Tunable Thermal Expansion from Negative, Zero, to Positive in Cubic

4 days ago - The thermal expansion of GaFe(CN)6 can be continuously tuned from strong negative, to zero, and to positive by the insertion of guest ion...
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Tunable Thermal Expansion from Negative, Zero, to Positive in Cubic Prussian Blue Analogues of GaFe(CN)6 Qilong Gao,† Naike Shi,† Andrea Sanson,‡ Yu Sun,† Ruggero Milazzo,‡ Luca Olivi,§ He Zhu,† Saul H. Lapidus,∥ Lirong Zheng,⊥ Jun Chen,*,† and Xianran Xing†

Inorg. Chem. Downloaded from pubs.acs.org by NEWCASTLE UNIV on 11/03/18. For personal use only.

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Beijing Advanced Innovation Center for Materials Genome Engineering and Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, China ‡ Department of Physics and Astronomy, University of Padova, Padova I-35131, Italy § Elettra Sincrotrone Trieste, 34149 Basovizza, Italy ∥ Argonne National Laboratory, X-ray Science Division, Argonne, Illinois 60439, United States ⊥ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100039, China S Supporting Information *

MOF,21 H2O in ZnPt(CN)6,22 and Rb ions and H2O molecules in Rb0.97Mn[Fe(CN)6]0.99·0.3H2O.23 Compared with M−O−M (M is metal) in the NTE oxides, the linkage of −M−NC−M− in Prussian blue analogues (PBAs) is more flexible,24 and thus it is easy to produce NTE from the transverse vibrations of the whole CN atoms. So, many PBAs with NTE have been reported, such as FeCo(CN)6,25 Ag3Co(CN)6,26 and YFe(CN)6.19 However, a satisfactory control of thermal expansion in PBAs has not yet been achieved. In the present study, we adopt the GaFe(CN)6 PBAs as a representative to realize the continuous thermal expansion from NTE, to zero thermal expansion (ZTE), to positive thermal expansion (PTE) by guest Na+ ions and H2O molecules. Here the thermal expansion and the effect of Na+ and H2O were evaluated by high-resolution synchrotron X-ray diffraction (SXRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The structure of GaFe(CN)6 is formed with FeC6 and GaN6 octahedra (Figure 1a) and is equivalent to ABX3 perovskite, where the A-site is vacant. The NTE comes from transverse thermal vibrations of CN ions, which give the shrinkage of the −Ga−CN−Fe− linkages

ABSTRACT: The achievement of controlling thermal expansion is important for open-framework structures. The present work proposes a feasible way to adjust the coefficient of thermal expansion continuously from negative to positive via inserting guest Na+ ions or H2O molecules into a GaFe(CN)6 framework. The guest ions or molecules have an intense dampening effect on the transverse vibrations of CN atoms in the −Ga−NC− Fe− linkage, especially for the N atoms. This study demonstrates that electrochemical or redox intercalation of guest ions will be an effective way to tune thermal expansion in those negative thermal expansion openframework materials induced by low-frequency phonons.

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ontrol of thermal expansion is an important issue for solid-state materials. The inherent physical property of thermal expansion generally correlates with phonons, electrons, orbitals, spin, and so on.1 Negative thermal expansion (NTE), as a novel phenomenon, brings a possible way to tune the thermal expansion of materials.2,3 NTE has achieved great progress in the last two decades, and many NTE materials have been found.1,4,5 For the issue of controlling the thermal expansion of NTE materials, chemical substitution is the general method used.1 In fact, thermal expansion has been effectively tuned for those electronic-state-driven NTE functional materials, like intermetallic charge-transfer in BiNiO3,6 Mott phase transition in Ca2RuO4,7,8 magnetovolume effect in magnetics alloy,9−11 and spontaneous volume ferroelectrostriction in PbTiO3-based ferroelectrics.12−14 However, for many open-framework NTE materials whose NTE is driven by low-frequency phonons, such as ZrW2O8, chemical substitution is not a promising method.15 For systems strongly related to transverse vibrations, the control of thermal expansion can be achieved by inserting/removing guest small molecules or ions into the pore of the open-framework structure to affect transverse vibrations. Interestingly, such dampening behavior has been observed in many open-framework NTE compounds, like H2O in ZrW2O8,16 CCl4 in Cd(CN)2,17 Li in (Sc,Fe)F3,18 K and H2O in YFe(CN)6,19 He2 in CaZrF6,20 CO2/H2 in © XXXX American Chemical Society

