Compositional dependence of uniaxial zero thermal expansion and zero linear compressibility in metal-organic framework MIL-122 (Al, Ga, In)

Lei Wang; Ying Chen; Cong Wang

doi:10.1039/d4dt02080d

Compositional dependence of uniaxial zero thermal expansion and zero linear compressibility in metal-organic framework MIL-122 (Al, Ga, In)

Dalton Trans. 2024 Sep 23. doi: 10.1039/d4dt02080d. Online ahead of print.

Authors

Lei Wang¹, Ying Chen², Cong Wang^{3

4}

Affiliations

¹ Department of Physics, Institute of Theoretical Physics, University of Science and Technology Beijing, Beijing 100083, China. leiw_phy@ustb.edu.cn.
² Fracture and Reliability Research Institute, Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan.
³ School of Integrated Circuit Science and Engineering, Beihang University, Beijing 100191, China.
⁴ National Key Laboratory of Spintronics, Hangzhou International Innovation Institute, Beihang University, Hangzhou 311115, China.

PMID: 39311879
DOI: 10.1039/d4dt02080d

Abstract

The responses of MIL-122(Al, Ga, In) to pressure or temperature have been investigated. The findings suggest that the a-axis in the lattice exhibits minimal compressibility, particularly zero linear compressibility (ZLC) behavior observed in MIL-122(In), consistent with experimental reports. Additionally, as the radius of metal atoms increases, the compressibility of the b-axis and c-axis gradually strengthens. There is a notable compositional dependence on volume thermal expansion in MIL-122(Al, Ga, In), where an increase in the metal atom radius leads to gradual weakening of volume thermal expansion. In particular, MIL-122(In) demonstrates pronounced volume negative thermal expansion (NTE) behavior, with the a-axis displaying zero thermal expansion (ZTE) behavior and both the b-axis and c-axis exhibiting NTE behavior. The temperature-dependent relative change in the bulk modulus of MIL-122(Al, Ga, In) has also been explored, revealing abnormal thermal hardening specifically within MIL-122(Ga, In). We attribute these unique uniaxial ZTE and ZLC behaviors in MIL-122(In) to its distinctive wine-rack topology, anomalous phonons (negative Grüneisen parameters), and internal structural flexibility.