Abstract：Efficient waste heat recovery via thermoelectric materials offers a promising way to boost energy efficiency, making performance enhancement strategies crucial in thermoelectric research. Here, we propose an effective synergistic optimization strategy for thermoelectric materials, focusing on enhancing mechanical properties, reducing thermal conductivity, and improving Seebeck coefficients. To achieve this, metal-organic frameworks (MOFs) with alkaline and amphoteric groups are synthesized and incorporated into poly(3,4- ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) to fabricate UiO-66-NH2/PEDOT:PSS (UNPP) and UiO-66-NH-SO3H/PEDOT:PSS (UNSPP) composite films. The electrostatic interactions between MOFs and PEDOT:PSS significantly reinforce the mechanical properties of UNPP and UNSPP. Furthermore, due to the isolation and “dragging effect” of MOFs on flexible PEDOT: PSS chains during the drying process, UNPP and UNSPP films exhibit hierarchical porous structures, achieving ultra-low thermal conductivity of 0.021 and 0.042 W.m−1.K−1 respectively, with the former, to the best of our knowledge, being the lowest reported value for PEDOT:PSS-based thermoelectric films. Additionally, MOF doping influences carrier transport within the com- posite films, leading to an improved Seebeck coefficient of up to 30.8 μV.K−1. The UNSPP show a maximum ZT of 0.263. This work presents an innovative strategy for efficient synergistic optimization of MOF/PEDOT:PSS films, highlighting their potential in wearable electronics and waste heat recovery.
