This perspective outlines recent developments in the field of NMR spectroscopy, enabling new opportunities for in situ studies on bulk and confined clathrate hydrates. These hydrates are crystalline ice-like materials, built up from hydrogen-bonded water molecules, forming cages occluding non-polar gaseous guest molecules, including CH, CO and even H and He gas. In nature, they are found in low-temperature and high-pressure conditions. Synthetic confined versions hold immense potential for energy storage and transportation, as well as for carbon capture and storage. Using previous studies, this report highlights static and magic angle spinning NMR hardware and strategies enabling the study of clathrate hydrate formation in situ, in bulk and in nano-confinement. The information obtained from such studies includes phase identification, dynamics, gas exchange processes, mechanistic studies and the molecular-level elucidation of the interactions between water, guest molecules and confining interfaces.
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http://dx.doi.org/10.3390/molecules29143369 | DOI Listing |
J Phys Chem Lett
January 2025
DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence (TUE), Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India.
Clathrate hydrates (CHs) are believed to exist in cold regions of space, such as comets and icy moons. While spectroscopic studies have explored their formation under similar laboratory conditions, direct structural characterization using diffraction techniques has remained elusive. We present the first electron diffraction study of tetrahydrofuran (THF) and 1,3-dioxolane (DIOX) CHs in the form of nanometer-thin ice films under an ultrahigh vacuum at cryogenic temperatures.
View Article and Find Full Text PDFInt J Biol Macromol
December 2024
Department of Petroleum Engineering, School of Energy Technology, Pandit Deendayal Energy University, Gandhinagar, Gujarat 382426, India. Electronic address:
Naturally occurring gas clathrates are a significant methane resource-the primary component of natural gas, regarded as the cleanest hydrocarbon and a key feedstock for producing gray and blue hydrogen. Despite the global abundance of gas hydrate reserves, extraction via depressurization has yet to achieve commercially viable production rates. The primary limitation lies in the low permeability of hydrate-bearing sediments, where solid clathrates obstruct porous pathways, hindering dissociation and slowing gas recovery.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, Osaka 560-8531, Japan.
We explore the solubilities of guest CH4 and/or CO2 in the aqueous state coexisting with the corresponding hydrate. The equilibrium conditions are estimated by calculating the chemical potentials of water and guest species in the hydrate on the basis of a statistical mechanical theory using pairwise intermolecular potentials. This requires the least computational cost while covering a wide range of temperature, pressure, and composition of guest species, even for the binary hydrate.
View Article and Find Full Text PDFJ Phys Chem A
November 2024
Department of Physics, Sikkim University, Samdur, East Sikkim 737102, India.
We consider carbon monoxide (CO) confined in the hydrogen-bonded building blocks of sI and sII clathrate hydrates, viz., (5, 56, 56) cages, within the density functional theory-based calculations. We study their response to the applied electric fields in terms of changes in the geometrical parameters, dipole moment, HOMO-LUMO gap, and vibrational frequency shift.
View Article and Find Full Text PDFNat Commun
October 2024
Department of Chemistry, University of Antwerp, Universiteitsplein 1, Wilrijk, Belgium.
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