Bifunctional {Pb₁₀K₂}–Organic Framework for High Catalytic Activity in Cycloaddition of CO₂ with Epoxides and Knoevenagel Condensation

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(16), P. 10373 - 10383

Published: Aug. 9, 2022

Seeking strategies to enhance the chemical stability of metal–organic framework (MOF) materials has become a focus for practical applications, which prompts us carry out exploratory self-assembly microporous heterometallic MOFs by introducing alkali metal ions. Herein, exquisite combination scarcely reported S-shaped [Pb10K2(μ2-OH)2(COO)24] clusters and 2,4,6-tri(2,4-dicarboxyphenyl)pyridine (H6TDP) ligands under solvothermal conditions generated highly robust {(Me2NH2)2[Pb5K(TDP)2(μ2-OH)]·4DMF·6H2O}n (NUC-45) with one-dimensional (1D) open channels along a-axis. Thanks excellent confined pore environments, such as large surface area, rich Lewis acid sites including Pb2+ K+, plentiful base μ2-OH group Npyridine atom, channels, activated NUC-45a exhibits catalytic performance in cycloaddition CO2 various epoxides mild conditions. Moreover, NUC-45a, heterogeneous catalyst, shows high activity Knoevenagel condensation aldehydes malononitrile recyclability. Meanwhile, both reactions have turnover number frequency. This work that use multifunctional organic introduction ions are conducive construction porous cluster-based catalysis.

Language: Английский

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Thermocatalytic Conversion of CO₂ to Valuable Products Activated by Noble‐Metal‐Free Metal‐Organic Frameworks

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: May 12, 2023

Thermocatalysis of CO2 into high valuable products is an efficient and green method for mitigating global warming other environmental problems, which Noble-metal-free metal-organic frameworks (MOFs) are one the most promising heterogeneous catalysts thermocatalysis, many excellent researches have been published. Hence, this review focuses on obtained from various conversion reactions catalyzed by noble-metal-free MOFs, such as cyclic carbonates, oxazolidinones, carboxylic acids, N-phenylformamide, methanol, ethanol, methane. We classified these published references according to types products, analyzed methods improving catalytic efficiency MOFs in reaction. The advantages using MOF were also discussed along text. This concludes with future perspectives challenges be addressed potential research directions. believe that will helpful readers attract more scientists join topic conversion.

Language: Английский

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Fluorine-Functionalized NbO-Type {Cu₂}-Organic Framework: Enhanced Catalytic Performance on the Cycloaddition Reaction of CO₂ with Epoxides and Deacetalization-Knoevenagel Condensation

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 61(30), P. 11949 - 11958

Published: July 15, 2022

The high catalytic activity of metal-organic frameworks (MOFs) can be realized by increasing their effective active sites, which prompts us to perform the functionalization on selected linkers introducing a strong Lewis basic group fluorine. Herein, exquisite combination paddle-wheel [Cu2(CO2)4(H2O)] clusters and meticulously designed fluorine-funtionalized tetratopic 2',3'-difluoro-[p-terphenyl]-3,3″,5,5″-tetracarboxylic acid (F-H4ptta) engenders one peculiar nanocaged {Cu2}-organic framework {[Cu2(F-ptta)(H2O)2]·5DMF·2H2O}n (NUC-54), features two types voids (9.8 Å × 17.2 10.1 12.4 Å) shaped 12 [Cu2(COO)4H2O)2] secondary building units, leaving calculated solvent-accessible void volume 60.6%. Because introduction plentifully base sites fluorine groups, activated NUC-54a exhibits excellent performance cycloaddition reaction CO2 with various epoxides under mild conditions. Moreover, expand scope, deacetalization-Knoevenagel condensation reactions benzaldehyde dimethyl acetal malononitrile were performed using heterogenous catalyst NUC-54a. Also, recyclability stability in subsequent tests. Therefore, this work not only puts forward new solution for developing high-efficiency heterogeneous catalysts, but also enriches strategies nanoporous MOFs.

Language: Английский

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Recent progress in host–guest metal–organic frameworks: Construction and emergent properties

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 476, P. 214921 - 214921

Published: Nov. 16, 2022

Language: Английский

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Robust Fluorine-Functionalized {Ln₅}-Organic Frameworks for Excellent Catalytic Performance on Cycloaddition of CO₂ with Epoxides and Knoevenagel Condensation

ACS Applied Materials & Interfaces, Journal Year: 2023, Volume and Issue: 15(29), P. 35052 - 35061

