Исследование гидратов диоксида углерода в тонких пленках методом FTIR-спектроскопии при температурах 11–180 К

Голиков О.Ю., Ережеп Д.Е., Соколов Д.Ю. Исследование гидратов диоксида углерода в тонких пленках методом FTIR-спектроскопии при температурах 11–180 К // Научно- технический вестник информационных технологий, механики и оптики. 2023. Т. 23, № 3. С. 483–492. doi: 10.17586/2226-1494-2023-23-3-483-492

Введение. Исследованы инфракрасные спектры тонких пленок смеси диоксида углерода (CO₂) и воды (H₂O), полученных методом осаждения из паровой фазы, в диапазоне температур 11–180 К. По результатам анализа спектров изучено образование гидратов и клатратов. Метод. Для исследования образующихся тонких пленок применены методы инфракрасной спектроскопии, масс-спектроскопии и оптического анализа. Инфракрасная спектроскопия с преобразованием Фурье (Fourier transform infrared, FTIR) позволила идентифицировать молекулярный состав и структурное состояние молекулярных смесей. Масс-спектроскопия и анализ интерференционной картины применены для дополнительного подтверждения образования определенных структур смеси CO₂ и H₂O. Основные результаты. Показано, что в смеси CO₂ и H₂O происходит образование гидратных и газово-гидратных структур CO₂. Образованные гидратные соединения удерживают молекулы CO₂ в своих структурах и не позволяют ему сублимировать при температуре сублимации свободного CO₂ (93 К) при давлении Р = 0,5 мкторр. При этом температура сублимации связанных в гидратные структуры молекул CO₂ лежит в интервале 147–150 К. Для выбранного соотношения концентраций CO₂ (25 %) и H₂O (75 %) показано, что изменение в спектрах и результаты масс-спектроскопии свидетельствуют о неполной гидрадизации смеси. Часть молекул CO₂ остаются в свободном состоянии и сублимируют при более низкой температуре. Подтверждено, что увеличение показателя преломления при уменьшении концентрации H₂O в смеси от 100 % до 25 % свидетельствует об увеличении менее плотных образований в сравнении с аморфными структурами конденсатов CO₂ и H₂O. Обсуждение. Полученные результаты расширяют знания о процессах клатратного и гидратного образований в смесях CO₂ и H₂O, о физических характеристиках их строения и изменении характеристик в зависимости от способа образования. Исследование представляет интерес для современной физики конденсированного состояния.

1. Smith S.J., Wigley M.L. Global warming potentials: 1. Climatic implications of emissions reductions // Climatic Change. 2000. V. 44. N 4. P. 445–457. https://doi.org/10.1023/A:1005584914078
2. Pierrehumbert R.T. Short-lived climate pollution // Annual Review of Earth and Planetary Sciences. 2014. V. 42. N 1. P. 341–379. https://doi.org/10.1146/annurev-earth-060313-054843
3. Edwards M.R., McNerney J., Trancik J.E. Testing emissions equivalency metrics against climate policy goals // Environmental Science & Policy. 2016. V. 66. P. 191–198. https://doi.org/10.1016/j.envsci.2016.08.013
4. Schrag D.P. Storage of carbon dioxide in offshore sediments // Science. 2009. V. 325. N 5948. P. 1658–1659. https://doi.org/10.1126/science.1175750
5. Kvenvolden K.A. Gas hydrates-geological perspective and global change // Reviews of Geophysics. 1993. V. 31. N 2. P. 173–187. https://doi.org/10.1029/93rg00268
6. Konno Y., Fujii T., Sato A., Akamine K., Naiki M., Masuda Y., Yamamoto K., Nagao J. Key findings of the world’s first offshore methane hydrate production test off the coast of Japan: Toward future commercial production // Energy & Fuels. 2017. V. 31. N 3. P. 2607–2616. https://doi.org/10.1021/acs.energyfuels.6b03143
