Metal-organic frameworks and covalent-organic frameworks in thermal transport

Understanding and modulating the inherently low thermal conductivity of crystalline porous frameworks is critical for their deployment in thermal-sensitive applications like gas storage, catalysis, and thermoelectrics. This comprehensive review systematically examines thermal transport fundamentals and recent progress in regulating thermal conductivity for both metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). We detail primary strategies centered on framework architecture design (optimizing density, connectivity, and topology), pore environment modification (via guest molecule inclusion), interfacial bonding enhancement (strengthening vibrational coupling), and composite integration (embedding conductive additives), all aimed at overcoming intrinsic phonon scattering bottlenecks imposed by high porosity and chemical heterogeneity. Key challenges include reconciling structural porosity with phonon transport efficiency, accurately characterizing complex systems, and minimizing interfacial thermal resistance. Addressing these requires synergistic advances in multiscale computational modeling, high-resolution characterization techniques, and targeted interfacial engineering. The review ultimately establishes essential structure–thermal property relationships, providing a foundational guide for the rational design of next-generation framework materials in thermal energy science and technology.