The crystal orientation of THF clathrates in nano-confinement by in situ polarized Raman spectroscopy

Sharma, Mrityunjay K.; Leong, Xin Ning; Koh, Carolyn A.; Hartman, Ryan L.

doi:10.1039/d3lc00884c

Title: The crystal orientation of THF clathrates in nano-confinement by in situ polarized Raman spectroscopy

Journal Article · 27 December 2023 · Lab on a Chip

DOI: https://doi.org/10.1039/d3lc00884c · OSTI ID:2337945

^[1]; Leong, Xin Ning ^[2];

^[3];

^[2]

New York Univ. (NYU), NY (United States); NYU Tandon School of Engineering
New York Univ. (NYU), NY (United States)
Colorado School of Mines, Golden, CO (United States)

Gas hydrates form at high pressure and low temperatures in marine sediments and permafrost regions of the earth. Despite forming in nanoporous structures, gas hydrates have been extensively studied only in bulk. Understanding nucleation and growth of gas hydrates in nonporous confinement can help create ways for storage and utilization as a future energy source. Herein, we introduce a new method for studying crystal orientation/tilt during tetrahydrofuran (THF) hydrate crystallization under the influence of nano-confinement using polarized Raman spectroscopy. Uniform cylindrical nanometer size pores of anodic aluminum oxide (AAO) are used as a model nano-confinement, and hydrate experiments are performed in a glass microsystem for control of the flash hydrate nucleation kinetics and analysis via in situ polarized Raman spectroscopy. The average THF hydrate crystal tilt of 56 ± 1° and 30.5 ± 0.5° were observed for the 20 nm and 40 nm diameter pores, respectively. Crystal tilt observed in 20 and 40-nanometer-size pores was proportional to the pore diameter, resulting in lower tilt relative to the axis of the confinement at larger diameter pores. Finally, the results indicate that the hydrates nucleation and growth mechanism can depend on the nanoconfinement size. A 1.6 ± 0.01 °C to 1.8 ± 0.01 °C depression in melting point compared to the bulk is predicted using the Gibbs–Thomson equation as a direct effect of nucleation in confinement on the hydrate properties.

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Research Organization:: New York Univ. (NYU), NY (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022161; SC0022162

OSTI ID:: 2337945

Journal Information:: Lab on a Chip, Journal Name: Lab on a Chip Journal Issue: 4 Vol. 24; ISSN 1473-0197

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Title: The crystal orientation of THF clathrates in nano-confinement by in situ polarized Raman spectroscopy

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