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Title: Tunable thermal expansion in framework materials through redox intercalation

Journal Article · · Nature Communications
 [1];  [1];  [2];  [3];  [4];  [2];  [5]; ORCiD logo [5];  [6];  [1];  [1];  [7];  [3];  [6];  [3];  [1]; ORCiD logo [8];  [1]
  1. Univ. of Science and Technology Beijing, Beijing (China)
  2. Univ. of Padova, Padova (Italy)
  3. Chinese Academy of Sciences (CAS), Beijing (China)
  4. National Institute of Standards and Technology, Gaithersburg, MD (United States)
  5. Elettra Sicrotrone Trieste, Basovizza (Italy)
  6. Beihang Univ., Beijing (China)
  7. Argonne National Lab. (ANL), Argonne, IL (United States)
  8. Univ. of Edinburgh, Edinburgh (United Kingdom)

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present, offering a potential route for control. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF3, doped with 10% Fe to enable reduction. The small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. As a result, redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1367161
Journal Information:
Nature Communications, Vol. 8; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 95 works
Citation information provided by
Web of Science

References (60)

Generalized Gradient Approximation Made Simple journal October 1996
The Distortion‐Adjusted Change of Thermal Expansion Behavior of Cubic Magnetic Semiconductor (Sc 1− x M x )F 3 (M = Al, Fe) journal July 2016
Large Negative Thermal Expansion and Anomalous Behavior on Compression in Cubic ReO 3 -Type A II B IV F 6 : CaZrF 6 and CaHfF 6 journal May 2015
Core–shell strain structure of zeolite microcrystals journal July 2013
Relaxation of Crystals with the Quasi-Newton Method journal February 1997
Tunable Anisotropic Thermal Expansion of a Porous Zinc(II) Metal–Organic Framework journal April 2013
A fresh twist on shrinking materials journal December 2011
Negative Thermal Expansion in LnCo(CN) 6 (Ln=La, Pr, Sm, Ho, Lu, Y): Mechanisms and Compositional Trends journal April 2013
Recent advances in magnetic structure determination by neutron powder diffraction journal October 1993
The widespread occurrence of negative thermal expansion in zeolites journal January 2001
Further Contraction of ZrW2O8 journal October 1999
Colossal Positive and Negative Thermal Expansion in the Framework Material Ag3[Co(CN)6] journal February 2008
Negative Thermal Expansion from 0.3 to 1050 Kelvin in ZrW2O8 journal April 1996
Exceptional Negative Thermal Expansion in Isoreticular Metal–Organic Frameworks journal June 2007
Synthesis and physical properties of negative thermal expansion materials Zr1−xMxW2O8−y (M=Sc, In, Y) substituted for Zr(IV) sites by M(III) ions journal October 2003
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) journal May 2006
Pronounced Negative Thermal Expansion from a Simple Structure: Cubic ScF 3 journal November 2010
Zero Thermal Expansion in PbTiO 3 -Based Perovskites journal January 2008
Direct visualization of a guest-triggered crystal deformation based on a flexible ultramicroporous framework journal September 2013
Zero Thermal Expansion and Ferromagnetism in Cubic Sc 1– x M x F 3 (M = Ga, Fe) over a Wide Temperature Range journal September 2014
A century of zero expansion journal July 1999
Chemical Control of Thermal Expansion in Cation-Exchanged Zeolite A journal February 2014
Symmetry Switching of Negative Thermal Expansion by Chemical Control journal March 2016
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) journal December 2005
Giant Negative Thermal Expansion in NaZn 13 -Type La(Fe, Si, Co) 13 Compounds journal July 2013
A systematic study of Nasicon-type Li1+xMxTi2−x(PO4)3 (M: Cr, Al, Fe) by neutron diffraction and impedance spectroscopy journal November 2014
Colossal negative thermal expansion in BiNiO3 induced by intermetallic charge transfer journal June 2011
Colossal Positive and Negative Thermal Expansion in the Framework Material Ag3[Co(CN)6] journal February 2008
Nanoporosity and Exceptional Negative Thermal Expansion in Single-Network Cadmium Cyanide journal February 2008
New Insights into the Negative Thermal Expansion: Direct Experimental Evidence for the “Guitar-String” Effect in Cubic ScF 3 journal June 2016
Self-Consistent Equations Including Exchange and Correlation Effects journal November 1965
Giant negative thermal expansion in Ge-doped anti-perovskite manganese nitrides journal December 2005
History-dependent thermal expansion in NbO2F journal May 2014
Solid solubility, phase transitions, thermal expansion, and compressibility in Sc1−Al F3 journal February 2015
The heat capacities of thermomiotic ScF3 and ScF3–YF3 solid solutions journal February 2015
Zero Thermal Expansion in a Flexible, Stable Framework: Tetramethylammonium Copper(I) Zinc(II) Cyanide journal January 2010
Colossal negative thermal expansion in BiNiO3 induced by intermetallic charge transfer journal June 2011
Phonons and related crystal properties from density-functional perturbation theory journal July 2001
Exceptional Negative Thermal Expansion in Isoreticular Metal–Organic Frameworks journal June 2007
Special points for Brillouin-zone integrations journal June 1976
Direct visualization of a guest-triggered crystal deformation based on a flexible ultramicroporous framework journal September 2013
Negative thermal expansion and compressibility of Sc 1– x Y x F 3 (x≤0.25) journal December 2013
Giant Negative Thermal Expansion in NaZn 13 -Type La(Fe, Si, Co) 13 Compounds journal July 2013
Thermodynamics and Kinetics of the Li/FeF 3 Reaction by Electrochemical Analysis journal February 2012
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) journal May 2006
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation journal September 1992
Structural Relationship between Negative Thermal Expansion and Quartic Anharmonicity of Cubic ScF 3 journal November 2011
New Insights into the Negative Thermal Expansion: Direct Experimental Evidence for the “Guitar-String” Effect in Cubic ScF 3 journal June 2016
Observation of Uniaxial Negative Thermal Expansion in an Organic Crystal journal March 2002
Negative thermal expansion materials: technological key for control of thermal expansion journal February 2012
Negative thermal expansion in functional materials: controllable thermal expansion by chemical modifications journal January 2015
A combined stretching–tilting mechanism produces negative, zero and positive linear thermal expansion in a semi-flexible Cd( ii )-MOF journal January 2014
Iterative minimization techniques for ab initio total-energy calculations: molecular dynamics and conjugate gradients journal October 1992
Pronounced Negative Thermal Expansion from a Simple Structure: Cubic ScF 3 journal November 2010
Negative thermal expansion materials † journal January 1999
Exceptionally large positive and negative anisotropic thermal expansion of an organic crystalline material journal November 2009
Zero Thermal Expansion in a Prussian Blue Analogue journal December 2004
Optimized pseudopotentials journal January 1990
The widespread occurrence of negative thermal expansion in zeolites journal January 2001
First principles methods using CASTEP journal January 2005

