Engineering pore surface and morphology of microporous organic polymers for improved affinity towards CO2

Metal Catalysis with Knitting Aryl Polymers: Design, Catalytic Applications, and Future Trends

“…The resulting KAPs exhibited high CO 2 adsorption capacities between 11.32 and 33.22%. 13−18 Besides, the KAPs can be easily postfunctionalized with groups to improve the gas capture or to be used as acid−base catalysts, for example, by incorporation of −NH 2 and −SO 3 H groups into a preformed KAP, 19−21 by amidation of carbonyl-rich KAPs, 22 or by postfunctionalization with polyamines of chlorine or bromine-based KAPs. 23,24 The incorporation of metals in POPs opens new possibilities of application to these materials, especially in the field of heterogeneous catalysis being an interesting alternative to inorganic supports.…”

“…The list of building blocks employed is large: phenols, polycyclic aromatic hydrocarbons, and heterocyclic based monomers, tetraphenylsilane and tetraphenylgermanium, triptycene, triazine and spirobifluorene, phenyl and naphthyl-amine monomers, or fluoranthene and binaphthalene, among others. The resulting KAPs exhibited high CO 2 adsorption capacities between 11.32 and 33.22%. − Besides, the KAPs can be easily postfunctionalized with groups to improve the gas capture or to be used as acid–base catalysts, for example, by incorporation of −NH 2 and −SO 3 H groups into a preformed KAP, − by amidation of carbonyl-rich KAPs, or by postfunctionalization with polyamines of chlorine or bromine-based KAPs. , …”

Exceptionally Stable Microporous Organic Frameworks with Rigid Building Units for Efficient Small Gas Adsorption and Separation

“…However, MOPs incorporating heteroatoms have been found to have undesirable physicochemical stability for long-term gas adsorption use under harsh conditions. For example, the initial degradation temperatures of the MOPs TAP, PTPNH-1, and HMC-1 mentioned above was 300 °C ( T 20% ), 220 °C ( T 10% ), and 280 °C ( T 5% ), respectively. Therefore, to improve the MOPs’ physicochemical stability, an effective strategy has been the introduction of rigid and stable building units into their networks .…”

“…Microporous organic polymers (MOPs) as emerging porous materials, are currently of considerable academic and industrial interest, − in applications ranging from gas adsorption and separation, − catalysis, − to energy storage. − In particular, MOPs can serve as excellent platforms for small gas (e.g., CO 2 , CH 4 , and N 2 ) adsorption and separation, owing to their large specific surface area, intrinsic and rich porosity, tunable pore structure, and high flexibility in structural design. The incorporation of heteroatoms, such as, nitrogen and oxygen into the MOP framework was also found to be especially useful in improving small gas adsorption capacity/selectivity because of the enhanced interaction between the gas molecules and polymers. , For instance, Bera et al designed azo-based porous polymers (TAP) through the incorporation of nitrogen-rich functional groups, which displayed gas adsorption capacities of 76.5 cm 3 g –1 for CO 2 , 30.4 cm 3 g –1 for CH 4 at 273 K, 1.0 bar, and 14.4 mg g –1 for H 2 at 77 K, 1.0 bar .…”

“…The incorporation of heteroatoms, such as, nitrogen and oxygen into the MOP framework was also found to be especially useful in improving small gas adsorption capacity/selectivity because of the enhanced interaction between the gas molecules and polymers. , For instance, Bera et al designed azo-based porous polymers (TAP) through the incorporation of nitrogen-rich functional groups, which displayed gas adsorption capacities of 76.5 cm 3 g –1 for CO 2 , 30.4 cm 3 g –1 for CH 4 at 273 K, 1.0 bar, and 14.4 mg g –1 for H 2 at 77 K, 1.0 bar . Tao and co-workers reported two amine-functionalized MOPs that exhibited a CO 2 uptake of 72.4 and 63.2 cm 3 g –1 for PTPNH-1 and PTPNH-2, respectively, at 273 K and 1.0 bar, while Bhaumik reported a nitrogen and sulfur-rich microporous copolymer (HMC-1) with an ultrahigh CO 2 adsorption capacity of 235.7 cm 3 g –1 at 273 K and 3.0 bar.…”