Bifunctional two-dimensional copper-organic framework for high catalytic performance on cycloaddition of CO2 with epoxides and deacetalization-Knoevenagel condensation

Journal of Molecular Structure, Год журнала: 2024, Номер 1306, С. 137849 - 137849

Опубликована: Фев. 22, 2024

Язык: Английский

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Robust Nitro-Functionalized {Zn₃}-Organic Framework for Excellent Catalytic Performance on Cycloaddition Reaction of CO₂ with Epoxides and Knoevenagel Condensation

Crystal Growth & Design, Год журнала: 2024, Номер 24(8), С. 3473 - 3482

Опубликована: Апрель 8, 2024

Adjusting the Lewis acid–base sites in MOF-based catalysts to meet demand for catalytic CO2 chemical fixation is a huge challenge. Herein, highly robust rectilinear {Zn3}-based metal–organic framework of {[Zn3(TNTNB)2(4,4′-bip)(H2O)2]·5DMF·9H2O}n (NUC-80) was generalized from solvothermal condition (H3TNTNB = 1,3,5-tri(3-nitro-4-carboxyphenyl)-2,4,6-trinitrobenzene, 4,4′-bip 4,4′-bipyridine). Activated NUC-80a not only owns large void volume (58%) and two kinds solvent-accessible channels: rhombic-like (ca. 14.24 × 14.57 Å) along axis rectangular-like 11.72 14.48 b axis, but also functionalized by rich metal plentiful nitro groups on its inner surface. Performed experiments confirmed that could efficiently catalyze cycloaddition reaction with epoxides Knoevenagel condensations aldehydes malononitrile under mild conditions high turnover frequency (TOF). Hence, this work provides nitro-functionalized cluster-based nanoporous wide range potential applications such as catalysis, gas adsorption, separation.

Язык: Английский

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Structure regulation and catalytic performance of amine-functionalized zeolitic imidazolate frameworks for CO2 cycloaddition

Separation and Purification Technology, Год журнала: 2024, Номер 348, С. 127465 - 127465

Опубликована: Апрель 16, 2024

Язык: Английский

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Revealing the roles of the dual active-sites on a polyoxometalate-based metal–organic framework in catalyzing Knoevenagel condensations

Applied Surface Science, Год журнала: 2024, Номер 654, С. 159459 - 159459

Опубликована: Янв. 20, 2024

Язык: 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, Год журнала: 2024, Номер 1318, С. 139223 - 139223

Опубликована: Июль 6, 2024

Язык: Английский

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High‐Entropy Lanthanide‐Organic Framework as an Efficient Heterogeneous Catalyst for Cycloaddition of CO2 with Epoxides and Knoevenagel Condensation

Chemistry - A European Journal, Год журнала: 2024, Номер 30(39)

Опубликована: Май 10, 2024

Multimetallic synergistic effects have the potential to improve CO

Язык: Английский

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Engineering the Activity and Stability of the Zn-MOF Catalyst via the Interaction of Doped Zr with Zn

Inorganic Chemistry, Год журнала: 2024, Номер 63(22), С. 10346 - 10357

Опубликована: Май 17, 2024

Metallic atoms within metal–organic framework (MOF) materials exhibit a distinctive and adaptable coordination structure. The three-dimensional (3D) pore configuration of MOFs enables the complete exposure metal active sites, rendering them prevalent in various catalytic reactions. In this study, zinc (Zn) Zn-based MOF materials, characterized by an abundance valence electrons, are utilized for transesterification dimethyl carbonate (DMC). Additionally, introduction zirconium (Zr) effectively addresses susceptibility MOFs' crystal structure to dissolution organic solvents. formulated catalyst, Zn-10%Zr-MOF(300), demonstrates remarkable performance with 91.5% DMC selectivity, 61.9% propylene (PC) conversion, 56.6% yield. Impressively, catalyst maintains its high over five cycles. Results indicate that Zr interacts Zn, forming new bonds enhancing stability. Moreover, electron transfer intensifies alkalinity Zn atoms, overall performance. This research informs development heterogeneous catalysts broadens application scope catalysts.