Figure 1. (a) Sketch of the cubic structure of GaFe(CN)6. The empty space indicated by the dashed circle can host guest ions or molecules. (b) Negative thermal expansion of GaFe(CN)6 is derived from the transverse vibrations of CN cyanogen ions. (c) Transverse vibrations of CN cyanogen ions can be hindered by guest ions or molecules. Received: August 28, 2018

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DOI: 10.1021/acs.inorgchem.8b02428 Inorg. Chem. XXXX, XXX, XXX−XXX

Communication

Inorganic Chemistry

Figure 3, one can find that for GaFe(CN)6 the “apparent” Ga− N and Fe−C bonds display NTE, whereas the “true” ones

(Figure 1b).26 We infer that if guest ion or molecule intercalation led to sterically hinder or reduce the transverse vibrations (Figure 1c), thus inhibiting the NTE, then it would effectively control the thermal expansion. The insertion of Na+ ions into the pore was performed by both Na-ion battery technology and NaI redox. According to the charge/discharge profiles of GaFe(CN)6, we can obtain the samples of Na0.25GaFe(CN)6 and Na0.5GaFe(CN)6 (see Figure S3 in the Supporting Information). For the synthesis of NaGaFe(CN)6·2H2O, GaFe(CN)6·2H2O was mixed with NaI acetonitrile solution at 60 °C for 24 h in an Ar-filled glovebox. The content of H2O and Na+ in NaGaFe(CN)6·2H2O was confirmed by TG and ICP, respectively (see Figure S4 in the Supporting Information). Clearly, the valence state of Fe in GaFe(CN)6 is +3, whereas it translated to +2 in NaGaFe(CN)6, which can be revealed by the shift of K-edge of X-ray absorption near-edge structure (XANES) of NaGaFe(CN)6· 2H2O (see Figure S5 in the Supporting Information).27 GaFe(CN)6 has a strong NTE from 100 to 475 K (Figure 2) (αl = −3.95(5) × 10−6 K−1).26 Interestingly, its thermal

Figure 3. Ga−N and Fe−C bond expansion in (a) GaFe(CN)6 (red) and (b) NaGaFe(CN)6 (blue).

show an opposite PTE. Obviously, the difference come from the transverse vibrations. After Na+ ions insert into the pores in GaFe(CN)6, the thermal expansion of the Ga−N bond is dramatically affected (Figure 3a), whereas the effect on the Fe−C bonds is much less evident (Figure 3b). This suggests that the guest Na+ ions have a strong effect on the lattice dynamics of Ga−N bonds and much less on that of Fe−C bonds. Here, combined with the bond expansion data by SXRD and EXAFS data, we can extract mean-square relative displacements (MSRDs)29 to describe the vibrational dynamics of CN cyanide. As shown in Figure 4a,b, the MSRD⊥ values of Ga−N and Fe−C bonds are much larger than the MSRD∥ values in GaFe(CN)6. In specific, the perpendicular MSRD⊥ of Ga−N is about twice that of Fe−C at room temperature. This is direct experiment evidence that the NTE of GaFe(CN)6 comes from

Figure 2. Thermal expansion of GaFe(CN)6-based compounds.

