Impact of adsorption on thermal conductivity dynamics of adsorbate and adsorbent: Molecular dynamics study of methane and Cu-BTC.

Understanding changes in thermodynamic and transport properties during adsorption is crucial for the thermal management of metal-organic frameworks, which also imposes significant challenges for improved performance and energy density of adsorption system. Because of phase transitions in the intermolecular interactions involved in the adsorption phenomena, transport properties including the thermal conductivity exhibit interesting behaviors, yet fully understood. This study employs detailed molecular dynamics simulations to replicate the methane/Cu-BTC adsorption phenomenon for the evaluation of their thermal conductivities across different pressures and temperatures. The molecular simulations show that the thermal conductivities of both the adsorbent (Cu-BTC) and adsorbate (methane, adsorbed phase) vary notably during adsorption processes. Using the concepts of the change in the degree of free movements of the adsorbate molecules and atomic vibration of adsorbent, the reduction of the adsorbate thermal conductivity (∼70-93%) and increase thermal conductivity of the adsorbent (up to 3 times) in Cu-BTC+CH pair are explained.