Published: July 12, 2023

Lanthanide-organic frameworks (LnOFs) are a class of promising catalysts on large number organic reactions because the higher coordination Ln3+ ions, inspired by which exploratory preparation cluster-based LnOFs was carried out us. Herein, exquisite combination spindly [Ln5(μ3-OH)6(CO2)6(H2O)6] clusters (abbreviated as {Ln5}) and fluorine-functionalized tetratopic ligand 2',3'-difluoro-[p-terphenyl]-3,3″,5,5″-tetracarboxylic acid (F-H4PTTA) engendered two highly robust isomorphic nanoporous {[Ln5(FPTTA)2(μ3-OH)6(H2O)6](NO3)}n (NUC-61, Ln = Ho Dy). NUC-61 compounds rarely reported {Ln5}-based 3D with nano-caged voids (19 Å × 17 Å), shaped twelve [Ln5(μ3-OH)6(COO)8] eight completely deprotonated F-PTTA4- ligands. Activated NUC-61a characterized plentiful coexisted Lewis acid-base sites open LnIII sites, capped μ3-OH, -F. Judged ideal adsorbed solution theory (IAST), activated NUC-61Ho-a had high CO2/CH4 adsorptive selectivity value 12.7 (CO2/CH4 50/50) 9.1 5/95) at 298 K, could lead to high-purity CH4 (≥99.9996%). Furthermore, catalytic experiments exhibited that NUC-61Ho-a, representative, efficiently catalyze cycloaddition CO2 epoxides well Knoevenagel condensation aldehydes malononitrile. This work proves skeletons chemical stability, heterogeneity, recyclability an excellent bifunctional catalyst for some reactions.

Language: Английский

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Zn-MOF as a Single Catalyst with Dual Lewis Acidic and Basic Reaction Sites for CO₂ Fixation

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(8), P. 3757 - 3768

Published: Feb. 14, 2024

Continuous increase in carbon dioxide (CO2) emissions are causing imbalances the environment, which impact biodiversity and human health. The conversion of CO2 to cyclic carbonates by means metal–organic frameworks (MOFs) as a heterogeneous catalyst is prominent strategy for rectifying this imbalance. Herein, we have developed nitrogen-rich Zn (II) based framework, [Zn(CPMT)(bipy)]n (CPMT = 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole; bipy 4,4′-bipyridine), synthesized via mixed ligand strategy. This Zn-MOF showed high chemical stability both acidic basic conditions, organic solvents long time. On account concurrent presence acid–base active sites strong under abrasive was employed an effective coupling epoxides, atmospheric pressure, mild temperature, neat conditions. shows remarkable activity producing yields epichlorohydrin carbonate (98%) styrene (82%) at 70 °C 24 h reaction time, with turnover numbers (TON) 217 181, respectively. could be reused up seven cycles structural framework integrity. Overall, work demonstrates synthesis novel highly efficient MOF conversion.

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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Combination of dimensional reduction and active site addition strategies for preparing unique {RE₉}-cluster-based MOFs: efficient CO₂ fixation and Knoevenagel condensation

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(7), P. 2071 - 2080

Published: Jan. 1, 2024

A series of 2D {RE 9 }-cluster-based rare-earth MOFs were built by dimensional reduction and active site addition strategies. They exhibit excellent catalytic activity in CO 2 fixation Knoevenagel condensation under mild conditions.

Language: Английский

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Nanocage-Based Tb³⁺-Organic Framework for Efficiently Catalyzing the Cycloaddition Reaction of CO₂ with Epoxides and Knoevenagel Condensation

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 61(39), P. 15558 - 15568

Published: Sept. 16, 2022

The catalytic performance of metal-organic framework (MOF)-based catalysts can be enhanced by increasing their sites, which prompts us to explore the multicore cluster-based skeletons using designed functional ligands. Herein, exquisite combination [Tb4(μ2-OH)2(CO2)8] cluster and 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (H5BDCP) ligand generated a highly robust nanoporous {[Tb4(BDCP)2(μ2-OH)2]·3DMF·5H2O}n (NUC-58), in each four {Tb4} clusters are woven together generate an elliptical nanocage (aperature ca. 12.4 Å). As far as we know, NUC-58 is excellent nanocage-cluster-based {Tb4}-organic with outstanding confined pore environments large specific surface area, high porosity, plentiful coexisting Lewis acid-base sites Tb3+, μ2-OH Npyridine atoms. Performed experiments exhibited that owns better for cycloaddition reactions under mild conditions turnover number frequency. Furthermore, NUC-58, eminent heterogeneous catalyst, enormously boost Knoevenagel condensation reactions. Thus, this work opens path precise design polynuclear metal MOFs catalysis, stability, regenerative behavior.

Language: Английский

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Nanoporous {Co3}-Organic framework for efficiently seperating gases and catalyzing cycloaddition of epoxides with CO2 and Knoevenagel condensation

Journal of Colloid and Interface Science, Journal Year: 2023, Volume and Issue: 656, P. 127 - 136

Published: Nov. 17, 2023

Language: Английский

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