Robust Cationic Calix[4]arene Polymer as an Efficient Catalyst for Cycloaddition of Epoxides with CO₂

Abstract

The development of green solid polymer materials bearing multiple active sites as highly efficient heterogeneous catalysts with cooperative effects toward the conversion of carbon dioxide (CO 2 ) to high-value-added cyclic carbonate is highly in need. Here a novel cationic polymer based on the moieties of 1-bromomethyl-4-hydroxy calix[4]arene and tri(4-imidazolylphenyl)amine has been synthesized, characterized, and used as a metal-free bifunctional heterogeneous catalyst for CO 2 utilization. The presence of abundant phenolic OH groups as hydrogen bond donors and bromide anions as nucleophilic agents provides this polymer with brilliant activities in catalyzing the epoxides into cyclic carbonates under atmospheric pressure and solvent-free conditions. More importantly, this bifunctional catalyst can be conveniently recycled and keeps catalytic ability well. This work not only offers a new method to synthesize a competitive green heterogeneous catalyst but also provides the first example of an ionic polymer that contains calixarene for synthesizing cyclic carbonate through the CO 2 cycloaddition reaction.

Macrocycle‐Based Porous Organic Polymers for Separation, Sensing, and Catalysis

“…For instance, Yuan and co‐workers developed a novel cationic polymer based on CAs, through nucleophilic substitution of 1‐bromomethyl‐4‐hydroxy CA[4] with tri(4‐imidazolylphenyl)amine ( Figure a). [ 117 ] The resulting polymer exhibits a moderate CO 2 adsorption capacity (19 cm 3 g –1 at 273 K) although the porosity is low ( S BET = 46 m 2 g –1 ). The presence of CA[4] phenolic hydroxyl groups and bromide ions of imidazolium groups as nucleophile, that can open the epoxide ring, provides network with prominent activities in converting the epoxides into cyclic carbonates.…”

CO2 Capture and Utilization Editorial

“…Zhang et al contributed to these efforts by reporting a green bifunctional heterogeneous catalyst that can be used for the formation of cyclic carbonates through the CO 2 cycloaddition reaction. 42 Similarly, efficient CO 2 electrochemical reduction under mild conditions also requires high-performance catalysts. Different catalyst electrodes (Sn/Cu, BiSn/Cu, Bi 2 Sn/Cu, Bi 3 Sn/Cu, Bi 4 Sn/Cu, and Bi/Cu) were fabricated by electrodeposition, and their activity, stability, and selectivity toward CO 2 reduction to formic acid was measured.…”

Water-stable hydrazone-linked porous organic cages

“…[60][61][62][63][64][65] Our group is particularly interested in preparing new C4RA-based porous materials and their applications in energy and environment aspects. [66][67][68][69][70]…”