Functional Porous Organic Polymers with Conjugated Triaryl Triazine as the Core for Superfast Adsorption Removal of Organic Dyes

ACS Applied Materials & Interfaces, Journal Year: 2021, Volume and Issue: 13(5), P. 6359 - 6366

Published: Feb. 1, 2021

Developing efficient adsorbents for the removal of water pollutants is great significance environmental protection. In this study, conjugated triaryl triazines (CTT), containing intramolecular hydrogen-bonding patterns, were recognized to be intriguing building blocks construction porous organic polymer (POP) adsorbents. These planar monomers with multiple phenolic hydroxyl groups facilitated formation aza-linked polymers hierarchical structures, sheet-like morphology, good surface wettability, and high degree functionality. Such structural characteristics CTT-POP provided superfast adsorption various cationic dyes from water. For methylene blue dye, pseudo-second-order rate constant CTT-POP-1 12.9 g mg–1 min–1, superior those reported in existing literature. addition, can regenerated at least seven times no loss performance, indicating its potential application treatment.

Language: Английский

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Copper-Based Bio-MOF/GO with Lewis Basic Sites for CO₂ Fixation into Cyclic Carbonates and C–C Bond-Forming Reactions

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(27), P. 12667 - 12680

Published: June 25, 2024

Several measures, including crude oil recovery improvement and carbon dioxide (CO2) conversion into valuable chemicals, have been considered to decrease the greenhouse effect ensure a sustainable low-carbon future. The Knoevenagel condensation CO2 fixation introduced as two principal solutions these challenges. In present study for first time, bio-metal–organic frameworks (MOF)(Cu)/graphene oxide (GO) nanocomposites used catalytic agents reactions. view of attendance amine groups, biological MOFs with NH2 functional groups Lewis base sites protruding on channels' internal surface were used. bio-MOF(Cu)/20%GO performs efficaciously in fixation, leading more than 99.9% TON = 525 via solvent-free reaction under 1 bar atmosphere. It has shown that are highly due basic sites, i.e., NH2, pyrimidine, C═O groups. Besides, active exert synergistic effects render bio-MOF(Cu)/10%GO nanostructures efficient catalysts, significantly accelerating reactions aldehydes malononitrile substrates, thanks high TOF (1327 h–1) acceptable reusability. Bio-MOFs can be stabilized using GO oxygen-containing contribute substitutes, an expeditious speed facilitating substrate absorption.

Language: Английский

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Highly Robust 3s–3d {CaZn}–Organic Framework for Excellent Catalytic Performance on Chemical Fixation of CO₂ and Knoevenagel Condensation Reaction

ACS Applied Materials & Interfaces, Journal Year: 2020, Volume and Issue: 12(49), P. 54884 - 54892

Published: Nov. 24, 2020

In terms of ligand-directed synthetic strategy, multifunctional metal-organic frameworks (MOFs) could be assembled by employing organic ligands with nitrogen-containing heterocycles, which serve as Lewis base sites in crystallized porous frameworks. Here, the acidic one-pot hydrothermal reaction CaCl2, Zn(NO3)2, and 2,4,6-tri(2,4-dicarboxyphenyl)pyridine (H6TDP) generates one robust honeycomb-shaped double-walled material {[(CH3)2NH2]2[CaZn(TDP)(H2O)]·3DMF·3H2O}n (NUC-21), has excellent physicochemical characteristics nanoscopic channels, high porosity (58.3%), large specific surface area, heat/water-resisting property. To best our knowledge, this is first 3s-3d dinuclear [CaZn(CO2)6(OH2)]-based nanoporous host framework, whose activated state possesses coexistence acid-base including four-coordinated Zn2+ ions, Ca2+ uncoordinated carboxyl oxygen atoms, Npyridine atoms. As expected, because nature, desolvated NUC-21 displays satisfactory catalytic activity on chemical cycloaddition various epoxides CO2 into corresponding alkyl carbonates under comparatively mild conditions. Furthermore, efficient conversion benzaldehydes malononitrile confirms that simultaneously a bifunctional heterogeneous catalyst for Knoevenagel condensation reactions. Hence, achievements broaden way assembling MOFs can accelerate transformation from simple structural research to socially demanding applications.

