Structure-Property Relationship of Piezoelectric Properties in Zeolitic Imidazolate Frameworks

Structure-Property Relationship of Piezoelectric Properties in Zeolitic Imidazolate Frameworks: A Computational Study

Mula, S. (TU Delft ChemE/Catalysis Engineering)
Donà, Lorenzo (University of Turin)
Civalleri, Bartolomeo (University of Turin)
van der Veen, M.A. (TU Delft ChemE/Catalysis Engineering)

2022

Metal-organic frameworks (MOFs) are a class of nanoporous crystalline materials with very high structural tunability. They possess a very low dielectric permittivity ϵr due to their porosity and hence are favorable for piezoelectric energy harvesting. Even though they have huge potential as piezoelectric materials, a detailed analysis and structure-property relationship of the piezoelectric properties in MOFs are lacking so far. This work focuses on a class of cubic non-centrosymmetric MOFs, namely, zeolitic imidazolate frameworks (ZIFs) to rationalize how the variation of different building blocks of the structure, that is, metal node and linker substituents affect the piezoelectric constants. The piezoelectric tensor for the ZIFs is computed from ab initio theoretical methods. From the calculations, we analyze the different contributions to the final piezoelectric constant d14, namely, the clamped ion (e140) and the internal strain (e14int) contributions and the mechanical properties. For the studied ZIFs, even though e14 (e140 + e14int) is similar for all ZIFs, the resultant piezoelectric coefficient d14 calculated from piezoelectric constant e14 and elastic compliance constant s44 varies significantly among the different structures. It is the largest for CdIF-1 (Cd2+ and -CH3 linker substituent). This is mainly due to the higher elasticity or flexibility of the framework. Interestingly, the magnitude of d14 for CdIF-1 is higher than II-VI inorganic piezoelectrics and of a similar magnitude as the quintessential piezoelectric polymer polyvinylidene fluoride.

Born effective charge
CdIF-1
compliance constant
DFT
metal-organic frameworks
piezoelectric constant
shear modulus

http://resolver.tudelft.nl/uuid:df17dc25-5da0-4b58-86f3-35bace7c773b

https://doi.org/10.1021/acsami.2c13506

1944-8244

ACS applied materials & interfaces, 14 (45), 50803-50814

Institutional Repository

journal article

© 2022 S. Mula, Lorenzo Donà, Bartolomeo Civalleri, M.A. van der Veen