Inorganic and methane clathrates: Versatility of guest–host compounds for energy harvesting

Krishna, Lakshmi; Koh, Carolyn A.

doi:10.1557/mre.2015.9

Inorganic and methane clathrates: Versatility of guest–host compounds for energy harvesting

Journal Article · Thu Jan 01 04:00:00 EST 2015 · MRS Energy & Sustainability

DOI:https://doi.org/10.1557/mre.2015.9· OSTI ID:1387487

Krishna, Lakshmi; Koh, Carolyn A.

ABSTRACT

This review article evaluates the structure–property relations of inorganic clathrates and clathrate hydrates and their potential role in energy harvesting. There is potential cross-fertilization between the two research areas.

Guest–host clathrate compounds exhibit unique structural and physical properties, which lead to their versatile roles in energy applications. Prominent classes of clathrate compounds are gas hydrates and inorganic clathrates. That said, there is limited cross-fertilization between the clathrate hydrate and inorganic clathrate communities, with researchers in the respective fields being less informed on the other field. Yet the structures and unique guest–host interactions in both these compounds are common important features of these clathrates. Common features and procedures can inspire and inform development between the compound classes, which may be important to the technological advancements for the different clathrate materials, e.g., structure characterization techniques and guest–host dynamics in which the “guest” tends to be imprisoned in the host structure, until external forces are applied. Conversely, the diversity in chemical compositions of these two classes of materials leads to the different applications from methane capture and storage to converting waste heat to electricity (thermoelectrics). This article highlights the structural and physical similarities and differences of inorganic and methane clathrates. The most promising state-of-the-art applications of the clathrates are highlighted for harvesting energy from methane (clathrate) hydrate deposits under the ocean and for inorganic clathrates as promising thermoelectric materials.

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research in Extreme Environments (EFree)

Sponsoring Organization:: USDOE SC Office of Basic Energy Sciences (SC-22)

DOE Contract Number:: SC0001057

OSTI ID:: 1387487

Journal Information:: MRS Energy & Sustainability, Journal Name: MRS Energy & Sustainability Vol. 2; ISSN 2329-2229; ISSN applab

Publisher:: Materials Research Society - Cambridge University Press

Country of Publication:: United States

Language:: English

References (63)

