Guest-Induced Large and Tunable Negative Thermal Expansion in Soft Microporous Carbon

Osuagwu, Emmanuel U.; Compton, Dalton; Taylor, Erin E.; Nishihara, Hirotomo; Strange, Nicholas A.; Stadie, Nicholas P.

doi:10.1021/acsnano.5c17601

Title: Guest-Induced Large and Tunable Negative Thermal Expansion in Soft Microporous Carbon

Journal Article · Sat Jan 24 00:00:00 UTC 2026 · ACS Nano

DOI: https://doi.org/10.1021/acsnano.5c17601 · OSTI ID:3017131

Osuagwu, Emmanuel U. ^[1];

^[1];

^[2];

^[3];

^[1]

Montana State University, Bozeman, MT (United States)
Tohoku University, Miyagi (Japan)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Materials that exhibit negative thermal expansion (NTE) are of fundamental interest due to their rarity and counterintuitive behavior. While research in this area has been directed toward the discovery of materials that display NTE and explaining its origin, there has been less attention to describing the complexities of a secondary phase or other guests that could influence the magnitude and mechanism of NTE. We report herein that zeolite-templated carbon (ZTC), a soft carbonaceous framework solid with ordered microporosity, exhibits a large and widely tunable thermal expansion in the presence of adsorbed guests. For ZTC in the presence of CO₂ at 1 bar, the largest coefficient of isotropic NTE ever observed (−8.4 × 10^–4 K^–1) is measured between 200 and 220 K. These results comprise a tunable mechanism of thermal expansion based on the interaction between two independent, positively expanding phases that together give rise to an anomalous guest-induced NTE under certain conditions.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Montana State Univ., Bozeman, MT (United States); Montana State University, Bozeman, MT (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Tohoku University, Sendai (Japan)

Sponsoring Organization:: Japan Society for the Promotion of Science (JSPS) Grants-In-Aid for Scientific Research (KAKENHI); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; EE0008815

OSTI ID:: 3017131

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 5 Vol. 20; ISSN 1936-086X; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (59)

