Cobalt porphyrin-based hypercrosslinked ionic polymers as biomimetic nanoreactors for CO conversion to cyclic carbonates.

A simple and low-cost approach to construct one type of cobalt porphyrin-based hypercrosslinked ionic polymer with high specific surface areas, densely located ionic groups and highly dispersed cobalt sites has been demonstrated, which act as bifunctional catalysts for the solvent-additive-free conversion of CO into cyclic carbonates with outstanding biomimetic catalytic performance and good recyclability.

Two in one: aluminum porphyrin-based porous organic polymers containing symmetrical quaternary phosphonium salts for catalytic conversion of CO into cyclic carbonates.

Based on the double activation models of epoxides, the design and synthesis of ionic porous organic polymers (iPOPs) is considered to be very attractive and promising but has remained a great challenge in recent decades owing to electrostatic interactions between charged groups. In this contribution, we developed a two-in-one strategy to fabricate metalloporphyrin-based iPOPs with unique nanostructures (named AlPor-QP@POP), which are composed of aluminum porphyrin units and three-dimensional quaternary phosphonium salts that work synergistically in the cycloaddition of CO with epoxides under mild conditions. The high symmetry of two monomers allows them to possess similar reactivity ratios and thus endows AlPor-QP@POP with densely located active sites, a large surface area and good CO capture capacity.

In Situ Anchoring of Small-Sized Silver Nanoparticles on Porphyrinic Triazine-Based Frameworks for the Conversion of CO into α-Alkylidene Cyclic Carbonates with Outstanding Catalytic Activities under Ambient Conditions.

The preparation of catalytic hybrid materials by introducing highly dispersed metallic nanoparticles into porous organic polymers (POPs) may be an ideal and promising strategy for integrated CO capture and conversion. In terms of the carboxylative cyclization of propargyl alcohols with CO, the anchoring of silver nanoparticles (AgNPs) on functional POPs to fabricate efficient heterogeneous catalysts is considered to be quite intriguing but remains challenging. In the contribution, well-dispersed AgNPs were successfully anchored onto the porphyrinic triazine-based frameworks by a simple "liquid impregnation and in situ reduction" strategy.

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

Multifunctionalization of porous organic polymers toward synergistic CO 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 CO 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 m·g), abundant hierarchical micro-mesopores, and prominent CO adsorption capacities (up to 1.

High-Surface-Area Metalloporphyrin-Based Porous Ionic Polymers by the Direct Condensation Strategy for Enhanced CO Capture and Catalytic Conversion into Cyclic Carbonates.

Metalloporphyrin-based porous organic polymers (POPs) that behave as advanced biomimetic nanoreactors have drawn continuous attention for heterogeneous CO catalysis in the past decades. Inspired by the double activation model of epoxides, the design and synthesis of metalloporphyrin-based porous ionic polymers (PIPs) are considered as one of the most promising approaches for converting CO to cyclic carbonates under cocatalyst- and solvent-free conditions. To overcome the obstacle of poor reaction activity of ionic monomers or highly irregular stacking architecture, in this paper, we have proposed and demonstrated a modular bottom-up approach for constructing a series of high-surface-area metalloporphyrin-based PIPs in high yields by the direct condensation strategy, thus boosting the close contact of multiple active sites and achieving the enhanced CO capture and catalytic conversion into cyclic carbonates with high turnover frequencies under mild conditions.

A metal-free hydroxyl functionalized quaternary phosphine type ionic liquid polymer for cycloaddition of CO and epoxides.

Quaternary phosphine type hypercrosslinked polymer catalysts were successfully prepared using the Friedel-Crafts alkylation reactions, which benefit from the synergistic effects between the Brønsted acidity of the hydroxyl group and nucleophilicity of the Br group as well as the CO capture of the ionic liquids. The as-obtained metal-free catalysts facilitate the cycloaddition and synthesis of high value-added fine chemicals.

Covalent Triazine Frameworks Obtained from Nitrile Monomers for Sustainable CO Catalysis.

Carbon dioxide catalytic conversion (i. e., CO catalysis) is considered as one of the most promising technologies to control CO emissions, which is of great significance to build a sustainable society with green low-carbon cycle.

Recent Advances on Imidazolium-Functionalized Organic Cationic Polymers for CO Adsorption and Simultaneous Conversion into Cyclic Carbonates.

The cycloaddition reaction of CO with various epoxides to generate cyclic carbonates is one of the most promising and efficient approaches for CO fixation. Typical imidazolium-based ionic liquids possessing electrophilic cations and nucleophilic halogen anions have been identified as excellent and environmentally friendly candidates for synergistically activating epoxides to convert CO . Therefore, the feasible construction of a series of imidazolium-functionalized organic cationic polymers can bridge the gap between homogeneous and heterogeneous catalysis, thereby obtaining highly selective CO adsorption and simultaneous conversion ability.

Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO under Ambient Conditions.

A facile and one-pot synthesis of metalloporphyrin-based ionic porous organic polymers (M-iPOPs) was performed through a typical Yamamoto-Ullmann coupling reaction for the first time. We used various characterization techniques to demonstrate that these strongly polar Al-based materials (Al-iPOP) possessed a relatively uniform microporosity, good swellable features, and a good CO capture capacity. If we consider the particular physicochemical properties, heterogeneous Al-iPOP, which bears both a metal active center and halogen anion, acted as a bifunctional catalyst for the solvent- and additive-free synthesis of cyclic carbonates from various epoxides and CO with an excellent activity and good recyclability under mild conditions.

Metallosalen-Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO into Valuable Chemicals.

A series of new metallosalen-based ionic porous organic polymers (POPs) were synthesized for the first time using a simple unique strategy based on the free-radical copolymerization reaction. Various techniques were used to characterize the physicochemical properties of these catalysts. These well-designed materials endowed high surface area, hierarchical porous structures, and enhanced CO /N adsorptive selectivity.

Cooperative Catalytic Activation of Si-H Bonds: CO -Based Synthesis of Formamides from Amines and Hydrosilanes under Mild Conditions.

A simple cooperative catalytic system was successfully developed for the solvent-free N-formylation of amines with CO and hydrosilanes under ambient conditions, which was composed of a Zn(salen) catalyst and quaternary ammonium salt. These commercially available binary components activated the Si-H bonds effectively, owing to the intermolecular synergistic effect between Lewis base and transition metal center (LB-TM), and subsequently facilitated the insertion of CO to form the active silyl formats, thereby leading to excellent catalytic performance at a low catalyst loading. Furthermore, the bifunctional Zn(salen) complexes, with two imidazolium-based ionic-liquid (IL) units at the 3,3'-position of salen ligand, acted as intramolecularly cooperative catalysts, and the solvent-regulated separation resulted in facile catalyst recycling and reuse.