Intrinsically Microporous Polymer Retains Porosity in Vacuum Thermolysis to Electroactive Heterocarbon.

Vacuum carbonization of organic precursors usually causes considerable structural damage and collapse of morphological features. However, for a polymer with intrinsic microporosity (PIM-EA-TB with a Brunauer-Emmet-Teller (BET) surface area of 1027 m(2)g(-1)), it is shown here that the rigidity of the molecular backbone is retained even during 500 °C vacuum carbonization, yielding a novel type of microporous heterocarbon (either as powder or as thin film membrane) with properties between those of a conducting polymer and those of a carbon. After carbonization, the scanning electron microscopy (SEM) morphology and the small-angle X-ray scattering (SAXS) Guinier radius remain largely unchanged as does the cumulative pore volume. However, the BET surface area is decreased to 242 m(2)g(-1), but microporosity is considerably increased. The new material is shown to exhibit noticeable electrochemical features including two pH-dependent capacitance domains switching from ca. 33 Fg(-1) (when oxidized) to ca. 147 Fg(-1) (when reduced), a low electron transfer reactivity toward oxygen and hydrogen peroxide, and a four-point-probe resistivity (dry) of approximately 40 MΩ/square for a 1-2 μm thick film.