Zero Thermal Expansion Achieved by an Electrolytic Hydriding Method in La(Fe,Si) ₁₃ Compounds Li, Shaopeng; Huang, Rongjin; Zhao, Yuqiang Advanced Functional Materials, Vol. 27, Issue 5 https://doi.org/10.1002/adfm.201604195	journal	December 2016
Exceptional Negative Thermal Expansion in Isoreticular Metal–Organic Frameworks Dubbeldam, David; Walton, Krista S.; Ellis, Donald E. Angewandte Chemie, Vol. 119, Issue 24 https://doi.org/10.1002/ange.200700218	journal	June 2007
Nanoporosity and Exceptional Negative Thermal Expansion in Single-Network Cadmium Cyanide Phillips, Anthony E.; Goodwin, Andrew L.; Halder, Gregory J. Angewandte Chemie International Edition, Vol. 47, Issue 8 https://doi.org/10.1002/anie.200704421	journal	February 2008
Negative Thermal Expansion in the Metal-Organic Framework Material Cu ₃ (1,3,5-benzenetricarboxylate) ₂ Wu, Yue; Kobayashi, Atsushi; Halder, Gregory J. Angewandte Chemie International Edition, Vol. 47, Issue 46 https://doi.org/10.1002/anie.200803925	journal	November 2008
Crystallographic Observation of Dynamic Gas Adsorption Sites and Thermal Expansion in a Breathable Fluorous Metal-Organic Framework Yang, Chi; Wang, Xiaoping; Omary, Mohammad A. Angewandte Chemie International Edition, Vol. 48, Issue 14 https://doi.org/10.1002/anie.200804739	journal	March 2009
Thermal expansion of ultradrawn polystyrene Wang, Li‐Hui; Choy, C. L.; Porter, Roger S. Journal of Polymer Science: Polymer Physics Edition, Vol. 20, Issue 4 https://doi.org/10.1002/pol.1982.180200406	journal	April 1982
Thermal expansion, heat capacity, and compressibility of solid CO2 Manzhelii, V. G.; Tolkachev, A. M.; Bagatskii, M. I. Physica Status Solidi (b), Vol. 44, Issue 1 https://doi.org/10.1002/pssb.2220440104	journal	March 1971
Anisotropic Thermal Expansion of p-Terphenyl: a Self-Assembled Supramolecular Array of Poly-p-phenyl Nanoribbons Barba, Luisa; Chita, Giuseppe; Campi, Gaetano Journal of Superconductivity and Novel Magnetism, Vol. 31, Issue 3 https://doi.org/10.1007/s10948-017-4407-8	journal	November 2017
The lattice constant and expansion coefficient of solid carbon dioxide Keesom, W. H.; Köhler, J. W. L. Physica, Vol. 1, Issue 7-12 https://doi.org/10.1016/S0031-8914(34)80253-4	journal	May 1934
Graphene-based ordered framework with a diverse range of carbon polygons formed in zeolite nanochannels Nishihara, Hirotomo; Fujimoto, Hiroyuki; Itoi, Hiroyuki Carbon, Vol. 129 https://doi.org/10.1016/j.carbon.2017.12.055	journal	April 2018
Unique thermal contraction of zeolite-templated carbons enabling micropore size tailoring and its effects on methane storage Choi, Seokin; Alkhabbaz, Mustafa A.; Wang, Yuguo Carbon, Vol. 141 https://doi.org/10.1016/j.carbon.2018.09.045	journal	January 2019
Amorphous water in three-dimensional confinement of zeolite-templated carbon Kyakuno, Haruka; Matsuda, Kazuyuki; Nakai, Yusuke Chemical Physics Letters, Vol. 571 https://doi.org/10.1016/j.cplett.2013.04.016	journal	May 2013
A comparison between thermal expansion properties of hydrated and dehydrated orthorhombic HZSM-5 zeolite Jardim, P. M.; Marinkovic, B. A.; Saavedra, A. Microporous and Mesoporous Materials, Vol. 76, Issue 1-3 https://doi.org/10.1016/j.micromeso.2004.07.026	journal	December 2004
Atomic structure of the continuous random network of amorphous C[(C6H4)2]2 PAF-1 Cai, Guanqun; Lin, He; Zhao, Ziqiang Cell Reports Physical Science, Vol. 3, Issue 6 https://doi.org/10.1016/j.xcrp.2022.100899	journal	June 2022
Atomistic Structures of Zeolite-Templated Carbon Taylor, Erin E.; Garman, Kaitlin; Stadie, Nicholas P. Chemistry of Materials, Vol. 32, Issue 7 https://doi.org/10.1021/acs.chemmater.0c00535	journal	March 2020
Strong Negative Thermal Expansion of Cu ₂ PVO ₇ in a Wide Temperature Range Shi, Naike; Sanson, Andrea; Sun, Qiang Chemistry of Materials, Vol. 33, Issue 4 https://doi.org/10.1021/acs.chemmater.0c04336	journal	February 2021
Controlling Thermal Expansion: A Metal–Organic Frameworks Route Balestra, Salvador R. G.; Bueno-Perez, Rocio; Hamad, Said Chemistry of Materials, Vol. 28, Issue 22 https://doi.org/10.1021/acs.chemmater.6b03457	journal	November 2016
Chemical Diversity for Tailoring Negative Thermal Expansion Li, Qiang; Lin, Kun; Liu, Zhanning Chemical Reviews, Vol. 122, Issue 9 https://doi.org/10.1021/acs.chemrev.1c00756	journal	March 2022
Unusual Entropy of Adsorbed Methane on Zeolite-Templated Carbon Stadie, Nicholas P.; Murialdo, Maxwell; Ahn, Channing C. The Journal of Physical Chemistry C, Vol. 119, Issue 47 https://doi.org/10.1021/acs.jpcc.5b05021	journal	November 2015
