Synthesis of microporous organic polymers with high CO2-over-N2 selectivity and CO2 adsorption

Abstract

A series of microporous organic polymers (MOPs) were synthesized by Schiff base condensation of 1,3,5tris(4-aminophenyl)benzene and a number of dialdehyde monomers. The polymers were structurally characterized by in situ infrared and ex situ solid state 13 C{ 1 H} nuclear magnetic resonance (NMR) spectroscopy. Synthesis conditions were optimized to enhance CO 2 uptake by the MOPs. Synthesis at low temperatures results in the MOPs being linked by imine groups. Heating of the MOPs reduces the number of imine groups and after heating to >300 C nitrile groups were found to be present in the MOPs. The MOPs have specific surface areas up to 614 m 2 g À1 and narrow pore size distributions of $4 to 8 Å. The selectivity of CO 2 -over-N 2 at 273 K and 1 bar was 56-77, which requires either an influence of chemisorption on CO 2 or a molecular sieving (or kinetic selection) of CO 2 -over-N 2 . The materials had also heats of adsorption typical for physisorption of CO 2 .

Self-templated chemically stable hollow spherical covalent organic framework

“…21). The high surface area of COF-DhaTab as compared with its non-hydroxyl analogue MOP (A-B1) 63 was due to the presence of strong intramolecular H-bonding, which imparts structural rigidity to the material and also improves the planarity of the 2D layers( Supplementary Fig. 22).…”

Microporous Organic Polymers for Carbon Dioxide Capture

“…TpPa-2 (S BET = 339 m 2 g −1 ) showed a moderate CO 2 uptake of 64 cm 3 g −1 at the same temperature. In 2013, Xu et al [78] prepared a series of imine-linked MOPs by condensation of 1,3,5-tris(4-aminophenyl)benzene and a number of dialdehyde monomers. Synthesis conditions were optimized to enhance CO 2 uptake by the MOPs.…”

π‐Conjugated Microporous Polymer Films: Designed Synthesis, Conducting Properties, and Photoenergy Conversions

“…4,63.6,79.5,62.1,80.6, and 99.2 nm for TTB-CMP films ( Figure S6, Tables S2, S3), used different concentrations of C 60 of 5,10,15, and 20 mg mL À1 (Tables S4 and S5), and prepared more than 200 solar cells for each condition to optimize the photoactive layers ( Figures S7 and S8). Under optimal conditions,t he CMP film thickness was determined to be 60 nm for both CMPs and the C 60 concentration was 10 mg mL À1 .W e employed ion-sputtered X-ray photoelectron spectroscopy to evaluate the ratio of the sulfur atoms of the CMP films to the carbon atoms of C 60 .F igure 2f and gs ummarizes the depth-dependent distribution of C 60 .The BTT-CMP:C 60 films (Figure 2g,r ed curve) consist of at op 20 nm layer of C 60 , under which C 60 is homogeneously distributed throughout the 60 nm thick CMP film, as indicated by asharp increase in the sulfur content at 20 nm and an almost constant sulfur level over the depth from 20 to 80 nm.…”

“…[1] They show outstanding properties in gas storage, [2] sensing, [3] luminescence, [4] catalysis, [5] energy transfer, [6] and electric energy storage. [7, 8, 9a] CMPs are currently synthesized through solution-phase polymerizations,i ncluding Suzuki reaction, [3a, 4b,5a, 6a] Sonogashira reactions, [2b,d,e,5b, 6b,c,7] Yamamoto reactions, [3a,4a, 5c] oxidative coupling reaction, [2a,c,d, 3c] cyclotrimerization reaction, [5e,9] Schiff-base reaction, [10] phenazine ring-fusion reaction, [8] and Friedel-Crafts reaction. [11] These reactions covalently link organic building blocks into p-conjugated polymer skeletons.…”

“…We prepared films at scan cycles of 2,4,6,8,10,12, and 14 and measured the film thickness using ap rofilometer.F igure 1f presents plots of the thickness versus the cycle number. The …”