Language: Английский

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Tunable amine-functionalized silsesquioxane-based hybrid networks for efficient removal of heavy metal ions and selective adsorption of anionic dyes

Chemical Engineering Journal, Journal Year: 2021, Volume and Issue: 428, P. 131370 - 131370

Published: July 21, 2021

Language: Английский

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Organocatalytic Polymers from Affordable and Readily Available Building Blocks for the Cycloaddition of CO₂ to Epoxides

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(8), P. 4894 - 4924

Published: Jan. 24, 2023

The catalytic cycloaddition of CO2 to epoxides afford cyclic carbonates as useful monomers, intermediates, solvents, and additives is a continuously growing field investigation way carry out the atom-economic conversion value-added products. Metal-free organocatalytic compounds are attractive systems among various catalysts for such transformations because they inexpensive, nontoxic, readily available. Herein, we highlight discuss key advances in development polymer-based materials that match these requirements affordability availability by considering their synthetic routes, supports employed. discussion organized according number (monofunctional versus bifunctional materials) type catalytically active moieties, including both halide-based halide-free systems. Two general approaches identified based on postsynthetic functionalization polymeric or copolymerization monomers bearing moieties. After review material syntheses activities, chemical structural features affecting performance discussed. Based analysis, some strategies future design affordable available organocatalysts with enhanced activity under mild conditions considered.

Language: Английский

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Robust {Cd₄}-Organic Framework for Efficiently Catalyzing CO₂ Cycloaddition and Knoevenagel Condensation

Crystal Growth & Design, Journal Year: 2023, Volume and Issue: 23(5), P. 3320 - 3329

Published: April 20, 2023

The high-value-added carbonates generated from CO2 have attracted the attention of more and researchers because which optimization metal–organic framework (MOF)-based catalysts has seen a considerable upsurge at present. scarcely reported cadmium(II)-based MOFs inspire us to explore CdOFs with excellent catalytic activity high reusability. Herein, unification unreported {Cd4(μ3-OH)2(CH3CO2–)} cluster 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (H5BDCP) led highly robust nanoporous crystalline material {(Me2NH2)5[Cd4(BDCP)2(μ3-OH)2(CH3CO2)(H2O)2]·3DMF·2H2O}n (NUC-67) 57.4% void volume. Structural analysis displays that inner surface channels in activated NUC-67a is functionalized by Lewis acid sites unsaturated Cd2+ ions base μ3-OH– groups, CH3CO2– anions, free pyridine, C═O groups. Under solvent-free conditions, exhibits performance on cycloaddition epoxides; for instance, conversion rate propylene oxide (PO) into carbonate (PC) 1 atm can reach 99% within 6 h 55 °C, resulting 660 turnover number 110 h–1 frequency. Moreover, Knoevenagel condensation reactions aldehydes malononitrile be efficiently catalyzed NUC-67a. Encouragingly, shows strong structural stability good reversible cyclicity above two organic metal leaching below 8 ppb. Hence, this work proves MOF-based should focus design selection ligands, plays decisive role regulation, such as cluster-based nodes, defect sites, unexpected insertion high-porosity channels.