Chemical Control of Thermal Expansion in Cation-Exchanged Zeolite A Carey, Thomas; Tang, Chiu C.; Hriljac, Joseph A. Chemistry of Materials, Vol. 26, Issue 4 https://doi.org/10.1021/cm403312q	journal	February 2014
Negative Thermal Expansion in ZrW ₂ O ₈ and HfW ₂ O ₈ Evans, J. S. O.; Mary, T. A.; Vogt, T. Chemistry of Materials, Vol. 8, Issue 12 https://doi.org/10.1021/cm9602959	journal	January 1996
Zero Thermal Expansion in a Prussian Blue Analogue Margadonna, Serena; Prassides, Kosmas; Fitch, Andrew N. Journal of the American Chemical Society, Vol. 126, Issue 47 https://doi.org/10.1021/ja044959o	journal	December 2004
Guest-Dependent Negative Thermal Expansion in Nanoporous Prussian Blue Analogues M ^II Pt ^IV (CN) ₆ · x {H ₂ O} (0 ≤ x ≤ 2; M = Zn, Cd) Goodwin, Andrew L.; Chapman, Karena W.; Kepert, Cameron J. Journal of the American Chemical Society, Vol. 127, Issue 51 https://doi.org/10.1021/ja056460f	journal	December 2005
Compositional Dependence of Negative Thermal Expansion in the Prussian Blue Analogues M ^II Pt ^IV (CN) ₆ (M = Mn, Fe, Co, Ni, Cu, Zn, Cd) Chapman, Karena W.; Chupas, Peter J.; Kepert, Cameron J. Journal of the American Chemical Society, Vol. 128, Issue 21 https://doi.org/10.1021/ja060916r	journal	May 2006
Anomalous Isosteric Enthalpy of Adsorption of Methane on Zeolite-Templated Carbon Stadie, Nicholas P.; Murialdo, Maxwell; Ahn, Channing C. Journal of the American Chemical Society, Vol. 135, Issue 3 https://doi.org/10.1021/ja311415m	journal	January 2013
Tunable Anisotropic Thermal Expansion of a Porous Zinc(II) Metal–Organic Framework Grobler, Ilne; Smith, Vincent J.; Bhatt, Prashant M. Journal of the American Chemical Society, Vol. 135, Issue 17 https://doi.org/10.1021/ja401671p	journal	April 2013
Further Contraction of ZrW₂O₈ Duan, N.; Kameswari, U.; Sleight, A. W. Journal of the American Chemical Society, Vol. 121, Issue 44 https://doi.org/10.1021/ja992569+	journal	October 1999
Metal−Organic Frameworks Provide Large Negative Thermal Expansion Behavior Han, Sang Soo; Goddard, William A. The Journal of Physical Chemistry C, Vol. 111, Issue 42 https://doi.org/10.1021/jp075389s	journal	October 2007
Elucidating Negative Thermal Expansion in MOF-5 Lock, Nina; Wu, Yue; Christensen, Mogens The Journal of Physical Chemistry C, Vol. 114, Issue 39 https://doi.org/10.1021/jp103212z	journal	September 2010
Negative Thermal Expansion in Covalent Organic Framework COF-102 Zhao, Lei; Zhong, Chongli The Journal of Physical Chemistry C, Vol. 113, Issue 39 https://doi.org/10.1021/jp906806k	journal	September 2009
Isosteric Heat of Adsorption: Theory and Experiment Sircar, S.; Mohr, R.; Ristic, C. The Journal of Physical Chemistry B, Vol. 103, Issue 31 https://doi.org/10.1021/jp9903817	journal	August 1999
Tunable thermal expansion in framework materials through redox intercalation Chen, Jun; Gao, Qilong; Sanson, Andrea Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14441	journal	February 2017
Force-driven reversible liquid–gas phase transition mediated by elastic nanosponges Nomura, Keita; Nishihara, Hirotomo; Yamamoto, Masanori Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-10511-7	journal	June 2019
Predicting the phase diagram of solid carbon dioxide at high pressure from first principles Han, Yanqiang; Liu, Jinfeng; Huang, Lei npj Quantum Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41535-019-0149-0	journal	March 2019
A thermodynamic explanation of the Invar effect Lohaus, S. H.; Heine, M.; Guzman, P. Nature Physics, Vol. 19, Issue 11 https://doi.org/10.1038/s41567-023-02142-z	journal	July 2023
Giant isotropic negative thermal expansion in Y-doped samarium monosulfides by intra-atomic charge transfer Takenaka, Koshi; Asai, Daigo; Kaizu, Ryoichi Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-018-36568-w	journal	January 2019
Effect of gas pressure on negative thermal expansion in MOF-5 Lock, Nina; Christensen, Mogens; Kepert, Cameron J. Chem. Commun., Vol. 49, Issue 8 https://doi.org/10.1039/C2CC37415C	journal	January 2013
Scrutinizing negative thermal expansion in MOF-5 by scattering techniques and ab initio calculations Lock, Nina; Christensen, Mogens; Wu, Yue Dalton Trans., Vol. 42, Issue 6 https://doi.org/10.1039/C2DT31491F	journal	January 2013
Acoustic phonons and negative thermal expansion in MOF-5 Rimmer, Leila H. N.; Dove, Martin T.; Goodwin, Andrew L. Phys. Chem. Chem. Phys., Vol. 16, Issue 39 https://doi.org/10.1039/C4CP01701C	journal	January 2014
