Amide Functionalized Microporous Organic Polymer (Am-MOP) for Selective CO₂ Sorption and Catalysis

Abstract

We report the design and synthesis of an amide functionalized microporous organic polymer (Am-MOP) prepared from trimesic acid and p-phenylenediamine using thionyl chloride as a reagent. Polar amide (-CONH-) functional groups act as a linking unit between the node and spacer and constitute the pore wall of the continuous polymeric network. The strong covalent bonds between the building blocks (trimesic acid and p-phenylenediamine) through amide bond linkages provide high thermal and chemical stability to Am-MOP. The presence of a highly polar pore surface allows selective CO2 uptake at 195 K over other gases such as N2, Ar, and O2. The CO2 molecule interacts with amide functional groups via Lewis acid-base type interactions as demonstrated through DFT calculations. Furthermore, for the first time Am-MOP with basic functional groups has been exploited for the Knoevenagel condensation reaction between aldehydes and active methylene compounds. Availability of a large number of catalytic sites per volume and confined microporosity gives enhanced catalytic efficiency and high selectivity for small substrate molecules.

Preparation and Characterization of Polyamides and Nitrogen‐doped Carbons for Enhanced CO2 Capture

“…The morphologies of polyamides and carbon‐based materials were further confirmed using SEM analysis (Figure ). The images illustrate the fabricated polymers as agglomerates of small particles, as prevalent in many covalent organic polymers . The PA1‐600 and PA2‐600 exhibit porosity which is attributed to space free structures with low compactness and high free volume, while the polymers themselves possessed less‐porous structures.…”

Design and synthesis of a new porous organic polymer equipped with N‐propyl sulfamic acid functionalities: As an efficient heterogeneous catalyst for the synthesis of 1,8‐dioxo‐octahydroxanthene derivatives

“…Considering the acidic nature of catalyst 4, a possible mechanism is designated in Scheme 3 for 1,8-dioxo-octahydroxanthenes formation. As illustrated, in the presence of acidic catalyst 4, dimedone (6) in its enol form is induced for easier nucleophilic attack to the activated aldehyde (5) to give rise to intermediate (A). In the following, (A) is transformed to (B) as a Michael acceptor via dehydration.…”

“…In this regard, heterogenizing homogeneous catalysts [6,[24][25][26], utilizing green solvents, and also developing reactions under solvent-free conditions are the subject of great interest. The majority of multi-component reactions were performed between carbonyl containing compounds (5) and dimedone (6) into the corresponding 1,8-dioxo-octahydroxanthenes (7) in the presence of catalyst 4 under solvent-free conditions a .…”

Design and Catalytic Application of Functional Porous Organic Polymers: Opportunities and Challenges

“…Apart from offering highly reactive functional groups in the POP, these can be easily tuned and modified by varying synthetic approaches and selection of organic building blocks (monomers). The structure of POPs is greatly dependent on spatial geometry and the size of monomers . More importantly, organic cross linkers play a crucial role in the architecture of POPs.…”