7. Li J., Ye J., Qin X., Qiu H., Wu N., Lu H., Xie W., Lu J., Peng F., Xu Z., Lu C., Kuang Z., Wei J., Liang Q., Lu H., Kou B. The first offshore natural gas hydrate production test in South China Sea // China Geology. 2018. V. 1. N 1. P. 5–16. https://doi.org/10.31035/cg2018003
8. Sloan Jr. E.D., Koh C.A., Koh C.A. Clathrate Hydrates of Natural Gases. CRC Press, 2007. 752 p. https://doi.org/10.1201/9781420008494
9. Ricaurte M., Dicharry Ch., Renaud X., Torré J.-Ph. Combination of surfactants and organic compounds for boosting CO2 separation from natural gas by clathrate hydrate formation // Fuel. 2014. V. 122. P. 206–217. https://doi.org/10.1016/j.fuel.2014.01.025
10. Tomita S., Akatsu S., Ohmura R. Experiments and thermodynamic simulations for continuous separation of CO2 from CH4 + CO2 gas mixture utilizing hydrate formation // Applied Energy. 2015. V. 146. P. 104–110. https://doi.org/10.1016/j.apenergy.2015.01.088
11. Mimachi H., Takahashi M., Takeya S., Gotoh Y., Yoneyama A., Hyodo K., Takeda T., Murayama T. Effect of long-term storage and thermal history on the gas content of natural gas hydrate pellets under ambient pressure // Energy & Fuels. 2015. V. 29. N 8. P. 4827–4834. https://doi.org/10.1021/acs.energyfuels.5b00832
12. Malla B.K., Vishwakarma G., Chowdhury S., Selvarajan P., Pradeep T. Formation of ethane clathrate hydrate in ultrahigh vacuum by thermal annealing // Journal of Physical Chemistry C. 2022. V. 126. N 42. P. 17983–17989. https://doi.org/10.1021/acs.jpcc.2c06264
13. Li M., Li K., Yang L., Su Y., Zhao J., Song Y. Evidence of guest–guest interaction in clathrates based on in situ Raman spectroscopy and density functional theory // Journal of Physical Chemistry Letters. 2022. V. 13. N 1. P. 400–405. https://doi.org/10.1021/acs.jpclett.1c03857
14. Koide H., Takahashi M., Tsukamoto H., Shindo Y. Self-trapping mechanisms of carbon dioxide in the aquifer disposal // Energy Conversion and Management. 1995. V. 36. N 6–9. P. 505–508. https://doi.org/10.1016/0196-8904(95)00054-h
15. Tohidi B., Yang J., Salehabadi M., Anderson R., Chapoy A. CO2 hydrates could provide secondary safety factor in subsurface sequestration of CO2 // Environmental Science & Technology. 2010. V. 44. N 4. P. 1509–1514. https://doi.org/10.1021/es902450j
16. Zheng J., Chong Z.R., Qureshi M.F., Linga P. Carbon dioxide sequestration via gas hydrates: a potential pathway toward decarbonization // Energy & Fuels. 2020. V. 34. N 9. P. 10529–10546. https://doi.org/10.1021/acs.energyfuels.0c02309
17. Qureshi M.F., Dhamu V., Usadi A., Barckholtz T.A., Mhadeshwar A.B., Linga P. CO2 Hydrate formation kinetics and morphology observations using high-pressure liquid CO2 applicable to sequestration // Energy & Fuels. 2022. V. 36. N 18. P. 10627–10641. https://doi.org/10.1021/acs.energyfuels.1c03840
18. Takahashi T., Sato T. Inclusive environmental impact assessment indices with consideration of public acceptance: Application to power generation technologies in Japan // Applied Energy. 2015. V. 144. P. 64–72. https://doi.org/10.1016/j.apenergy.2015.01.053
19. Englezos P., Kalogerakis N., Dholabhai P.D., Bishnoi P.R. Kinetics of formation of methane and ethane gas hydrates // Chemical Engineering Science. 1987. V. 42. N 11. P. 2647–2658. https://doi.org/10.1016/0009-2509(87)87015-x
20. Ribeiro C.P., Lage P.L.C. Gas-liquid direct-contact evaporation: A review // Chemical Engineering & Technology. 2005. V. 28. N 10. P. 1081–1107. https://doi.org/10.1002/ceat.200500169
21. Linga P., Kumar R., Englezos P. Gas hydrate formation from hydrogen/carbon dioxide and nitrogen/carbon dioxide gas mixtures // Chemical Engineering Science. 2007. V. 62. N 16. P. 4268–4276. https://doi.org/10.1016/j.ces.2007.04.033
