Cobalt porphyrin-based hypercrosslinked ionic polymers as biomimetic nanoreactors for CO2 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 CO2 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 CO2 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 CO2 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 CO2 capture capacity. More importantly, bifunctional AlPor-QP@POP has enormous potential to produce cyclic carbonates with simulated flue gas under ambient conditions. Moreover, AlPor-QP@POP can be readily recycled and efficiently reused more than ten times without an obvious decrease in catalytic activity. Finally, kinetic investigations and a comparative study have been conducted to understand the possible mechanism of CO2 catalytic cycloaddition.

In Situ Anchoring of Small-Sized Silver Nanoparticles on Porphyrinic Triazine-Based Frameworks for the Conversion of CO2 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 CO2 capture and conversion. In terms of the carboxylative cyclization of propargyl alcohols with CO2, 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. The presence of N-rich dual active sites, porphyrin and triazine, which acted as the electron donor and acceptor, respectively, offered a huge opportunity for the nucleation and growth of metal nanoparticles. Significantly, the as-prepared catalyst Ag/TPP-CTF shows excellent catalytic activity (up to 99%) toward the carboxylative cyclization of propargyl alcohols with CO2 at room temperature, achieving record-breaking activities (TOF up to 615 h-1 at 1 bar and 3077 h-1 at 10 bar). Moreover, the catalyst can be easily recovered and reused at least 10 times with retention of high catalytic activity. The possible mechanism involves small-sized AgNP-mediated alkyne activation, which may promote highly efficient and green conversion of CO2. This work paves the way for immobilizing metal nanoparticles onto functional POPs by surface structure changes for enhanced CO2 catalysis.

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.

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.

High-Surface-Area Metalloporphyrin-Based Porous Ionic Polymers by the Direct Condensation Strategy for Enhanced CO2 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 CO2 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 CO2 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 CO2 capture and catalytic conversion into cyclic carbonates with high turnover frequencies under mild conditions. These recyclable aluminum-porphyrin-based PIPs are featured with high surface areas, prominent CO2 adsorptive capacities, rigid porphyrin skeletons, and flexible ionic pendants, as well as the matched amounts and spatial positions of metal centers and ionic sites, in which is demonstrated to be one of the quite competitive catalysts. Therefore, this strategy of introducing ionic components into the porphyrin frameworks as flexible side chains rather than main chains and adjusting the reactivity ratios of comonomers by structure-oriented methods, provides feasible guidance for the multifunctionalization of metalloporphyrin-based POPs, thereby increasing the accessibility of multiple active sites and improving their synergistic catalytic behavior.

A metal-free hydroxyl functionalized quaternary phosphine type ionic liquid polymer for cycloaddition of CO2 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 CO2 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 CO2 Catalysis.

Carbon dioxide catalytic conversion (i. e., CO2 catalysis) is considered as one of the most promising technologies to control CO2 emissions, which is of great significance to build a sustainable society with green low-carbon cycle. In view of its thermodynamic stability and kinetic inertness, CO2 selective activation is still desired. Nowadays, the traditional strategy is to selectively capture and efficiently convert atmospheric CO2 into high value-added chemicals and fuels. Covalent triazine frameworks (CTFs) as a newly emerging and attractive kind of porous organic polymer (POP) have drawn worldwide attention among heterogeneous catalysis because of their nitrogen-rich porous structures and exceptional physicochemical stabilities. In this Minireview, the focus was mainly placed on the structural design and synthesis of CTFs and their applications in CO2 catalysis including CO2 cycloaddition, CO2 carboxylation, CO2 hydrogenation, CO2 photoreduction, and CO2 electroreduction. By discussing the structure-property relationship, valuable guidance from a sustainable perspective may be provided for developing precisely designed CTFs with high performance and excellent industrial application prospects in sustainable CO2 catalysis.

Recent Advances on Imidazolium-Functionalized Organic Cationic Polymers for CO2 Adsorption and Simultaneous Conversion into Cyclic Carbonates.

The cycloaddition reaction of CO2 with various epoxides to generate cyclic carbonates is one of the most promising and efficient approaches for CO2 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 CO2 . 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 CO2 adsorption and simultaneous conversion ability. This Review describes the recent advancements made with regard to the design and synthesis of this type of polymeric networks having imidazolium functionality. They are considered as an outstanding heterogeneous catalyst for the cycloaddition of CO2 to epoxides. Based on the perspective from the design of building blocks to the synthesis of cationic polymers, the focus mainly lies on how to introduce imidazole units into the material backbone via a covalent linking approach and how to incorporate other active sites capable of activating CO2 and/or epoxides into such polymeric materials.

Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO2 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 CO2 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 CO2 with an excellent activity and good recyclability under mild conditions. Interestingly, these CO2 -philic materials could catalyze the cycloaddition reaction smoothly by using simulated flue gas (15 % CO2 in N2 , v/v) as a raw material, which indicates that a stable local microenvironment and polymer swellability might promote the transformation. Thus, the introduction of polar ionic liquid units into metalloporphyrin-based porous materials is regarded as a promising new strategy for the chemical conversion of CO2 .

Metallosalen-Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO2 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 CO2 /N2 adsorptive selectivity. Moreover, these POPs having both metal centers (Lewis acid) and ionic units (nucleophile) could serve as bifunctional catalysts in the catalytic conversion of CO2 into high value-added chemicals without any additional co-catalyst under mild and solvent-free conditions, for example, CO2 /epoxides cycloaddition and Nformylation of amines from CO2 and hydrosilanes. The results demonstrated that the irregular porous structure was very favorable for the diffusion of substrates and products, and the microporous structural property resulted in the enrichment of CO2 near the catalytic centers in the CO2 -involved transformations. Additionally, the superhydrophobic property could not only enhance the chemoselectivity of products but also promote the stability and recyclability of catalysts.

Cooperative Catalytic Activation of Si-H Bonds: CO2 -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 CO2 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 CO2 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.