Bifunctional MOFs in Heterogeneous Catalysis

ACS Organic & Inorganic Au, Journal Year: 2023, Volume and Issue: 4(1), P. 59 - 90

Published: Nov. 11, 2023

The ever-increasing landscape of heterogeneous catalysis, pure and applied, utilizes many different catalysts. Academic insights along with industrial adaptations paved the way for growth. In designing a catalyst, it is desirable to have priori knowledge what structure needs be targeted help in achieving goal. When focusing on one cope vast corpus information. overwhelming desire exploit catalysis toward commercial ends irresistible. today's world, requirements developing new catalyst address environmental concerns. well-established catalysts microporous structures (<25 Å), which find use processes. metal–organic framework (MOF) compounds, being pursued vigorously during last two decades, similar microporosity well-defined pores channels. MOFs possess large surface area assemble delicate structural compositional variations either preparation or through postsynthetic modifications (PSMs). MOFs, fact, offer excellent scope as simple Lewis acidic, Brönsted basic, more importantly bifunctional (acidic well basic) agents carrying out catalysis. advances that happened over years biology helped design good biocatalysts. tools techniques (advanced preparative approaches coupled computational insights), other hand, generating interesting inorganic this review, recent employing are presented. doing so, we concentrated developments past decade so.

Language: Английский

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Thermally activated bipyridyl-based Mn-MOFs with Lewis acid–base bifunctional sites for highly efficient catalytic cycloaddition of CO₂ with epoxides and Knoevenagel condensation reactions

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(12), P. 3671 - 3681

Published: Jan. 1, 2023

Metal-organic frameworks (MOFs) have become preferred heterogeneous catalytic materials for many reactions due to their advantages such as porosity and abundant active sites. Here, a 3D Mn-MOF-1 [Mn2(DPP)(H2O)3]·6H2O (DPP = 2,6-di(2,4-dicarboxyphenyl)-4-(pyridine-4-yl)pyridine) was successfully synthesized under solvothermal conditions. This possesses structure constructed by the combination of 1D chain DPP4- ligand features micropore with drum-like shaped channel. Interestingly, can maintain unchanged removal coordinated lattice water molecules, whose activated state (denoted Mn-MOF-1a) contains rich Lewis acid sites (tetra- pentacoordinated Mn2+ ions) base (Npyridine atoms). Furthermore, Mn-MOF-1a shows excellent stability, which be used catalyze CO2 cycloaddition efficiently eco-friendly, solvent-free In addition, synergistic effect resulted in its promising potential Knoevenagel condensation ambient More importantly, catalyst recycled reused without an obvious decrease activity at least 5 reaction cycles. work not only paves way construction acid-base bifunctional MOFs based on pyridyl-based polycarboxylate ligands but also demonstrates that Mn-based hold great promise toward both epoxidation reactions.

Language: Английский

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Coordination Unsaturation and Basic Site-Immobilized Nanochannel in a Chemorobust MOF for 3-Fold-Increased High-Temperature Selectivity and Fixation of CO₂ under Mild Conditions with Nanomolar Recognition of Roxarsone

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(29), P. 11528 - 11540

Published: July 13, 2023

A multifaceted metal-organic framework (MOF) with task-specific site-engineered pores can promise high-temperature and moisture-tolerant capture non-redox fixation of CO2 under mild conditions as well ultrasensitive detection carcinogenic contaminants in water. Herein, we report a pillar-bilayered MOF that holds nanochannel contrasting functionalities for both these sustainable applications improved performance characteristics. The twofold entangled robust exhibits adsorption at elevated temperatures considerable MOF-gas interaction. Interestingly, selectivity unveils nearly 3-fold improvement upon the rise temperature, affording CO2/N2 value 820 313 K, which outperforms many porous adsorbents. Additionally, breakthrough simulation establishes complete separation attests potential this flue gas mixture. Importantly, minor loss during multiple capture-release cycles relative humidity 75% practical usability material. Density functional theory (DFT) not only portrays atomistic level snapshots temperature-triggered inclusion inside microporous vessel alongside role diverse CO2-philic sites but also validates basis N2-phobicity an azo-functionalized linker on such increased selectivity. guest-free further demonstrates recyclable wide epoxide tolerance solvent-free even works atmospheric pressure room temperature. crucial roles high-density acid-base catalysis are supported by control experiments comparing activity unfunctionalized MOF. hydrolytic stability strong luminescence signature benefit aqueous-phase selective fast responsive detrimental roxarsone (ROX) high quenching (7.56 × 104 M-1) very low sensitivity (68 nM). Apart from varying degrees energy-transfer mechanism, fluorosensing ROX is comprehensively in-depth DFT studies manifest alteration energy levels presence organoarsenic compounds depict MOF-analyte supramolecular interactions.

Language: Английский

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A new Eu(III)-based metal-organic framework: synthesis, characterization, fluorescence detection of nitrobenzene and catalytic conversion of CO2

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1302, P. 137504 - 137504

Published: Jan. 5, 2024

Language: Английский

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Ultrahigh Stable Heterometallic InCo-Organic Framework for Efficiently Catalyzing Cycloaddition of CO2 with Epoxides and Knoevenagel condensation

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1318, P. 139223 - 139223

Published: July 6, 2024

Language: Английский

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