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Intrinsic zero thermal expansion in cube cyanurate K 6 Cd 3 (C 3 N 3 O 3 ) 4 journal January 2019
Giant isotropic negative thermal expansion in Y-doped samarium monosulfides by intra-atomic charge transfer journal January 2019
Guest-dependent negative thermal expansion in a lanthanide-based metal–organic framework journal January 2019
Perovskite-related ReO3-type structures journal January 2020
Polymorphism of griseofulvin: concomitant crystallization from the melt and a single crystal structure of a metastable polymorph with anomalously large thermal expansion journal January 2018
Group 3 metal trihalide complexes with neutral N-donor ligands – exploring their affinity towards fluoride journal January 2018
On the switching between negative and positive thermal expansion in framework materials text January 2019
Colossal Negative Thermal Expansion in Electron‐Doped PbVO 3 Perovskites journal July 2018
Control of thermal expansion in a low-density framework modification of silicon journal April 2018
Progress of Research in Negative Thermal Expansion Materials: Paradigm Shift in the Control of Thermal Expansion journal July 2018
Colossal Negative Thermal Expansion in Electron-Doped PbVO 3 Perovskites journal June 2018
On the switching between negative and positive thermal expansion in framework materials journal May 2019
Crossover of thermal expansion from positive to negative by removing the excess fluorines in cubic ReO 3 -type TiZrF 7−x journal January 2018
Giant isotropic negative thermal expansion in Y-doped samarium monosulfides by intra-atomic charge transfer journal January 2019
Negative thermal expansion behavior in orthorhombic Sc 2 (MoO 4 ) 3 and Sc 2 (WO 4 ) 3 journal September 2019
Switching from positive to negative axial thermal expansion in two organic crystalline compounds with similar packing journal January 2018