22. Cai J., Zhang Y., Xu C.-G., Xia Z.-M., Chen Z.-Y., Li X.-S. Raman spectroscopic studies on carbon dioxide separation from fuel gas via clathrate hydrate in the presence of tetrahydrofuran // Applied Energy. 2018. V. 214. P. 92–102. https://doi.org/10.1016/j.apenergy.2018.01.055
23. Li X.-S., Xu C.-G., Chen Z.-Y., Wu H.-J. Hydrate-based pre-combustion carbon dioxide capture process in the system with tetra-n-butyl ammonium bromide solution in the presence of cyclopentane // Energy. 2011. V. 36. N 3. P. 1394–1403. https://doi.org/10.1016/j.energy.2011.01.034
24. Liu H., Wang J., Chen G., Liu B., Dandekar A., Wang B., Zhang X., Sun C., Ma Q. High-efficiency separation of a CO2/H2 mixture via hydrate formation in W/O emulsions in the presence of cyclopentane and TBAB // International Journal of Hydrogen Energy. 2014. V. 39. N 15. P. 7910–7918. https://doi.org/10.1016/j.ijhydene.2014.03.094
25. Kumar R., Wu H., Englezos P. Incipient hydrate phase equilibrium for gas mixtures containing hydrogen, carbon dioxide and propane // Fluid Phase Equilibria. 2006. V. 244. N 2. P. 167–171. https://doi.org/10.1016/j.fluid.2006.04.008
26. Wang X., Zhang F., Lipiński W. Research progress and challenges in hydrate-based carbon dioxide capture applications // Applied Energy. 2020. V. 269. P. 114928. https://doi.org/10.1016/j.apenergy.2020.114928
27. Uchida T. Physical property measurements on CO2 clathrate hydrates. Review of crystallography, hydration number, and mechanical properties // Waste Management. 1998. V. 17. N 5–6. P. 343–352. https://doi.org/10.1016/s0956-053x(97)10047-2
28. Lee Y.-J., Han K.W., Jang J.S., Jeon T.-I., Park J., Kawamura T., Yamamoto Y., Sugahara T., Vogt T., Lee J.-W., Lee Y., Yoon J.-H. Selective CO2 trapping in guest-free hydroquinone clathrate prepared by gas-phase synthesis // ChemPhysChem. 2011. V. 12. N 6. P. 1056–1059. https://doi.org/10.1002/cphc.201001047
29. Arismendi-Arrieta D.J., Valdés Á., Prosmiti R. A systematic protocol for benchmarking guest-host interactions by first-principles computations: capturing CO2 in clathrate hydrates // Chemistry - A European Journal. 2018. V. 24. N 37. P. 9353–9363. https://doi.org/10.1002/chem.201800497
30. Aldiyarov A., Aryutkina M., Drobyshev A., Kurnosov V. IR spectroscopy of ethanol in nitrogen cryomatrices with different concentration ratios // Low Temperature Physics. 2011. V. 37. N 6. P. 524–531. https://doi.org/10.1063/1.3622633
31. Sanz-Hervás A., Iborra E., Clement M., Sangrador J., Aguilar M. Influence of crystal properties on the absorption IR spectra of polycrystalline AlN thin films // Diamond and Related Materials. 2003. V. 12. N 3–7. P. 1186–1189. https://doi.org/10.1016/s0925-9635(02)00228-5
32. Karamancheva I., Stefov V., Šoptrajanov B., Danev G., Spasova E., Assa J. FTIR spectroscopy and FTIR microscopy of vacuum-evaporated polyimide thin films // Vibrational Spectroscopy. 1999. V. 19. N 2. P. 369–374. https://doi.org/10.1016/s0924-2031(99)00011-9
33. Oancea A., Grasset O., Le Menn E., Bollengier O., Bezacier L., Le Mouélic S., Tobie G. Laboratory infrared reflection spectrum of carbon dioxide clathrate hydrates for astrophysical remote sensing applications // Icarus. 2012. V. 221. N 2. P. 900–910. https://doi.org/10.1016/j.icarus.2012.09.020
34. Myshakin E.M., Saidi W.A., Romanov V.N., Cygan R.T., Jordan K.D. Molecular dynamics simulations of carbon dioxide intercalation in hydrated na-montmorillonite // Journal of Physical Chemistry C. 2013. V. 117. N 21. P. 11028–11039. https://doi.org/10.1021/jp312589s
35. Valdés Á., Arismendi-Arrieta D.J., Prosmiti R. Quantum dynamics of carbon dioxide encapsulated in the cages of the si clathrate hydrate: Structural guest distributions and cage occupation // Journal of Physical Chemistry C. 2015. V. 119. N 8. P. 3945–3956. https://doi.org/10.1021/jp5123745
