D.
Akcakayiran
, and A.
Schreiber
, “Freezing and melting of water confined in silica nanopores
,” ChemPhysChem
9
, 2651
–2659
(2008
).34.
M.
Brodrecht
, E.
Klotz
, C.
Lederle
, H.
Breitzke
, B.
Stuhn
, M.
Vogel
, and G.
Buntkowsky
, “A combined solid-state NMR, dielectric spectroscopy and calorimetric study of water in lowly hydrated MCM-41 samples
,” Z. Phys. Chem.
232
, 1003
–1015
(2018
).35.
M.
Sattig
, S.
Reutter
, F.
Fujara
, M.
Werner
, G.
Buntkowsky
, and M.
Vogel
, “NMR studies on the temperature-dependent dynamics of confined water
,” Phys. Chem. Chem. Phys.
16
, 19229
–19240
(2014
).36.
J.
Rault
, R.
Neffati
, and P.
Judeinstein
, “Melting of ice in porous glass: Why water and solvents confined in small pores do not crystallize?
,” The European Physical Journal B - Condensed Matter
36
, 627
–637
(2003
).37.
Y. P.
Handa
, M.
Zakrzewski
, and C.
Fairbridge
, “Effect of restricted geometries on the structure and thermodynamic properties of ice
,” J. Phys. Chem.
96
, 8594
–8599
(1992
).38.
X.
Zhu
, M.
Vandamme
, Z.
Jiang
, and L.
Brochard
, “Molecular simulation of the confined crystallization of ice in cement nanopore
,” J. Chem. Phys.
159
, 154704
(2023
).39.
N.
Floquet
, J. P.
Coulomb
, N.
Dufau
, G.
Andre
, and R.
Kahn
, “Confined water in mesoporous MCM-41 and nanoporous AlPO4-5: Structure and dynamics
,” Adsorption
11
(S1
), 139
–144
(2005
).40.
M.
Rescigno
, M.
Lucioli
, F. G.
Alabarse
, U.
Ranieri
, B.
Frick
, B.
Coasne
, and L. E.
Bove
, “Low-temperature dynamics of water confined in unidirectional hydrophilic zeolite nanopores
,” J. Phys. Chem. B
127
, 4570
–4576
(2023
).41.
H.
Bian
, L.
Ai
, K.
Hellgardt
, G. C.
Maitland
, and J. Y. Y.
Heng
, “Phase behaviour of methane hydrates in confined media
,” Crystals
11
, 201
(2021
).42.
I. L.
Moudrakovski
, C. I.
Ratcliffe
, and J. A.
Ripmeester
, “Specialized methods of nuclear magnetic resonance spectroscopy and magnetic resonance imaging applied to characterization of clathrate hydrates
,” in Clathrate Hydrates: Molecular Science and Characterization
, edited by J. A.
Ripmeester
and S.
Alavi
(Wiley
, Weinheim, Germany
, 2022
).43.
V.
Beschieru
, B.
Rathke
, and S.
Will
, “Particle diffusion in porous media investigated by dynamic light scattering
,” Microporous Mesoporous Mater.
125
, 63
–69
(2009
).44.
M.
Tiemann
and C.
Weinberger
, “Selective modification of hierarchical pores and surfaces in nanoporous materials
,” Adv. Mater. Interfaces
8
, 2001153
(2021
).45.
W.
Zhang
, C. I.
Ratcliffe
, I. L.
Moudrakovski
, J. S.
Tse
, C.-Y.
Mou
, and J. A.
Ripmeester
, “Characterization of the location and interfacial states of gallium in gallium/MCM-41 composites
,” Microporous Mesoporous Mater.
79
, 195
–203
(2005
).46.
M.
Kruk
, M.
Jaroniec
, and A.
Sayari
, “New insights into pore-size expansion of mesoporous silicates using long-chain amines
,” Microporous Mesoporous Mater.
35–36
, 545
–553
(2000
).47.
D.
Massiot
, F.
Fayon
, M.
Capron
, I.
King
, S.
Le Calvé
, B.
Alonso
, J.-O.
Durand
, B.
Bujoli
, Z.
Gan
, and G.
Hoatson
, “Modelling one- and two-dimensional solid state NMR spectra
,” Magn. Reson. Chem.
40
, 70
–76
(2002
).48.
I. L.
Moudrakovski
, Y.-T.
Seo
, G. E.
McLaurin
, and J. A.
Ripmeester
, “13C NMR and 1H NMR microimaging of CH4 and CO2 gas hydrates formation
,” in 46th Rocky Mountain Conference on Analytical Chemistry, Rocky Mountain Conference on Magnetic Resonance
(University of Denver
, 2004
), Vol. 46
, Abst. 226, p. 116
, https://digitalcommons.du.edu/rockychem/vol46/iss1/1.49.
J. A.
Ripmeester
, C. I.
Ratcliffe
, and J. S.
Tse
, “The nuclear magnetic resonance of 129Xe trapped in clathrates and some other solids
,” J. Chem. Soc., Faraday Trans. 1: Phys. Chem. Condens. Phases
84
, 3731
–3745
(1988
).50.
I. L.
Moudrakovski
, C. I.
Ratcliffe
, and J. A.
Ripmeester
, “Characterization of clathrate hydrates using nuclear magnetic resonance spectroscopy
,” in Clathrate Hydrates: Molecular Science and Characterization
, edited by J. A.
Ripmeester
and S.
Alavi
(Wiley
, Weinheim, Germany
, 2022
), Chap. 10, Vol. 2
.51.
L.
Yang
, C. A.
Tulk
, D. D.
Klug
, I. L.
Moudrakovski
, C. I.
Ratcliffe
, J. A.
Ripmeester
, B. C.
Chakoumakos
, L.
Ehm
, C. D.
Martin
, and J. B.
Parise
, “Synthesis and characterization of a new structure of gas hydrate
,” Proc. Natl. Acad. Sci. U. S. A.
106
, 6060
–6064
(2009
).52.
Y.
Liu
and L.
Ojamäe
, “13C chemical shift in natural gas hydrates from first-principles solid-state NMR calculations
,” J. Phys. Chem. C
120
, 1130
–1136
(2016
).53.
M. J.
Duer
, “Essential techniques for spin-1/2 nuclei
,” in Solid State NMR Spectroscopy Principles and Applications
, edited by M. J.
Duer
(Blackwell Science Ltd.
, Oxford
, 2002
), Chap. 2, p. 102
.54.
S. F.
Dec
, K. E.
Bowler
, L. L.
Stadterman
, C. A.
Koh
, and E. D.
Sloan
, “Direct measure of the hydration number of aqueous methane
,” J. Am. Chem. Soc.
128
, 414
–415
(2006
).55.
H.
Nakayama
, D. D.
Klug
, C. I.
Ratcliffe
, and J. A.
Ripmeester
, “Ordering and clathrate hydrate formation in co-deposits of xenon and water at low temperatures
,” Chem.-Eur. J.
9
, 2969
–2973
(2003
).56.
J.
Vatamanu
and P. G.
Kusalik
, “Unusual crystalline and polycrystalline structures in methane hydrates
,” J. Am. Chem. Soc.
128
, 15588
–15589
(2006
).© 2024 Author(s). Published under an exclusive license by AIP Publishing.
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