expansion can be effectively controlled from strong NTE to PTE with increasing content of guest Na+ ions and H2O molecules. NTE is weakened by the insertion of Na+ ions in Na0.25GaFe(CN)6 (αl = −2.83(3) × 10−6 K−1) and Na0.5GaFe(CN)6 (αl = −1.51(2) × 10−6 K−1). An interesting ZTE behavior is obtained in NaGaFe(CN)6 (αl = +0.30(2) × 10−6 K−1). With the further introduction of H2O molecules, a PTE behavior appeared in NaGaFe(CN)6·2H2O (αl = +3.98(4) × 10−6 K−1). So, we can effectively control thermal expansion in the GaFe(CN)6 framework through adjusting the content of Na+ ions and H2O molecules. It is interesting to highlight that a wide controllable CTE range has been achieved in the present PBAs, which was rarely observed in framework materials. Moreover, an interesting ZTE property is found in NaGaFe(CN)6 over a wide temperature range when compared with other ZTE materials, such as Zn4B6O13 (13−110 K),28 and FeCo(CN)6 (4.2−300 K).25 Now, we aim to gain new insights into the role of guests by the comparison between SXRD and EXAFS spectroscopy based on average and local structure. First, let us recall that the bond length obtained by SXRD is the so-called “apparent” bond length, whereas the one between neighboring atoms measured by EXAFS is the “true” bond length. As shown in

Figure 4. Local vibrational dynamics in GaFe(CN)6 and NaGaFe(CN)6. (a) Perpendicular MSRD⊥ and (b) parallel MSRD∥ of Ga−N (solid symbols) and Fe−C (open symbols) bonds. Anisotropy factor γ of (c) Ga−N and (d) Fe−C bonds. (e) Representation of the CN atom thermal ellipsoids of Ga−N and Fe−C thermal vibrations. B

DOI: 10.1021/acs.inorgchem.8b02428 Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry

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the transverse thermal vibrations of CN atoms, with the predominant contribution from N atoms. However, with the presence of Na in NaGaFe(CN)6, the values of perpendicular Ga−N and Fe−C sharply reduce, whereas those of parallel ones nearly do not change. This reveals that the insertion of Na+ ions inhibits or weakens the transverse vibrations of cyanogen (Figure 4a), with a remarkable effect on the transverse vibrations of N atoms and a smaller effect on C atoms. For a given atomic pair, the anisotropy of the relative thermal vibrations can be evaluated by the ratio γ = MSRD⊥/ MSRD∥. In the NTE GaFe(CN)6, the ratio γ of Ga−N bonds is ∼50 at high temperature (Figure 4c). Differently, in the ZTE NaGaFe(CN)6, the ratio γ of Ga−N bonds assumes a much lower value. A similar behavior, although less pronounced, is also observed for the ratio γ of Fe−C bonds (Figure 4d). The present results reflect that Na+ insertion has a significant inhibition for the transverse vibrations of CN atoms. The thermal ellipsoids of relative thermal vibrations of CN atoms, reconstructed from the data reported in Figure 4a,b, are shown in Figure 4e. These ellipsoids give an immediate visualization of the large transverse vibrations of CN atoms. The Na+ ion insertion weakens the transverse thermal vibrations of CN atoms, in particular, for N atoms. In summary, this work shows that guest Na ions or H2O molecules can control the thermal expansion of GaFe(CN)6 PBAs. The guests in the interstitial void can significantly hinder or dampen the transverse vibrations of CN cyanogen, in particular, for N atoms. This method of tuning the coefficient of thermal expansion in GaFe(CN)6 PBAs could be used in other NTE materials with an open framework.

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S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b02428.

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Materials synthesis, experimental details, data analysis procedures and supporting figure (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Jun Chen: 0000-0002-7330-8976 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Grant Nos. 21825102, 21731001, 21590793), the Fundamental Research Funds for the Central Universities, China (FRF-TP-17-001B), and the Changjiang Young Scholars Award. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357. We acknowledge ELETTRA Synchrotron for the provision of synchrotron radiation (Experiment 20175297) as well as all of the staff of XAFS Beamline for technical assistance. C

DOI: 10.1021/acs.inorgchem.8b02428 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.8b02428 Inorg. Chem. XXXX, XXX, XXX−XXX