Die K�figverbindungen Ge38A8X8mit A = P, As. Sb und X = Cl, Br, J Menke, Heinz; von Schnering, Hans Georg Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 395, Issue 2-3 https://doi.org/10.1002/zaac.19733950211	journal	January 1973
Guest–Framework Interaction in Type I Inorganic Clathrates with Promising Thermoelectric Properties: On the Ionic versus Neutral Nature of the Alkaline-Earth Metal Guest A in A8Ga16Ge30 (A=Sr, Ba) Gatti, Carlo; Bertini, Luca; Blake, Nick P. Chemistry - A European Journal, Vol. 9, Issue 18 https://doi.org/10.1002/chem.200304837	journal	September 2003
Phonon-glass electron-crystal thermoelectric clathrates: Experiments and theory Takabatake, Toshiro; Suekuni, Koichiro; Nakayama, Tsuneyoshi Reviews of Modern Physics, Vol. 86, Issue 2 https://doi.org/10.1103/RevModPhys.86.669	journal	June 2014
Stable Low-Pressure Hydrogen Clusters Stored in a Binary Clathrate Hydrate Florusse, L. J. Science, Vol. 306, Issue 5695 https://doi.org/10.1126/science.1102076	journal	October 2004
Computations of diffusivities in ice and CO2 clathrate hydrates via molecular dynamics and Monte Carlo simulations Demurov, Alexander; Radhakrishnan, Ravi; Trout, Bernhardt L. The Journal of Chemical Physics, Vol. 116, Issue 2 https://doi.org/10.1063/1.1425821	journal	January 2002
Coupling of localized guest vibrations with the lattice modes in clathrate hydrates Tse, J. S.; Shpakov, V. P.; Belosludov, V. R. Europhysics Letters (EPL), Vol. 54, Issue 3 https://doi.org/10.1209/epl/i2001-00250-2	journal	May 2001
High-Pressure Synthesis of a New Silicon Clathrate Superconductor, Ba ₈ Si ₄₆ Yamanaka, Shoji; Enishi, Eiji; Fukuoka, Hiroshi Inorganic Chemistry, Vol. 39, Issue 1 https://doi.org/10.1021/ic990778p	journal	January 2000
Low-density framework form of crystalline silicon with a wide optical band gap Gryko, Jan; McMillan, Paul F.; Marzke, Robert F. Physical Review B, Vol. 62, Issue 12 https://doi.org/10.1103/PhysRevB.62.R7707	journal	September 2000
Application of gas hydrate formation in separation processes: A review of experimental studies Eslamimanesh, Ali; Mohammadi, Amir H.; Richon, Dominique The Journal of Chemical Thermodynamics, Vol. 46 https://doi.org/10.1016/j.jct.2011.10.006	journal	March 2012
Formation and properties of ice XVI obtained by emptying a type sII clathrate hydrate Falenty, Andrzej; Hansen, Thomas C.; Kuhs, Werner F. Nature, Vol. 516, Issue 7530 https://doi.org/10.1038/nature14014	journal	December 2014
Theoretical studies of CH4(H2O)20, (H2O)21, (H2O)20, and fused dodecahedral and tetrakaidecahedral structures: How do natural gas hydrates form? Khan, Arshad The Journal of Chemical Physics, Vol. 110, Issue 24 https://doi.org/10.1063/1.479128	journal	June 1999
Semiconducting Clathrates Meet Gas Hydrates: Xe ₂₄ [Sn ₁₃₆ ] Karttunen, Antti J.; Fässler, Thomas F. Chemistry - A European Journal, Vol. 20, Issue 22 https://doi.org/10.1002/chem.201402251	journal	April 2014
On the Design of High-Efficiency Thermoelectric Clathrates through a Systematic Cross-Substitution of Framework Elements Shi, Xun; Yang, Jiong; Bai, Shengqiang Advanced Functional Materials, Vol. 20, Issue 5 https://doi.org/10.1002/adfm.200901817	journal	March 2010
Off-center rattling and cage vibration of the carrier-tuned type-I clathrate Ba 8 Ga 16 Ge 30 studied by Raman scattering Takasu, Y.; Hasegawa, T.; Ogita, N. Physical Review B, Vol. 82, Issue 13 https://doi.org/10.1103/PhysRevB.82.134302	journal	October 2010
Thermodynamic properties of R13 (CClF3), R23 (CHF3), R152a (C2H4F2), and propane hydrates for desalination of sea water. Kubota, Hironobu; Shimizu, Kunihiko; Tanaka, Yoshiyuki Journal of Chemical Engineering of Japan, Vol. 17, Issue 4 https://doi.org/10.1252/jcej.17.423	journal	January 1984
