Ma, Tzu-LingTzu-LingMaMohamed, Mohamed GamalMohamed GamalMohamedKarim, HiraHiraKarimKuo, Shiao-WeiShiao-WeiKuoCHENG-LIANG LIU2026-04-142026-04-142026-03-1513858947https://www.scopus.com/record/display.uri?eid=2-s2.0-105030927532&origin=resultslisthttps://scholars.lib.ntu.edu.tw/handle/123456789/737156Porous organic polymers (POPs), characterized by intrinsic porosity, structural tunability, and low thermal conductivity, offer promising potential for thermoelectric (TE) applications. Herein, a porphyrin-pyrene-based POP (Por-Py POP) is designed to integrate the extended π-conjugation and metal-coordination capability of porphyrins with the planar π-rich architecture of pyrene, thereby promoting charge transport. Post-synthetic metalation with Fe2+, Cu2+, or Zn2+ further introduces dπ-π orbital interactions, thereby strengthening the interfacial coupling with single-walled carbon nanotubes (CNTs) and facilitating efficient charge transfer. Among the resulting composites, the ZnPor-Py POP/CNT exhibits a power factor (PF) of 55.8 ± 6.3 μW m−1 K−2, which represents a 40% improvement over the non-metalated analogue and is attributed to an enhanced electrical conductivity (σ) via dπ-π orbital interactions. Meanwhile, the porous POP framework contributes to suppressing lattice thermal transport relative to pristine CNTs, resulting in a thermal conductivity (κ) of 8.8 ± 0.2 W m−1 K−1 for the ZnPor-Py POP/CNT composite and an improved figure of merit (zT) of 1.89 × 10−3 ± 0.22 × 10−3 at 300 K, corresponding to a 8.6% enhancement over pristine CNTs. Overall, this work demonstrates a synergetic design strategy that combines metal coordination for σ enhancement and porous frameworks for κ suppression, thus providing a versatile pathway toward next-generation high-performance porous composite TE materials.falseCarbon nanotubesCompositeMetal coordinationPorous organic polymersPorphyrinThermoelectricjournal article10.1016/j.cej.2026.1743352-s2.0-105030927532