Zeolite-templated carbons – three-dimensional microporous graphene frameworks Nishihara, H.; Kyotani, T. Chemical Communications, Vol. 54, Issue 45 https://doi.org/10.1039/C8CC01932K	journal	January 2018
Strong negative thermal expansion in siliceous faujasite Attfield, Martin P. Chemical Communications, Issue 5 https://doi.org/10.1039/a707141h	journal	January 1998
Negative thermal expansion materials † Evans, John S. O. Journal of the Chemical Society, Dalton Transactions, Issue 19 https://doi.org/10.1039/a904297k	journal	January 1999
Composites with extremal thermal expansion coefficients Sigmund, O.; Torquato, S. Applied Physics Letters, Vol. 69, Issue 21 https://doi.org/10.1063/1.117961	journal	November 1996
Anisotropic Thermal Expansion of Pyrolytic Graphite at Low Temperatures Bailey, A. C.; Yates, B. Journal of Applied Physics, Vol. 41, Issue 13 https://doi.org/10.1063/1.1658609	journal	December 1970
Evidence for liquid water during the high-density to low-density amorphous ice transition Kim, C. U.; Barstow, B.; Tate, M. W. Proceedings of the National Academy of Sciences, Vol. 106, Issue 12 https://doi.org/10.1073/pnas.0812481106	journal	March 2009
XCII.The crystal structure of solid methane McLennan, J. C.; Plummer, W. G. The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 7, Issue 45 https://doi.org/10.1080/14786440508564804	journal	May 1929
Negative thermal expansion Barrera, G. D.; Bruno, J. A. O.; Barron, T. H. K. Journal of Physics: Condensed Matter, Vol. 17, Issue 4 https://doi.org/10.1088/0953-8984/17/4/R03	journal	January 2005
The thermal expansion of graphite from 15 c. to 800 c.: part I. Experimental Nelson, J. B.; Riley, D. P. Proceedings of the Physical Society, Vol. 57, Issue 6 https://doi.org/10.1088/0959-5309/57/6/303	journal	November 1945
Origin of the exceptional negative thermal expansion in metal-organic framework-5 Zn 4 O ( 1 , 4 − benzenedicarboxylate ) 3 Zhou, W.; Wu, H.; Yildirim, T. Physical Review B, Vol. 78, Issue 5 https://doi.org/10.1103/PhysRevB.78.054114	journal	August 2008
Single-crystal refinement of the structure of carbon dioxide Simon, A.; Peters, K. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 36, Issue 11 https://doi.org/10.1107/S0567740880009879	journal	November 1980
In situ observation of phase changes of a silica-supported cobalt catalyst for the Fischer–Tropsch process by the development of a synchrotron-compatible in situ/operando powder X-ray diffraction cell Hoffman, Adam S.; Singh, Joseph A.; Bent, Stacey F. Journal of Synchrotron Radiation, Vol. 25, Issue 6 https://doi.org/10.1107/S1600577518013942	journal	October 2018
Re-examining the crystal structure behaviour of nitrogen and methane Maynard-Casely, Helen E.; Hester, James R.; Brand, Helen E. A. IUCrJ, Vol. 7, Issue 5 https://doi.org/10.1107/S2052252520007460	journal	July 2020
Gas Adsorption Sites in a Large-Pore Metal-Organic Framework Rowsell, Jesse L. C.; Spencer, Elinor C.; Eckert, Juergen Science, Vol. 309, Issue 5739, p. 1350-1354 https://doi.org/10.1126/science.1113247	journal	August 2005
Colossal Positive and Negative Thermal Expansion in the Framework Material Ag3[Co(CN)6] Goodwin, A. L.; Calleja, M.; Conterio, M. J. Science, Vol. 319, Issue 5864 https://doi.org/10.1126/science.1151442	journal	February 2008
Negative Thermal Expansion from 0.3 to 1050 Kelvin in ZrW2O8 Mary, T. A.; Evans, J. S. O.; Vogt, T. Science, Vol. 272, Issue 5258 https://doi.org/10.1126/science.272.5258.90	journal	April 1996
The Thermal Expansion of Crystals in Relation to their Structure Megaw, Helen D. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 100, Issue 1-6 https://doi.org/10.1524/zkri.1939.100.1.58	journal	November 1939
Adsorption properties of templated nanoporous carbons comprising 1–2 graphene layers Nishihara, Hirotomo; Zhao, Hong-Wei; Kanamaru, Kazuya Carbon Reports, Vol. 1, Issue 3 https://doi.org/10.7209/carbon.010301	journal	September 2022
The role of alkali metal exchange in zeolite-templated carbon synthesis Taylor, Erin E.; Compton, Dalton; Wyss, Gary F. Carbon Reports, Vol. 1, Issue 4 https://doi.org/10.7209/carbon.010404	journal	December 2022
Mechanical properties of zeolite-templated carbons from approximate density functional theory calculations Szilagyi, Robert K.; Stadie, Nicholas P.; Irle, Stephan Carbon Reports, Vol. 1, Issue 4 https://doi.org/10.7209/carbon.010407	journal	December 2022