Hydrogen Encapsulation in a Silicon Clathrate Type I Structure: Na _5.5 (H ₂ ) _2.15 Si ₄₆ : Synthesis and Characterization Neiner, Doinita; Okamoto, Norihiko L.; Condron, Cathie L. Journal of the American Chemical Society, Vol. 129, Issue 45 https://doi.org/10.1021/ja0724700	journal	November 2007
Synthesis of the Clathrate-II K _8.6(4) Ge ₁₃₆ by Oxidation of K ₄ Ge ₉ in an Ionic Liquid Guloy, Arnold M.; Tang, Zhongjia; Ramlau, Reiner European Journal of Inorganic Chemistry, Vol. 2009, Issue 17 https://doi.org/10.1002/ejic.200801073	journal	June 2009
On the clathrate form of elemental silicon, Si136: preparation and characterisation of NaxSi136 (x→0) Ammar, Abdelaziz; Cros, Christian; Pouchard, Michel Solid State Sciences, Vol. 6, Issue 5 https://doi.org/10.1016/j.solidstatesciences.2004.02.006	journal	May 2004
Efficient route to phase selective synthesis of type II silicon clathrates with low sodium occupancy Krishna, Lakshmi; Baranowski, Lauryn L.; Martinez, Aaron D. CrystEngComm, Vol. 16, Issue 19 https://doi.org/10.1039/C3CE42626B	journal	January 2014
Thermoelectric clathrates of type I Christensen, Mogens; Johnsen, Simon; Iversen, Bo Brummerstedt Dalton Trans., Vol. 39, Issue 4 https://doi.org/10.1039/B916400F	journal	January 2010
An ESR study on the thermal electron excitation of a sodium atom incorporated in a silicon clathrate compound Yahiro, Hidenori; Yamaji, Kazumitsu; Shiotani, Masaru Chemical Physics Letters, Vol. 246, Issue 1-2 https://doi.org/10.1016/0009-2614(95)01110-U	journal	November 1995
Methane hydrates and global climate Kvenvolden, Keith A. Global Biogeochemical Cycles, Vol. 2, Issue 3 https://doi.org/10.1029/GB002i003p00221	journal	September 1988
Microsecond Simulations of Spontaneous Methane Hydrate Nucleation and Growth Walsh, M. R.; Koh, C. A.; Sloan, E. D. Science, Vol. 326, Issue 5956 https://doi.org/10.1126/science.1174010	journal	October 2009
Silicon clathrates as anode materials for lithium ion batteries? Yang, Jianjun; Tse, John S. Journal of Materials Chemistry A, Vol. 1, Issue 26 https://doi.org/10.1039/c3ta11050h	journal	January 2013
Rational Design of Advanced Thermoelectric Materials Yang, Jihui; Yip, Hin-Lap; Jen, Alex K. -Y. Advanced Energy Materials, Vol. 3, Issue 5 https://doi.org/10.1002/aenm.201200514	journal	February 2013
Wide-band-gap Si in open fourfold-coordinated clathrate structures Adams, Gary B.; O’Keeffe, Michael; Demkov, Alexander A. Physical Review B, Vol. 49, Issue 12 https://doi.org/10.1103/PhysRevB.49.8048	journal	March 1994
Gas hydrates: Unlocking the energy from icy cages Koh, Carolyn A.; Sum, Amadeu K.; Sloan, E. Dendy Journal of Applied Physics, Vol. 106, Issue 6 https://doi.org/10.1063/1.3216463	journal	September 2009
Path Sampling Calculation of Methane Diffusivity in Natural Gas Hydrates from a Water-Vacancy Assisted Mechanism Peters, Baron; Zimmermann, Nils E. R.; Beckham, Gregg T. Journal of the American Chemical Society, Vol. 130, Issue 51 https://doi.org/10.1021/ja802014m	journal	December 2008
Structural and electronic properties of p -doped silicon clathrates Connétable, D. Physical Review B, Vol. 75, Issue 12 https://doi.org/10.1103/PhysRevB.75.125202	journal	March 2007
A new clathrate hydrate structure Ripmeester, John A.; Tse, John S.; Ratcliffe, Christopher I. Nature, Vol. 325, Issue 6100 https://doi.org/10.1038/325135a0	journal	January 1987
