Browse
Submit Data
Databases
API
Help

Dataset Information

25 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Functional Porous Ionic Polymers as Efficient Heterogeneous Catalysts for the Chemical Fixation of CO₂ under Mild Conditions.

ABSTRACT: The development of efficient and metal-free heterogeneous catalysts for the chemical fixation of CO₂ into value-added products is still a challenge. Herein, we reported two kinds of polar group (-COOH, -OH)-functionalized porous ionic polymers (PIPs) that were constructed from the corresponding phosphonium salt monomers (v-PBC and v-PBH) using a solvothermal radical polymerization method. The resulting PIPs (POP-PBC and POP-PBH) can be used as efficient bifunctional heterogeneous catalysts in the cycloaddition reaction of CO₂ with epoxides under relatively low temperature, ambient pressure, and metal-free conditions without any additives. It was found that the catalytic activities of the POP-PBC and POP-PBH were comparable with the homogeneous catalysts of Me-PBC and PBH and were higher than that of the POP-PPh₃-COOH that was synthesized through a post-modification method, indicating the importance of the high concentration catalytic active sites in the heterogeneous catalysts. Reaction under low CO₂ concentration conditions showed that the activity of the POP-PBC (with a conversion of 53.8% and a selectivity of 99.0%) was higher than that of the POP-PBH (with a conversion of 32.3% and a selectivity of 99.0%), verifying the promoting effect of the polar group (-COOH group) in the porous framework. The POP-PBC can also be recycled at least five times without a significant loss of catalytic activity, indicating the high stability and robustness of the PIPs-based heterogeneous catalysts.

SUBMITTER: Dai Z

PROVIDER: S-EPMC9269538 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Facile synthesis of crystalline viologen-based porous ionic polymers with hydrogen-bonded water for efficient catalytic CO2 fixation under ambient conditions.

Project description:In this work, we report a series of crystalline viologen-based porous ionic polymers (denoted VIP-X, X = Cl or Br), that have in situ formed dicationic viologens paired with halogen anions and intrinsic hydrogen-bonded water molecules, towards metal-free heterogeneous catalytic conversion of carbon dioxide (CO2) under mild conditions. The targeted VIP-X materials were facilely constructed via the Menshutkin reaction of 4,4'-bipyridine with 4,4'-bis(bromomethyl)biphenyl (BCBMP) or 4,4'-bis(chloromethyl)biphenyl (BBMBP) monomers. Their crystalline and porous structures, morphological features and chemical structures and compositions were fully characterized by various advanced techniques. The optimal catalyst VIP-Br afforded a high yield of 99% in the synthesis of cyclic carbonate by CO2 cycloaddition with epichlorohydrin under atmospheric pressure (1 bar) and a low temperature (40 °C), while other various epoxides could be also converted into cyclic carbonates under mild conditions. Moreover, the catalyst VIP-Br could be separated easily and reused with good stability. The remarkable catalytic performance could be attributed to the synergistic effect of the enriched Br- anions and available hydrogen bond donors -OH groups coming from H-bonded water molecules.

| S-EPMC9048747 | biostudies-literature

Ionic Porous Organic Polymers Based on Functionalized Tetraarylborates.

Project description:Lithium tetrakis(4-boronatoaryl)borates were subjected to polycondensation reactions with selected polyhydroxyl monomers such as 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7-tetrahydroxy-9,10-dimethylanthracene (THDMA). Obtained boronate-type ionic porous polymers TAB1-4 were characterized by PXRD, 6Li and 11B magic-angle spinning nuclear magnetic resonance (MAS NMR), FT-IR, SEM, and TGA. They exhibit relatively good sorption of H2 (up to 75 cm3/g STP), whereas N2 uptake at 77 K for lower pressure range is relatively poor (up to 50 cm3/g STP below P/P0 = 0.8). In addition, the effect of elongation of aryl arms in the tetraarylborate core on the materials' properties was studied. Thus, it was found that replacement of the 4-boronatophenyl with 4-boronatobiphenylyl group has a negative impact on the sorption characteristics.

| S-EPMC6630441 | biostudies-literature

One-pot construction of nitrogen-rich polymeric ionic porous networks for effective CO2 capture and fixation.

