Abstract: Metal-organic frameworks (MOFs) have attracted significant interest as self-templates and precursors for the synthesis of carbon-based composites aimed at electromagnetic wave (EMW) absorption. However, the utilization of high-temperature treatments has introduced uncertainties regarding the compositions and microstructures of resulting derivatives. Additionally, complete carbonization has led to diminished yields of the produced carbon composites, significantly limiting their practical applications. Consequently, the exploration of pristine MOF-based EMW absorbers presents an intriguing yet challenging endeavor, primarily due to inherently low electrical conductivity. In this study, we showcase the utilization of structurally robust Zr-MOFs as scaffolds to build highly conductive Zr-MOF/PPy composites via an inner-outer dual-modification approach, which involves the production of conducting polypyrrole (PPy) both within the confined nanoporous channels and the external surface of Zr-MOFs via post-synthetic modification. The interconnection of confined PPy and surface-lined PPy together leads to a consecutive and extensive conducting network to the maximum extent. This therefore entails outstanding conductivity up to ∼14.3 S cm^-1 in Zr-MOF/PPy composites, which is approximately 1-2 orders of magnitude higher than that for conductive MOF nanocomposites constructed from either inner or outer modification. Benefiting from the strong and tunable conduction loss, as well as the induced dielectric polarization originated from the porous structures and MOF-polymer interfaces, Zr-MOF/PPy exhibits excellent microwave attenuation capabilities and a tunable absorption frequency range. Specifically, with only 15 wt.% loading, the minimum reflection loss (RL_min) can reach up to -67.4 dB, accompanied by an effective absorption bandwidth (EAB) extending to 6.74 GHz. Furthermore, the microwave absorption characteristics can be tailored from the C-band to the Ku-band by adjusting the loading of PPy. This work provides valuable insights into the fabrication of conductive MOF composites by presenting a straightforward pathway to enhance and regulate electrical conduction in MOF-based nanocomposites, thus paving a way to facilely fabricate pristine MOF-based microwave absorbers.

Key words: Conductive mof nanocomposites, Electromagnetic wave absorption, MOF/conducting polymer, Electrical conductivity, Zr-MOF/PPy