Observation of Interstitial Molecular Hydrogen in Clathrate Hydrates Grim, R. Gary; Barnes, Brian C.; Lafond, Patrick G. Angewandte Chemie International Edition, Vol. 53, Issue 40 https://doi.org/10.1002/anie.201406546	journal	August 2014
Structural and electronic properties of type-I and type-VIII Ba8Ga16Sn30 clathrates under compression Li, D. C.; Fang, L.; Deng, S. K. Physica B: Condensed Matter, Vol. 407, Issue 8 https://doi.org/10.1016/j.physb.2012.01.109	journal	April 2012
Sequestering carbon dioxide into complex structures of naturally occurring gas hydrates Park, Y.; Kim, D. -Y.; Lee, J. -W. Proceedings of the National Academy of Sciences, Vol. 103, Issue 34 https://doi.org/10.1073/pnas.0602251103	journal	August 2006
Towards a fundamental understanding of natural gas hydrates Koh, Carolyn A. Chemical Society Reviews, Vol. 31, Issue 3 https://doi.org/10.1039/b008672j	journal	April 2002
Semiconducting Ge clathrates: Promising candidates for thermoelectric applications Nolas, G. S.; Cohn, J. L.; Slack, G. A. Applied Physics Letters, Vol. 73, Issue 2 https://doi.org/10.1063/1.121747	journal	July 1998
Theoretical Studies of Host–Guest Interaction in Gas Hydrates Kumar, Pradeep; Sathyamurthy, N. The Journal of Physical Chemistry A, Vol. 115, Issue 50 https://doi.org/10.1021/jp2089565	journal	December 2011
Using magnetic resonance imaging to monitor CH4 hydrate formation and spontaneous conversion of CH4 hydrate to CO2 hydrate in porous media Baldwin, Bernard A.; Stevens, Jim; Howard, James J. Magnetic Resonance Imaging, Vol. 27, Issue 5 https://doi.org/10.1016/j.mri.2008.11.011	journal	June 2009
Group IV clathrates: synthesis, optoelectonic properties, and photovoltaic applications Krishna, Lakshmi; Martinez, Aaron D.; Baranowski, Lauryn L. SPIE OPTO, SPIE Proceedings https://doi.org/10.1117/12.2040056	conference	March 2014
Feste Gashydrate Stackelberg, M. v. Die Naturwissenschaften, Vol. 36, Issue 11 https://doi.org/10.1007/BF00596788	journal	January 1949
Inorganic clathrate-II materials of group 14: synthetic routes and physical properties Beekman, M.; Nolas, G. S. J. Mater. Chem., Vol. 18, Issue 8 https://doi.org/10.1039/B706808E	journal	January 2008
Fundamentals and Applications of Gas Hydrates Koh, Carolyn A.; Sloan, E. Dendy; Sum, Amadeu K. Annual Review of Chemical and Biomolecular Engineering, Vol. 2, Issue 1 https://doi.org/10.1146/annurev-chembioeng-061010-114152	journal	July 2011
Properties of the clathrates of hydrogen and developments in their applicability for hydrogen storage Strobel, Timothy A.; Hester, Keith C.; Koh, Carolyn A. Chemical Physics Letters, Vol. 478, Issue 4-6 https://doi.org/10.1016/j.cplett.2009.07.030	journal	August 2009
Thermodynamic properties of gas hydrates Platteeuw, J. C.; van der Waals, J. H. Molecular Physics, Vol. 1, Issue 1 https://doi.org/10.1080/00268975800100111	journal	January 1958
Electrochemical Lithiation of Silicon Clathrate-II Langer, Thorsten; Dupke, Sven; Trill, Henning Journal of The Electrochemical Society, Vol. 159, Issue 8 https://doi.org/10.1149/2.082208jes	journal	January 2012
Thermopower enhancement by encapsulating cerium in clathrate cages Prokofiev, A.; Sidorenko, A.; Hradil, K. Nature Materials, Vol. 12, Issue 12 https://doi.org/10.1038/nmat3756	journal	September 2013
Hydrogen Clusters in Clathrate Hydrate Mao, W. L. Science, Vol. 297, Issue 5590 https://doi.org/10.1126/science.1075394	journal	September 2002
Rotational and Translational Motions of Trapped Methane. Incoherent Inelastic Neutron Scattering of Methane Hydrate ^† Tse, John S.; Ratcliffe, Christopher I.; Powell, Brian M. The Journal of Physical Chemistry A, Vol. 101, Issue 25 https://doi.org/10.1021/jp963006c	journal	June 1997