36. Tylinski M., Chua Y.Z., Beasley M.S., Schick C., Ediger M.D. Vapor-deposited alcohol glasses reveal a wide range of kinetic stability // Journal of Chemical Physics. 2016. V. 145. N 17. P. 174506. https://doi.org/10.1063/1.4966582
37. Shinbayeva A., Drobyshev A., Drobyshev N. The standardization and certification procedures of cryogenic equipment in Kazakhstan // Low Temperature Physics. 2015. V. 41. N 7. P. 571–573. https://doi.org/10.1063/1.4927050
38. Aldiyarov A., Nurmukan A., Sokolov D., Korshikov E. Investigation of vapor cryodeposited glasses and glass transition of tetrachloromethane films // Applied Surface Science. 2020. V. 507. P. 144857. https://doi.org/10.1016/j.apsusc.2019.144857
39. Drobyshev A., Aldiyarov A., Nurmukan A., Sokolov D., Shinbayeva A. Structure transformations in thin films of CF3-CFH2 cryodeposites. Is there a glass transition and what is the value of Tg? // Applied Surface Science. 2018. V. 446. P. 196–200. https://doi.org/10.1016/j.apsusc.2018.01.270
40. Drobyshev A., Aldiyarov A., Sokolov D., Shinbayeva A. Refractive indices and density of cryovacuum-deposited thin films of methane in the vicinity of the α-β-transition temperature // Low Temperature Physics. 2017. V. 43. N 6. P. 724–727. https://doi.org/10.1063/1.4985981
41. Aldiyarov A.U., Sokolov D.Y., Nurmukan A.Y., Ramos M.A. Refractive index at low temperature of tetrachloromethane and tetrafluoroethane cryovacuum condensates // ACS Omega. 2020. V. 5. N 20. P. 11671–11676. https://doi.org/10.1021/acsomega.0c00969
42. Sokolov D.Y., Yerezhep D., Vorobyova O., Ramos M.A., Shinbayeva A. Optical studies of thin films of cryocondensed mixtures of water and admixture of nitrogen and argon // Materials (Basel). 2022. V. 15. N 21. P. 7441. https://doi.org/10.3390/ma15217441
43. Sokolov D.Y., Yerezhep D., Vorobyova O., Golikov O., Aldiyarov A.U. Infrared analysis and effect of nitrogen and nitrous oxide on the glass transition of methanol cryofilms // ACS Omega. 2022. V. 7. N 50. P. 46402–46410. https://doi.org/10.1021/acsomega.2c05090
44. Golikov O.Y., Yerezhep D., Sokolov D.Y. Improvement of the automatic temperature stabilisation process in the cryovacuum unit // Научно-технический вестник информационных технологий, механики и оптики. 2023. Т. 23. № 1. С. 62–67. https://doi.org/10.17586/2226-1494-2023-23-1-62-67
45. Tempelmeyer K.E., Mills D.W. Refractive index of carbon dioxide cryodeposit // Journal of Applied Physics. 1968. V. 39. N 6. P. 2968–2969. https://doi.org/10.1063/1.1656707
46. Dartois E., Schmitt B. Carbon dioxide clathrate hydrate FTIR spectrum // Astronomy & Astrophysics. 2009. V. 504. N 3. P. 869–873. https://doi.org/10.1051/0004-6361/200911812
47. Rothman L.S., Young L.D.G. Infrared energy levels and intensities of carbon dioxide—II // Journal of Quantitative Spectroscopy and Radiative Transfer. 1981. V. 25. N 6. P. 505–524. https://doi.org/10.1016/0022-4073(81)90026-1
48. Bernstein M., Cruikshank D., Sandford S. Near-infrared laboratory spectra of solid H2O/CO2 and CH3OH/CO2 ice mixtures // Icarus. 2005. V. 179. N 2. P. 527–534. https://doi.org/10.1016/j.icarus.2005.07.009
49. Sandford S.A., Allamandola L.J. The physical and infrared spectral properties of CO2 in astrophysical ice analogs // Astrophysical Journal. 1990. V. 355. P. 357. https://doi.org/10.1086/168770
50. Bryson C.E., Cazcarra V., Levenson L.L. Sublimation rates and vapor pressures of water, carbon dioxide, nitrous oxide, and xenon // Journal of Chemical & Engineering Data. 1974. V. 19. N 2. P. 107–110. https://doi.org/10.1021/je60061a021
 

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