Molecular Insights into the Correlation between Microstructure and Thermal Conductivity of Zeolitic Imidazolate Frameworks

The thermal conductivity of metal–organic frameworks (MOFs) imposes significant impacts on the thermal transfer performance of related adsorption systems in engineering applications. However, how the structural properties of MOFs affect their thermal conductivities has yet to be unraveled. In this work, the thermal conductivities of 18 zeolitic imidazolate frameworks (ZIFs) were calculated by equilibrium molecular dynamics (MD) simulations. It was revealed that the thermal conductivities of ZIFs were not directly correlated with the commonly investigated structural properties. Thus, two parameters including alignment tensor (Ai) and pathway factor (Pf) were proposed to quantitatively evaluate the orientation and distribution of heat transfer pathways within frameworks, which was demonstrated to correlate better with the thermal conductivities of ZIFs. This study provides new insights into the thermal transfer mechanism within framework-based nanoporous materials, which may also facilitate fundamental understanding and guide the rational design of porous crystals with the thermal conductivity of interest.