Defects in Semiconductors: Some Fatal, Some Vital Queisser, H. J. Science, Vol. 281, Issue 5379 https://doi.org/10.1126/science.281.5379.945	journal	August 1998
Synthesis of Group IV Clathrates for Photovoltaics Martinez, Aaron D.; Krishna, Lakshmi; Baranowski, Lauryn L. IEEE Journal of Photovoltaics, Vol. 3, Issue 4 https://doi.org/10.1109/JPHOTOV.2013.2276478	journal	October 2013
NMR Study of Methane + Ethane Structure I Hydrate Decomposition Dec, Steven F.; Bowler, Kristen E.; Stadterman, Laura L. The Journal of Physical Chemistry A, Vol. 111, Issue 20 https://doi.org/10.1021/jp070442y	journal	May 2007
Ab initio studies of (H2O)28 hexakaidecahedral cluster with Ne, N2, CH4, and C2H6 guest molecules in the cavity Khan, Arshad The Journal of Chemical Physics, Vol. 116, Issue 15 https://doi.org/10.1063/1.1462619	journal	April 2002
Superconductivity in the Silicon Clathrate Compound (Na,Ba) x S i 46 Kawaji, Hitoshi; Horie, Hiro-omi; Yamanaka, Shoji Physical Review Letters, Vol. 74, Issue 8 https://doi.org/10.1103/PhysRevLett.74.1427	journal	February 1995
High-Pressure Synthesis and Structural Characterization of the Type II Clathrate Compound Na _30.5 Si ₁₃₆ Encapsulating Two Sodium Atoms in the Same Silicon Polyhedral Cages Yamanaka, Shoji; Komatsu, Masaya; Tanaka, Masashi Journal of the American Chemical Society, Vol. 136, Issue 21 https://doi.org/10.1021/ja502733e	journal	May 2014
Synthesis of Na8Si46 and Na24Si136 by oxidation of Na4Si4 from ionic liquid decomposition Blosser, M. C.; Nolas, G. S. Materials Letters, Vol. 99 https://doi.org/10.1016/j.matlet.2013.03.020	journal	May 2013
Clathrate Structure of Silicon Na8Si46 and NaxSi136 (x < 11) Kasper, J. S.; Hagenmuller, P.; Pouchard, M. Science, Vol. 150, Issue 3704 https://doi.org/10.1126/science.150.3704.1713	journal	December 1965
Avoided crossing of rattler modes in thermoelectric materials Christensen, Mogens; Abrahamsen, Asger B.; Christensen, Niels B. Nature Materials, Vol. 7, Issue 10 https://doi.org/10.1038/nmat2273	journal	August 2008
Complex thermoelectric materials Snyder, G. Jeffrey; Toberer, Eric S. Nature Materials, Vol. 7, Issue 2, p. 105-114 https://doi.org/10.1038/nmat2090	journal	February 2008
Formation of Gas Hydrates in Natural Gas Transmission Lines Hammerschmidt, E. G. Industrial & Engineering Chemistry, Vol. 26, Issue 8 https://doi.org/10.1021/ie50296a010	journal	August 1934
Atomic imaging of cage-like structures of silicon Nistor, L.; van Tendeloo, G.; Amelinckx, S. Physica Status Solidi (a), Vol. 146, Issue 1 https://doi.org/10.1002/pssa.2211460111	journal	November 1994
Copper position in type-I Ba8Cu4Si42 clathrate Yang, L.; Wang, Y.; Liu, T. Journal of Solid State Chemistry, Vol. 178, Issue 6 https://doi.org/10.1016/j.jssc.2005.03.015	journal	June 2005
Clathrate hydrates with hydrogen-bonding guests Buch, Victoria; Devlin, J. Paul; Monreal, I. Abrrey Physical Chemistry Chemical Physics, Vol. 11, Issue 44 https://doi.org/10.1039/b911600c	journal	January 2009
Electrochemical Cycling of Sodium-Filled Silicon Clathrate Wagner, Nicholas A.; Raghavan, Rahul; Zhao, Ran ChemElectroChem, Vol. 1, Issue 2 https://doi.org/10.1002/celc.201300104	journal	September 2013
Lead telluride alloy thermoelectrics LaLonde, Aaron D.; Pei, Yanzhong; Wang, Heng Materials Today, Vol. 14, Issue 11 https://doi.org/10.1016/S1369-7021(11)70278-4	journal	November 2011

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Inorganic and methane clathrates: Versatility of guest–host compounds for energy harvesting

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