Aluminum Porphyrin-Based Ionic Porous Aromatic Frameworks Having High Surface Areas and Highly Dispersed Dual-Function Sites for Boosting the Catalytic Conversion of CO₂ into Cyclic Carbonates

Abstract

Multifunctionalization of porous organic polymers toward synergistic CO2 catalysis has drawn much attention in recent decades, but it still faces many challenges. Herein, we develop a facile, simple, and efficient strategy to obtain a series of aluminum porphyrin-based ionic porous aromatic frameworks (iPAFs), which are considered excellent bifunctional catalysts for converting CO2 into cyclic carbonates without any cocatalyst under mild and solvent-free conditions. By increasing the amounts of tetraphenylmethane fragments in the porphyrin backbones, the cooperative effect between Lewis acidic metal centers and nucleophilic ionic sites has been enhanced and then the significant improvement of catalytic activity can be achieved owing to the high surface areas (up to 719 m2·g–1), abundant hierarchical micro–mesopores, and prominent CO2 adsorption capacities (up to 1.8 mmol·g–1 at 273 K) as well as highly dispersed dual-function sites. More fascinatingly, high-active AlPor-iPAF-3 enables CO2 cycloaddition to perform with diluted CO2 (15% CO2 in 85% N2, v/v) or under ambient conditions. Therefore, this postsynthetic modification procedure in combination with the framework dilution strategy provides a new approach to fabricating high-surface-area metalloporphyrin-based porous ionic polymers (PIPs) with hierarchical structures, which is conducive to improving the accessibility of multiple active sites around substrates.

Optimization and kinetics of crown ether-based hydroxyl-rich organic polymers for sustainable CO2 fixation and iodine vapor adsorption

“…The catalyst concentration being constant and CO 2 considered in excess, while assuming the reaction to be a primary one, the equation can be abbreviated to eqn (4), since the catalyst concentration is a constant and CO 2 is considered to be in excess, and assuming that the reaction is a primary reaction. [67][68][69] Integrating eqn (4) transforms to eqn ( 5) and ( 6) ((1 − x) means [epoxide], and x signies conversion rate). It follows that the value of K obs is ensured by the slope of the natural loglinear plot of the epoxide concentration over time.…”

Recent Progress of Amorphous Porous Organic Polymers as Heterogeneous Photocatalysts for Organic Synthesis

“…Recently, Luo and co‐workers [ 66 ] reported a paper on the synthesis of a porphyrin‐based porous aromatic framework, AlPor‐PAF, using aluminum porphyrins and tetraphenylmethane as building blocks in an Ullmann‐type coupling reaction. This novel catalyst was then methylated and quaternized with the corresponding acids to introduce imidazole cations and halogen anions to obtain three ionic porous aromatic frameworks (Figure 8c).…”

Fe(iii)-incorporated porphyrin-based conjugated organic polymer as a peroxidase mimic for the sensitive determination of glucose and H2O2

“…Because of their organic framework that bears suitable functional groups and their biocompatible nature, COPs have the potential for biosensing. They exhibit high thermal 42,43 and chemical stability, 44 making them a suitable candidate for enzyme-mimicking applications. Therefore, recent years have seen an increase in reports involving this type of organic polymer.…”