Microporous MOF as nanogen facilitating diffusion-coupled charge transfer near the percolation threshold in a polyaniline pseudo-supercapacitor

Several approaches have recently been investigated with the aim of enhancing the specific capacitance of polyaniline (PANI). We herein report a novel pathway to boost the specific capacitance of PANI, which is highly tunable and versatile, based on wet chemistry techniques. In this approach, utilization of a specific metal-organic framework (MOF), UiO-66-NH₂, as a nanopore generator (Nanogen) is demonstrated. This systematic study demonstrates a tight interplay between the enhanced electrolyte accessibility to the PANI chains, through the incorporation of MOF nanogens, and the optimal relative amount of the conductive PANI, necessary to attain a charge percolation threshold in the binary system (MOF@PANI). Satisfying the charge percolation while maintaining porosity is necessary to arrive at a maximized specific capacitance of the PANI as the active phase. The enhancement in the specific capacitance of the PANI was fully exploited through a systematic investigation that helped to pinpoint the saddle point at which the two orthogonal properties, namely porosity (electrolyte diffusivity) and charge mobility (PANI inter-chain electronic conductivity) can be fine-tuned via controlling the materials composition. Of the different compositions investigated, the composite containing 23 wt% PANI of the total weight, doped with MOF nanogens, resulted in an enhanced specific capacitance of 872 F g^-1 for the PANI, in comparison to only 469 F g^-1 for the pristine PANI investigated under identical conditions.