Adjustable Functionalization of Hyper-Cross-Linked Polymers of Intrinsic Microporosity for Enhanced CO2 Adsorption and Selectivity over N2 and CH4

In this paper, we report the design, synthesis, and characterization of a series of hyper-cross-linked polymers of intrinsic microporosity (PIMs), with high CO2 uptake and good CO2/N2 and CO2/CH4 selectivity, which makes them competitive for carbon capture and biogas upgrading. The starting hydrocarbon polymers’ backbones were functionalized with groups such as −NO2, −NH2, and −HSO3, with the aim of tuning their adsorption selectivity toward CO2 over nitrogen and methane. This led to a significant improvement in the performance in the potential separation of these gases. All polymers were characterized via Fourier transform infrared (FTIR) spectroscopy and 13C solid-state NMR to confirm their molecular structures and isothermal gas adsorption to assess their porosity, pore size distribution, and selectivity. The insertion of the functional groups resulted in an overall decrease in the porosity of the starting polymers, which was compensated with an improvement in the final CO2 uptake and selectivity over the chosen gases. The best uptakes were achieved with the sulfonated polymers, which reached up to 298 mg g–1 (6.77 mmol g–1), whereas the best CO2/N2 selectivities were recorded by the aminated polymers, which reached 26.5. Regarding CH4, the most interesting selectivities over CO2 were also obtained with the aminated PIMs, with values up to 8.6. The reason for the improvements was ascribed to a synergetic contribution of porosity, choice of the functional group, and optimal isosteric heat of adsorption of the materials

A porphyrin-based microporous network polymer that acts as an efficient catalyst for cyclooctene and cyclohexane oxidation under mild conditions

The highly efficient dibenzodioxin-forming reaction between the (pentafluorophenyl)porphyrin manganese(III) (MnP) and hexahydroxytriptycene (HHT) provide a new microporous network polymer (P1), which demonstrated a large surface area (1080 m2 g− 1) and proved to be an efficient solid for heterogeneous catalysis for cyclooctene and cyclohexane oxidation under mild conditions and with high capacity of recovery and reuse in many catalytic cycles

Highly active manganese porphyrin-based microporous network polymers for selective oxidation reactions

New microporous polymer networks, constructed by a nucleophilic substitution reaction between two different porphyrins and metalloporphyrins are reported. The meso-tetrakis-(pentafluorophenyl)porphyrin HP1 (monomer A1) and/or its manganese complex MP1 (monomer A2) was reacted with the meso-tetrakis-(3,4-dihydroxyphenyl)porphyrin HP2 (monomer B1) and/or its manganese complex MP2 (monomer B2), giving rise to four new porphyrin-based microporous network polymers (P1-P4) with apparent BET surface areas in the range 600–1200 m2 g−1. The catalytic performance of the polymers was evaluated by oxidation reactions using cyclooctene and cyclohexane as substrates and Iodosylbenzene as oxidant in cytochrome P-450 model reactions. The catalytic activity and selectivity of these porous polymer networks are similar or superior to those of the analogous homogeneous manganese porphyrins MP1 and MP2. The robustness of the materials in terms of thermal stability and good recyclability showed that they hold great promise as biomimetic heterogeneous catalysts