Similar Records

Temperature-regulated guest admission and release in microporous materials

Journal Article · Fri Jun 09 00:00:00 UTC 2017 · Nature Communications · OSTI ID:1374884

Li, Gang; Shang, Jin; Gu, Qinfen; +8 more

Tunable Thermal Expansion from Negative, Zero, to Positive in Cubic Prussian Blue Analogues of GaFe(CN)₆

Journal Article · Tue Oct 30 00:00:00 UTC 2018 · Inorganic Chemistry · OSTI ID:1493740

Gao, Qilong; Shi, Naike; Sanson, Andrea; +8 more

Intrinsic thermal expansion and tunability of thermal expansion coefficient in Ni-substituted Co ₂ V ₂ O ₇

Journal Article · Fri Oct 06 00:00:00 UTC 2023 · JPhys Materials · OSTI ID:2008000

Esteban, Erica T. B.; Garcia, Jasmine J.; Windover, Sophie R.; +1 more

Related Subjects

03 NATURAL GAS
08 HYDROGEN
25 ENERGY STORAGE
36 MATERIALS SCIENCE
Adsorption
Carbon
Carbon Dioxide
Host-Guest Systems
Hydrogen
Inorganic Carbon Compounds
Methane
Natural Gas
Storage
Thermal Expansion
Thermodynamic Properties
Zeolites

Title: Guest-Induced Large and Tunable Negative Thermal Expansion in Soft Microporous Carbon

Citation Formats

References (59)

Similar Records

Related Subjects