Pore Size Dictates Anisotropic Thermal Conductivity of Two-Dimensional Covalent Organic Frameworks with Adsorbed Gases

Two-dimensional covalent organic frameworks (2D COFs) are a class of modular polymeric crystals with high porosities and large surface areas, which position them as ideal candidates for applications in gas storage and separation technologies. In this work, we study the influence of pore geometry on the anisotropic heat transfer mechanisms in 2D COFs through systematic atomistic simulations. More specifically, by studying COFs with varying pore sizes and gas densities, we demonstrate that the cross-plane thermal conductivity along the direction of the laminar pores can either be decreased due to solid-gas scattering (for COFs with relatively smaller pores that are less than or similar to 2 nm) or increased due to additional heat transfer pathways introduced by the gas adsorbates (for COFs with relatively larger pores). Our simulations on COF/methane systems reveal the intricate relationship among gas diffusivities, pore geometries, and solid-gas interactions dictating the modular thermal conductivities in these materials. Along with the understanding of the fundamental nature of gas diffusion and heat conduction in the porous framework crystals, our results can also help guide the design of efficient 2D polymeric crystals for applications with improved gas storage, catalysis, and separation capabilities.