Project description:Facile preparation of ionic porous networks (IPNs) with large and permanent porosity is highly desirable for CO2 capture and transformation but remains a challenge. Here we report a one-pot base-mediated construction of nitrogen-rich IPNs through a combination of nucleophilic substitution and quaternisation chemistry from H-imidazole. This strategy, as proven by the model reactions of 1H-imidazole or 1-methyl-1H-imidazole with cyanuric chloride, allows for fine regulation of porosity and physicochemical properties, leading to nitrogen-rich IPNs featuring abundant ionic units and radicals. The as-prepared networks, termed IPN-CSUs, efficiently capture CO2 (80.1 cc g-1 at 273 K/1 bar) with an ideal CO2/N2 selectivity of 139.7. They can also effectively catalyse the cycloaddition reaction between CO2 and epoxides with high yields of up to 99% under mild conditions (0.1 MPa, 298 K), suggesting their possible applications in the fields of both selective molecular separation and conversion. Unlike the previously known strategies generally involving single coupling chemistry, our strategy combining two coupling routes in one pot appears to be unique and potentially applicable to other building blocks.

| S-EPMC8689585 | biostudies-literature

Ionic Liquid-Modified Porous Organometallic Polymers as Efficient and Selective Photocatalysts for Visible-Light-Driven CO2 Reduction.

Project description:In the photoreduction of CO2 to CO, the competitive H2 evolution is always inevitable due to the approximate reduction potentials of H+/H2 and CO2/CO, which results in poor selectivity for CO production. Herein, imidazolium-type ionic liquid- (IL-) modified rhenium bipyridine-based porous organometallic polymers (Re-POMP-IL) were designed as efficient and selective photocatalysts for visible-light CO2 photoreduction to CO based on the affinity of IL with CO2. Photoreduction studies demonstrated that CO2 photoreduction promoted by Re-POMP-IL functioning as the catalyst exhibits excellent CO selectivity up to 95.5% and generate 40.1 mmol CO/g of Re-POMP-IL1.0 (obtained by providing equivalent [(5,5'-divinyl-2,2'-bipyridine)Re(CO)3Cl] and 3-ethyl-1-vinyl-1H-imidazol-3-ium bromide) at 12 h, outperforming that attained with the corresponding Re-POMP analogue without IL, which highlights the crucial role of IL. Notably, CO2 adsorption, light harvesting, and transfer of photogenerated charges as key steps for CO2RR were studied by employing POMPs modified with different amounts of IL as photocatalysts, among which the CO2 affinity as an important factor for POMPs catalyzed CO2 reduction is revealed. Overall, this work provides a practical pathway to improve the CO2 photoreduction efficiency and CO selectivity by employing IL as a regulator.

| S-EPMC7533041 | biostudies-literature

A Porous Metal-Organic Framework Assembled by [Cu30] Nanocages: Serving as Recyclable Catalysts for CO2 Fixation with Aziridines.

Project description:Based on a novel ligand 5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid (H4BCP) with large skeletons, a unique porous framework {[Cu2(BCP)(H2O)2]·3DMF} n (1) assembled by nano-sized and censer-like [Cu30] cages is successfully obtained and structurally characterized. In 1, the large 1D channel in frameworks and window size in the nanocages can enrich methylene blue and capture CO2, exhibiting the promising applications in environmental protection. More importantly, the explorations on the cycloaddition reaction of CO2 and aziridines with various substituents suggest that 1 can serve as an efficient heterogeneous catalyst for CO2 conversion with aziridines in a solvent-free system, which can be reused at least ten times without any obvious loss in catalytic activity. This is the first example of metal-organic framework (MOF)-based catalysts in converting CO2 into high-value oxazolidinones through activating aziridines and CO2, further extending the applications of MOFs materials in catalysis.

| S-EPMC5111788 | biostudies-literature

Heterogeneous Rh and Rh/Ag bimetallic nanoparticle catalysts immobilized on chiral polymers.

Project description:The development of heterogeneous chiral catalysts has lagged far behind that of homogeneous chiral catalysts in spite of their advantages, such as environmental friendliness for a sustainable society. We describe herein novel heterogeneous chiral Rh and Rh/Ag bimetallic nanoparticle catalysts consisting of polystyrene-based polymers with chiral diene moieties. The catalysts enable high-to-excellent yields and enantioselectivities to be obtained in asymmetric 1,4-addition reactions of arylboronic acids with α,β-unsaturated carbonyl compounds such as ketones, esters, and amides, and in other asymmetric reactions. The catalysts could be readily recovered by simple filtration and reused; they could also be applied to continuous-flow synthesis. We also discuss the nature of possible reaction species based on XPS analysis.

| S-EPMC6761866 | biostudies-literature

Pyrrole-Based Conjugated Microporous Polymers as Efficient Heterogeneous Catalysts for Knoevenagel Condensation.

