Metal−Organic Frameworks Provide Large Negative Thermal Expansion Behavior

2007 ◽  
Vol 111 (42) ◽  
pp. 15185-15191 ◽  
Author(s):  
Sang Soo Han ◽  
William A. Goddard
Keyword(s):  
Thermal Expansion ◽  
Metal Organic Frameworks ◽  
Negative Thermal Expansion ◽  
Thermal Expansion Behavior ◽  
Expansion Behavior ◽  
Metal Organic

scholarly journals Tuning the Negative Thermal Expansion Behavior of the Metal–Organic Framework Cu3BTC2 by Retrofitting

2019 ◽  
Vol 141 (26) ◽  
pp. 10504-10509 ◽  
Author(s):  
Christian Schneider ◽  
David Bodesheim ◽  
Michael G. Ehrenreich ◽  
Valentina Crocellà ◽  
János Mink ◽  
...  
Keyword(s):  
Thermal Expansion ◽  
Metal Organic Framework ◽  
Negative Thermal Expansion ◽  
Thermal Expansion Behavior ◽  
Expansion Behavior ◽  
Metal Organic ◽  
Organic Framework

scholarly journals Retrofitting metal-organic frameworks

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Christian Schneider ◽  
David Bodesheim ◽  
Julian Keupp ◽  
Rochus Schmid ◽  
Gregor Kieslich
Keyword(s):  
Thermal Expansion ◽  
Low Cost ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Computational Framework ◽  
Expansion Behavior ◽  
Open Metal Sites ◽  
Metal Organic ◽  
Set Up ◽  
Linker Molecules

Abstract The post-synthetic installation of linker molecules between open-metal sites (OMSs) and undercoordinated metal-nodes in a metal-organic framework (MOF) — retrofitting — has recently been discovered as a powerful tool to manipulate macroscopic properties such as the mechanical robustness and the thermal expansion behavior. So far, the choice of cross linkers (CLs) that are used in retrofitting experiments is based on qualitative considerations. Here, we present a low-cost computational framework that provides experimentalists with a tool for evaluating various CLs for retrofitting a given MOF system with OMSs. After applying our approach to the prototypical system CL@Cu3BTC2 (BTC = 1,3,5-benzentricarboxylate) the methodology was expanded to NOTT-100 and NOTT-101 MOFs, identifying several promising CLs for future CL@NOTT-100 and CL@NOTT-101 retrofitting experiments. The developed model is easily adaptable to other MOFs with OMSs and is set-up to be used by experimentalists, providing a guideline for the synthesis of new retrofitted MOFs with modified physicochemical properties.

Assessing Negative Thermal Expansion in Mesoporous Metal-Organic Frameworks by Molecular Simulation

2019 ◽  
Author(s):  
Jack D. Evans ◽  
Johannes P. Dürholt ◽  
Stefan Kaskel ◽  
Rochus Schmid
Keyword(s):  
Thermal Expansion ◽  
Molecular Simulation ◽  
Mechanical Stability ◽  
Metal Organic Frameworks ◽  
Negative Thermal Expansion ◽  
Considerable Effect ◽  
Vibrational Modes ◽  
Opposite Behavior ◽  
Metal Organic ◽  
Mesoporous Metal

Most conventional materials display expansion upon heating, so there is considerable interest in identifying materials that display the opposite behavior, negative thermal expansion (NTE). In the current study, seven mesoporous metal-organic frameworks (MOFs) of varying topology and composition, which exhibit outstanding porosity, were investigated using molecular simulation for temperature-induced contraction. We find exceptional NTE for the most porous MOFs and a correlation between the coefficient of NTE and porosity. The large molecular subunits of the MOFs were further studied to find they intrinsically display NTE, corresponding to terahertz vibrational modes. As a result, NTE has a considerable effect on the mechanical properties of these MOFs and is an important consideration for understanding the mechanical stability of new extremely porous materials.

Exceptional Negative Thermal Expansion in Isoreticular Metal–Organic Frameworks

2007 ◽  
Vol 119 (24) ◽  
pp. 4580-4583 ◽  
Author(s):  
David Dubbeldam ◽  
Krista S. Walton ◽  
Donald E. Ellis ◽  
Randall Q. Snurr
Keyword(s):  
Thermal Expansion ◽  
Metal Organic Frameworks ◽  
Negative Thermal Expansion ◽  
Metal Organic

scholarly journals Negative thermal expansion in α-Zr2SP2O12 based on phase transition- and framework-type mechanisms

2020 ◽  
Vol 12 (1) ◽  
Author(s):  
Toshihiro Isobe ◽  
Yuko Hayakawa ◽  
Yuri Adachi ◽  
Ryosuke Uehara ◽  
Sachiko Matsushita ◽  
...  
Keyword(s):  
Phase Transition ◽  
Thermal Expansion ◽  
Hydrothermal Synthesis ◽  
Sulfur Content ◽  
Negative Thermal Expansion ◽  
Thermal Expansion Behavior ◽  
Temperature Range ◽  
Expansion Behavior

AbstractMaterials with negative coefficients of thermal expansion (CTEs) can be used to prepare composites with specific CTE values. Negative thermal expansion behavior can be primarily attributed to two types of mechanisms: phase transition- and framework-type mechanisms. This paper reports Zr2SP2O12, which has unique negative thermal expansion behavior involving both mechanisms. Zr2SP2O12 undergoes a framework-type mechanism at temperatures <393 K or >453 K and an isosymmetric phase transition at 393–453 K. The volumetric CTE of α-Zr2SP2O12 is ~−70 p.p.m./K during the isosymmetric phase transition, and this value can be decreased by decreasing the proportion of sulfur. The minimum volumetric CTE of α-Zr2S0.9P2O12-δ is ~−108 p.p.m./K in the temperature range of 393–453 K. Between 303 and 773 K, the volume of α-Zr2S0.9P2O12 − δ is reduced by ~1.3%. Finally, this paper presents methods for the hydrothermal synthesis of α-Zr2SP2O12 and for controlling the sulfur content.

scholarly journals Negative Thermal Expansion Design Strategies in a Diverse Series of Metal–Organic Frameworks

2019 ◽  
Vol 29 (48) ◽  
pp. 1904669 ◽  
Author(s):  
Nicholas C. Burtch ◽  
Samuel J. Baxter ◽  
Jurn Heinen ◽  
Ashley Bird ◽  
Andreas Schneemann ◽  
...  
Keyword(s):  
Thermal Expansion ◽  
Metal Organic Frameworks ◽  
Negative Thermal Expansion ◽  
Design Strategies ◽  
Metal Organic

scholarly journals Geometric switching of linear to area negative thermal expansion in uniaxial metal–organic frameworks

CrystEngComm ◽  
2014 ◽  
Vol 16 (17) ◽  
pp. 3498-3506 ◽  
Author(s):  
Ines E. Collings ◽  
Matthew G. Tucker ◽  
David A. Keen ◽  
Andrew L. Goodwin
Keyword(s):  
Thermal Expansion ◽  
Metal Organic Frameworks ◽  
Negative Thermal Expansion ◽  
Metal Organic

The direction of anisotropic negative thermal expansion switches for the two quartzlike metal–organic frameworks deuterium indium terephthalate and zinc isonicotinate; we show this inversion to be geometric, rather than chemical, in origin.

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