Rigid unit modes driven barocaloric effects in zeolitic imidazolate frameworks

doi:10.1016/j.jmst.2025.11.015

Abstract

Abstract: Barocaloric refrigeration has been attracting intensive attention as a promising candidate for next-generation refrigeration technology. Despite the significant progress enabled by orientational disorder-to-order transitions, barocaloric effects dominated by the lattice degree of freedom have not been well studied. Here, we report a route using the flexible metal-organic framework, zeolitic imidazolate framework-4(Zn), which exhibits exceptional barocaloric performance. The adiabatic temperature change reaches 15.1 K under 180 MPa at room temperature. In situ inelastic neutron scattering and Raman scattering measurements reveal that the impressive performance is attributed to vibrational modes of ultra-low-energy rigid units below 12 meV, which predominantly govern the vibrational entropy. This work highlights the potential of flexible metal-organic frameworks as barocaloric refrigerants and the demonstrated unique mechanism of rigid unit modes is expected to promote barocaloric materials exploration.

Key words: Barocaloric effects, Flexible metal-organic frameworks, Phase transitions, Vibrational entropy, Vibrational spectroscopy

Wanwu Li, Kun Zhang, Dehong Yu, Yuanwen Feng, Haoyu Wang, Xueting Zhao, Xiaoyan Fan, Dan Huang, Zhidong Zhang, Bing Li. Rigid unit modes driven barocaloric effects in zeolitic imidazolate frameworks[J]. J. Mater. Sci. Technol., 2026, 264: 82-89.

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