Project description:Conjugated microporous polymers (CMPs) with robust architectures, facilely tunable pore sizes and large specific surface areas have emerged as an important class of porous materials due to their demonstrated prospects in various fields, e.g. gas storage/separation and heterogeneous catalysis. Herein, two new pyrrole-based CMPs with large specific surface areas and good stabilities were successfully prepared by one-step oxidative self-polycondensation of 1,2,4,5-tetra (pyrrol-2-ly)benzene or 1,3,5-tri (pyrrol-2-ly)benzene, respectively. Interestingly, both CMPs showed very high catalytic activity toward Knoevenagel condensation reaction, which was attributed to the inherent pore channels, high specific surface areas and abundant nitrogen sites within CMPs. Additionally, both CMPs displayed excellent recyclability with negligible degradation after 10 cycles. This work provides new possibilities into designing novel nitrogen-rich high-performance heterogeneous catalysts.

| S-EPMC8141711 | biostudies-literature

CO2 Fixation with Epoxides under Mild Conditions with a Cooperative Metal Corrole/Quaternary Ammonium Salt Catalyst System.

Project description:The cooperative catalytic activity of several metal corrole complexes in combination with tetrabutyl-ammonium bromide (TBAB) has been investigated for the reaction of epoxides with CO2 leading to cyclic carbonates. It was found that the use of just 0.05 mol % of a manganese(III)corrole with 2 mol % TBAB exhibits excellent catalytic activity under an atmosphere of CO2 .

| S-EPMC5446785 | biostudies-literature

Dataset for the synthesis and application of single-component heterogeneous catalysts based on zinc and tin for the cycloaddition of pure, diluted, and impure CO2 to epoxides under mild conditions.

Project description:The cycloaddition of CO2 to epoxides under mild conditions is a growing field of research and a viable strategy to recycle CO2 in the form of cyclic carbonates as useful intermediates, solvents, and additives. This target requires readily accessible and recyclable catalysts whose synthesis does not involve expensive monomers, multistep procedures, coupling reagents, etc. Additionally, the catalysts should be active under atmospheric pressure and tolerate impurities such as methane and H2S. In a recent manuscript (Rational engineering of single-component heterogeneous catalysts based on abundant metal centers for the mild conversion of pure and impure CO2 to cyclic carbonates; Chemical Engineering Journal 422 (2021) 129930) we have developed strategies to prepare efficient heterogeneous catalysts for the cycloaddition reaction of CO2 to epoxides. Such materials consist of dispersions of metal halides (ZnCl2 or SnCl4) on silica support that is further functionalized with ionic liquids bearing nucleophilic halide moieties for cooperative epoxide activation and ring-opening. Herein, we provide useful complementary data for the characterization of the prepared materials in the form of: SEM images of materials (SEM: scanning electron microscope), SEM-EDS images of materials (EDS: Energy-dispersive X-ray spectroscopy), TEM images of materials (TEM: transmission electron microscope); XPS (X-ray photoelectron spectroscopy) survey spectra of most active catalysts and related high-resolution spectra in spectral regions of interest, BET (Brunauer-Emmett-Teller) physisorption isotherms of materials, raw 1H NMR spectra of catalytic reactions to verify the reproducibility of the reaction outcome and identify the reaction products.

| S-EPMC8192583 | biostudies-literature

Metal-salen molecular cages as efficient and recyclable heterogeneous catalysts for cycloaddition of CO2 with epoxides under ambient conditions.

Project description:A salen based molecular cage, salen@cage, was synthesized and complexed with Co and Al to yield metal-salen molecular cages, Co(ii)@cage, Co(iii)@cage and Al(iii)@cage. These cages were demonstrated to be efficient heterogeneous catalysts for the cycloaddition of CO2 with styrene oxide, achieving full conversion at 25 °C and 1 atm CO2. Good to excellent yields of various cyclic carbonates were also achieved under mild conditions. Al(iii)@cage can be reused up to five times without any significant loss of its high catalytic activity. The capability to access a variety of heterogeneous organometallic catalysts with salen@cage offers new prospects for practical CO2 utilization and chemical manufacturing.

| S-EPMC6357855 | biostudies-literature