Language: Английский

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A stable 3D Sr-MOF as an efficient heterogeneous catalyst for the cycloadditions of CO2 and knoevenagel condensation reactions

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1303, P. 137466 - 137466

Published: Jan. 5, 2024

Language: Английский

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Tailoring the Coordination Micro‐Environment in Nanotraps for Efficient Platinum/Palladium Separation

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(28)

Published: April 30, 2024

Abstract Recovering platinum group metals from secondary resources is crucial to meet the growing demand for high‐tech applications. Various techniques are explored, and adsorption using porous materials has emerged as a promising technology due its efficient performance environmental beingness. However, challenge lies in effectively recovering separating individual (PGMs) given their similar chemical properties. Herein, breakthrough approach presented by sophisticatedly tailoring coordination micro‐environment series of aminopyridine‐based organic polymers, which enables creation platinum‐specific nanotraps separation binary PGMs (platinum/palladium). The newly synthesized POP‐ o 2NH 2 ‐Py demonstrates record uptakes selectivity toward over palladium, with amino groups adjacent pyridine moieties being vital improving binding performance. Further experiments underline remarkable ability separate palladium. Spectroscopic analysis reveals that offers more favorable fashion ions compared palladium owing greater interaction between N Pt 4+ stronger intramolecular hydrogen bonding four coordinating chlorines at platinum. These findings underscore importance fine‐tuning through subtle modifications can greatly enhance desired metal ions.

Language: Английский

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Dicationic Ionic Liquid @MIL-101 for the Cycloaddition of CO₂ and Epoxides under Cocatalyst-free Conditions

Crystal Growth & Design, Journal Year: 2021, Volume and Issue: 21(7), P. 3689 - 3698

Published: May 27, 2021

Dicationic ionic liquid 1,1′-(hexane-1,6-diyl)-bis(3-methylimidazolium) dibromide was synthesized inside an MIL-101 metal–organic framework via a facile ship-in-bottle technique. The resultant dicationic @MIL-101 composite contains Cr sites as Lewis acidic center and Br– nucleophile. high BET surface area (1162 m2/g) good synergic effects between the resulted in CO2 sorption capacity (47.4 cm3/g at 273 K) catalytic activity for cycloaddition reaction of with epoxide without any cocatalyst or solvent, 92.5% propylene carbonate yield obtained under 100 °C, 1.0 MPa 2.5 h. Moreover, also showed better recycling stability easy separation reaction. Compared complex synthetic route reported functional frameworks, facilely exhibited comparable performance capture utilization.

Language: Английский

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A highly robust cluster-based indium(iii)–organic framework with efficient catalytic activity in cycloaddition of CO₂ and Knoevenagel condensation

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(11), P. 3420 - 3430

Published: Jan. 1, 2023

The efficient catalytic performance displayed by MOFs is decided an appropriate charge/radius ratio of defect metal sites, large enough solvent-accessible channels and Lewis base sites capable polarizing substrate molecules. Herein, the solvothermal self-assembly led to a highly robust nanochannel-based framework {[In4(CPDD)2(μ3-OH)2(DMF)(H2O)2]·2DMF·5H2O}n (NUC-66) with 56.8% void volume, which combination tetranuclear cluster [In4(μ3-OH)2(COO)10(DMF)(H2O)2] (abbreviated as {In4}) conjugated tetracyclic pentacarboxylic acid ligand 4,4'-(4-(4-carboxyphenyl)pyridine-2,6-diyl)diisophthalic (H5CPDD). To best our knowledge, NUC-66 rarely reported {In4}-based 3D embedded hierarchical triangular-microporous (2.9 Å) hexagonal-nanoporous (12.0 channels, are shaped six rows {In4} clusters. After solvent exchange vacuum drying, surface nanochannels in desolvated NUC-66a modified unsaturated In3+ ions, Npyridine atoms μ3-OH groups, all display polarization ability towards polar molecules due their acidity or basicity. experiments performed showed that had high activity cycloaddition reactions epoxides CO2 under mild conditions, should be ascribed its structural advantages including nanoscale rich bifunctional active areas chemical stability. Moreover, NUC-66a, heterogeneous catalyst, could greatly accelerate Knoevenagel condensation aldehydes malononitrile. Hence, this work confirms development rigid nanoporous cluster-based built on ions charge radius will more likely realize practical applications, such catalysis, adsorption separation gas, etc.

Language: Английский

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