Yuanyang Rong

Metastable Ionic Diodes Derived from an Amine‐Based Polymer of Intrinsic Microporosity

A highly rigid amine-based polymer of intrinsic microporosity (PIM), prepared by a polymerization reaction involving the formation of Trögers base, is demonstrated to act as an ionic diode with electrolyte-dependent bistable switchable states.

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.

Fuel cell anode catalyst performance can be stabilized with a molecularly rigid film of polymers of intrinsic microporosity (PIM)

There remains a major materials challenge in maintaining the performance of platinum (Pt) anode catalysts in fuel cells due to corrosion and blocking of active sites. Herein, we report a new materials strategy for improving anode catalyst stability based on a protective microporous coating with an inert and highly rigid (non-blocking) polymer of intrinsic microporosity (PIM-EA-TB). The “anti-corrosion” effect of the PIM-EA-TB coating is demonstrated with a commercial Pt catalyst (3–5 nm diameter, 40 wt% Pt on Vulcan-72) and for three important fuel cell anode reactions: (i) methanol oxidation, (ii) ethanol oxidation, and (iii) formic acid oxidation.

Platinum Nanoparticle Inclusion into a Carbonized Polymer of Intrinsic Microporosity: Electrochemical Characteristics of a Catalyst for Electroless Hydrogen Peroxide Production

The one-step vacuum carbonization synthesis of a platinum nano-catalyst embedded in a microporous heterocarbon (Pt@cPIM) is demonstrated. A nitrogen-rich polymer of an intrinsic microporosity (PIM) precursor is impregnated with PtCl62− to give (after vacuum carbonization at 700 °C) a nitrogen-containing heterocarbon with embedded Pt nanoparticles of typically 1–4 nm diameter (with some particles up to 20 nm diameter). The Brunauer-Emmett-Teller (BET) surface area of this hybrid material is 518 m2 g−1 (with a cumulative pore volume of 1.1 cm3 g−1) consistent with the surface area of the corresponding platinum-free heterocarbon. In electrochemical experiments, the heterocarbon-embedded nano-platinum is observed as reactive towards hydrogen oxidation, but essentially non-reactive towards bigger molecules during methanol oxidation or during oxygen reduction. Therefore, oxygen reduction under electrochemical conditions is suggested to occur mainly via a 2-electron pathway on the outer carbon shell to give H2O2. Kinetic selectivity is confirmed in exploratory catalysis experiments in the presence of H2 gas (which is oxidized on Pt) and O2 gas (which is reduced on the heterocarbon surface) to result in the direct formation of H2O2.