Effect of Phase Transition on the Thermal Transport in Isoreticular DUT Materials

Abstract

<p></p><p>Soft porous crystals (SPCs) can undergo large-amplitude phase transitions under external stimulus such as mechanical pressure, gas adsorption, and temperature while retaining their structural integrity. During the gas adsorption process, the generated latent heat is needed to be effectively removed. Thus, understanding the effect of phase transition on the thermal transport in SPCs becomes extremely important for their applications in storage and separation applications. </p> <p>In this paper, taking isorecticular DUT series as an example, the evolution of the thermal transport in SPCs during the phase transition from the large pore (lp) phase to the narrow pore (np) phase is comprehensively investigated by molecular dynamics (MD) simulations together with the Green-Kubo method. After the phase transition, an abnormal thermal transport property is found in the np phase of DUT materials. We find that although the transformed np phase of DUT-48 has a density much larger than its parent phase, the thermal conductivity of its np phase is smaller than its lp phase. This result is in contrast to the previous finding that SPCs with larger density possess a larger thermal conductivity. However, as for other DUT crystals including DUT-47, DUT-49, DUT-50, and DUT-151, the np phase is found to have a higher thermal conductivity than their lp phase counterpart, which is in accordance with the previous finding. This complicated effect of phase transition on thermal transport in SPCs can be explained by the porosity-dominated competition mechanism between the increased volumetric heat capacity and the aggravated phonon scattering during the phase transition process. Overall, the finding extracted from the present study can greatly expand current knowledge about the thermal conductivity of metal-organic frameworks that is previously found to grow usually with increasing porosity.</p><br><p></p>

Recent progress in strategies for preparation of metal-organic frameworks and their hybrids with different dimensions

“…The single-crystal-to-single-crystal (SCSC) conversion is an intriguing and essential process in chemistry and material science and is an important feature in the preparation of coordination polymers [132][133][134][135][136][137][138][139] . Over the last few decades, much research demonstrated that SCSC conversions of MOFs could be triggered by external stimuli, including physical and chemical processes, such as temperature, pressure, gas adsorption, etc.…”