Unveiling Thermal Transport Mechanisms in ZIFs: A Circuit Model Approach to Network and Functional Group Design

The thermal conductivity of metal-organic frameworks (MOFs) significantly impacts their performance in applications such as gas adsorption, separation, and catalysis. While prior studies have explored the thermal conductivity of MOFs, including MOF-5 derivatives, and through high-throughput simulations, the underlying principles for tuning thermal conductivity remain insufficiently understood. In this study, we performed thermal conductivity simulations on 196 ZIF structures, encompassing 49 topologies and four organic ligands. We proposed a novel circuit model that transforms crystal networks into electrical circuits, allowing "electrical conductivity" to serve as an analog for thermal conductivity. This method revealed a strong correlation between electrical and thermal conductivity, emphasizing the critical role of network topology in thermal transport. Additionally, we analyzed the interplay of van der Waals interactions and steric effects in modifying heat transfer pathways upon the introduction of functional groups. Our findings offer a systematic framework for screening MOF networks and provide guidance for the strategic decoration of MOFs to optimize their thermal performance. This study advances the understanding of structure-thermal property relationships in MOFs and supports their tailored design for enhanced functionality.