Язык: Английский

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Temperature-Variant CO₂ Separation in Entangled Meta-Organic Framework with Carboxamide Functionality-Fueled Atmospheric-Pressure Cycloaddition and Size-Exclusive Tandem Knoevenagel Condensation

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(42), С. 15432 - 15446

Опубликована: Окт. 7, 2024

The pressing need to lower atmospheric carbon dioxide (CO2) concentration has captivated global focus on point-source capture and transformation of this greenhouse gas chemicals. Purpose-driven pore-functionality engineering in metal–organic frameworks (MOFs) can lead high-temperature humid-condition adsorption efficient cycloaddition CO2 further assist achieving unconventional methodologies for sustainable tandem catalysis. Herein, we develop a [Zn2(COO)4N4] building unit-containing chemo-robust framework with carboxamide functionality, free oxygen atoms, π-electron-rich moieties affixed one-dimensional channels. This 3-fold entangled MOF exhibits strong framework–gas interactions unveils variable-temperature recurrent capture–release cycles even under 75% relative humidity. Interestingly, the CO2/N2 selectivity shows remarkable 82% increase an temperature from 273 K (79) 313 (143), which overpowers several porous adsorbents validates potential flue separation. microporous catalyzes solvent-free recyclable various epoxides pressure. In contrast classical Lewis acid-mediated reaction, controlled experiments, including performance comparison urea functionality-truncated isostructural corroborate unique two-point hydrogen bonding-mediated pathway. suitably oriented moiety within channels acts as bond donor (HBD) site deacetalization–Knoevenagel condensation reaction >99% conversion solvent-less mild conditions 4 h. cooperative role acid–base dual sites substrate activation is comprehensively supported by studies using external additives, fluoro-titration-derived interactions, unfunctionalized framework. To best our knowledge, one-pot acetals having larger molecular dimensions exhibit poor formation α,β-unsaturated dicyanides, demonstrate pore-fitting-mediated size-exclusive

Язык: Английский

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Mechanochemically Driven C–C Bond Formation via Cu-Complex-Functionalized Polyoxoniobate under Solvent-Free Conditions

Crystal Growth & Design, Год журнала: 2025, Номер 25(5), С. 1636 - 1643

Опубликована: Фев. 19, 2025

Developing a mechanochemical, solvent-free approach for forming C–C bonds in place of traditional solvent-based synthesis is significant green chemistry. Herein, novel Cu-complex-functionalized polyoxoniobate-based hybrid material [Cu(tpy)2]{[Cu(tpy)(H2O)]2[Nb10O28]}·5.5H2O (1, tpy = 2,2′:6′,2″-terpyridine) successfully synthesized and thoroughly characterized. 1 displays excellent thermal solvent stability highly mechanical force tolerant. Catalytic studies reveal that can catalyze the Knoevenagel condensations series aromatic aldehydes with malononitrile to build bond compounds under mechanochemical ball milling conditions. The catalytic system conducted no additional heating, lower oscillating frequency, without solvent. remarkable performance catalyst be attributed two factors: one sufficient contact between reagents facilitated by force, as well preactivated it; other synergistic effect Lewis acid–base sites (Cu2+ [Nb10O28]6–) within catalyst. exhibits outstanding recyclability applied gram-scale reactions. To best our knowledge, this work represents first example mechanochemically driven organic transformation using polyoxometalate-based

Язык: Английский

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A Precise Preparation Strategy for 2D Nanoporous Thulium-Organic Framework: High Catalytic Performance in CO₂-Epoxide Cycloaddition and Knoevenagel Condensation

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 22, 2025

Efficient conversion of carbon dioxide (CO2) into high-value chemicals is viewed as one the most promising approaches for solving problem an energy shortage and serious environment pollution. However, design synthesis confined multifunctional catalysts with in situ engineered task-specific sites nanoporous environments remain a complex challenging task due to lack in-depth understanding their structure reaction mechanism. Herein, we report highly robust 2D framework {[Tm(HFPDC)(DMF)2]·DMF·H2O}n (NUC-120) (H4FPDC = 4,4′-(4-(4-fluorophenyl)pyridine-2,6-diyl)diisophthalic acid). The thermally activated host [Tm(HFPDC)]n (NUC-120a) has following two merits: (i) structure, (ii) massive quantity functional sites. Moreover, NUC-120 NUC-120a display high thermal chemical stability, which have been proved by TGA soaking experiments acid–base water organic solvents. Catalytic that NUC-120a, presence n-Bu4NBr cocatalyst could efficiently catalyze coupling CO2 epoxides under comparatively mild conditions. Furthermore, also displays catalytic performance Knoevenagel condensation reactions aldehydes malononitrile, should be because coexisting Lewis acidic basic can separately activate aldehyde malononitrile molecules. Thereby, this work further provides insight desired materials generated using existing suitable secondary building units (SBUs) meticulously regulating growth environments.

Язык: Английский

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