Nanoporous {Y₂}-Organic Frameworks for Excellent Catalytic Performance on the Cycloaddition Reaction of Epoxides with CO₂ and Deacetalization–Knoevenagel Condensation

ACS Applied Materials & Interfaces, Год журнала: 2022, Номер 14(16), С. 18589 - 18599

Опубликована: Апрель 13, 2022

Stable metal-organic frameworks containing periodically arranged nanosized pores and active Lewis acid-base sites are considered as ideal candidates for efficient heterogeneous catalysis. Herein, the exquisite combination of [Y2(CO2)7(H2O)2] cluster (abbreviated {Y2}) multifunctional linker 2,4,6-tri(2,4-dicarboxyphenyl)pyridine (H6TDP) led to a nanoporous framework {[Y2(TDP)(H2O)2]·5H2O·4DMF}n (NUC-53, NUC = North University China), which is rarely reported binuclear three-dimensional (3D) with hierarchical tetragonal-microporous (0.78 nm) octagonal-nanoporous (1.75 channels. The inner walls these channels aligned by {Y2} clusters plentifully coexisted YIII ions Npyridine atoms. Furthermore, NUC-53 has quite large void volume ∼65.2%, significantly higher than most documented 3D rare-earth-based MOFs. performed catalytic experiments exhibited that activated showed high activity on cycloaddition reactions CO2 styrene oxide under mild conditions excellent turnover number (TON: 1980) frequency (TOF: 495 h-1). Moreover, deacetalization-Knoevenagel condensation benzaldehyde dimethyl acetal malononitrile could be efficiently prompted catalyst NUC-53. These findings not only pave way construction MOF based rare-earth variety activities but also provide some new insights into mechanism.

Язык: Английский

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Highly Robust {Ln₄}-Organic Frameworks (Ln = Ho, Yb) for Excellent Catalytic Performance on Cycloaddition Reaction of Epoxides with CO₂ and Knoevenagel Condensation

ACS Catalysis, Год журнала: 2021, Номер 11(24), С. 14916 - 14925

Опубликована: Ноя. 30, 2021

Due to the high electron charge, large ion radius, and plentiful outer hybrid orbitals of LnIII cations, microporous Ln-MOFs can be used as Lewis acidic catalysts with catalytic activity for a variety organic reactions, which prompts us explore cluster-based nanoporous by employing structure-oriented ligands. Herein, exquisite combination coplanar [Ln4(μ3–OH)2(μ2–HCO2)(H2O)2] clusters (abbreviated {Ln4}) multifunctional ligand 2,6-bis(2,4- dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (H5BDCP) led two isomorphic frameworks {(Me2NH2)[Yb4(BDCP)2(μ3–OH)2(μ2–HCO2)(H2O)2]·5DMF·H2O}n (NUC-38Yb) {(Me2NH2)[Ho4(BDCP)2(μ3–OH)2(μ2– HCO2)(H2O)2]·6DMF·3H2O}n (NUC-38Ho). To best our knowledge, NUC-38Ho NUC-38Yb are rarely reported {Ln4}-based three-dimensional (3D) embedded hierarchical triangular-microporous hexagonal-nanoporous channels, shaped six rows {Ln4} characterized coexisting acid–base sites on inner wall including open sites, Npyridine atoms, μ3–OH, μ2–HCO2. Catalytic experiments performed using representative exhibited that possessed cycloaddition reactions epoxides CO2 under mild conditions, ascribed its structural advantages nanoscale rich bifunctional active surface areas, chemical stability. Moreover, NUC-38Yb, heterogeneous catalyst, could greatly accelerate Knoevenagel condensation aldehydes malononitrile. Hence, this work paves way construction functional Ln-cluster-based metal–organic (MOFs) elaborately designing ligands transnormal connection modes.

Язык: Английский

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Surface science approach to the heterogeneous cycloaddition of CO2 to epoxides catalyzed by site-isolated metal complexes and single atoms: a review

Green Chemical Engineering, Год журнала: 2022, Номер 3(3), С. 210 - 227

Опубликована: Фев. 5, 2022

The cycloaddition of CO2 to epoxides afford cyclic organic carbonates is an increasingly relevant non-reductive strategy convert useful products able serve as high-boiling solvents, chemical intermediates, and monomers for the preparation more sustainable polymers. development efficient robust heterogeneous catalysts such transformation is, therefore, crucial can be carried out by several strategies that often require sophisticated and/or expensive networks, linkers, or compounds. A different approach CO2-epoxide coupling applying surface science methodologies graft molecular fragments single atoms on various supports leading well-defined active sites. In this context, organometallic chemistry (SOMC), along with comparable methodologies, a valuable efficient, single-site Lewis acids target reaction metal oxides, whereas, other grafting applied prepare analogous kinds surfaces. Finally, we discuss very recent advances in application atom towards highly epoxides. Overall, show prepared facile hold significant potential future synthesis from CO2.

Язык: 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, Год журнала: 2023, Номер 15(29), С. 35052 - 35061

Опубликована: Июль 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.

Язык: Английский

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Deep eutectic solvents as a versatile platform toward CO₂ capture and utilization

Green Chemistry, Год журнала: 2023, Номер 25(21), С. 8328 - 8348

Опубликована: Янв. 1, 2023

Deep eutectic solvents provide a versatile platform for CO 2 capture and subsequent conversion into value-added chemicals.

Язык: Английский

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Direct Air Capture and Integrated Conversion of Carbon Dioxide into Cyclic Carbonates with Basic Organic Salts

ACS Sustainable Chemistry & Engineering, Год журнала: 2023, Номер 11(26), С. 9613 - 9619

Опубликована: Июнь 23, 2023

Direct air capture and integrated conversion is a very attractive strategy to reduce CO2 concentration in the atmosphere. However, existing capturing processes are technologically challenging due costs of low CO2. The efficient valorization captured could help overcome many techno-economic limitations. Here, we present novel economical methodology for direct that able efficiently convert from into cyclic carbonates. new approach employs commercially available basic ionic liquids, works without need sophisticated expensive co-catalysts or sorbents under mild reaction conditions. atmospheric was by IL solution (0.98 molCO2/molIL) and, subsequently, completely converted carbonates using epoxides halohydrins potentially derived biomass as substrates. A mechanism evaluated, which helped identify relevant intermediates based on halohydrins, consequently, 100% selectivity obtained methodology.

Язык: Английский

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Cycloaddition of CO₂ to epoxides “around water”: a strategy to apply and recycle efficient water-soluble bio-based organocatalysts in biphasic media

Green Chemistry, Год журнала: 2023, Номер 25(11), С. 4336 - 4349

Опубликована: Янв. 1, 2023

A biphasic reaction approach is presented for the cycloaddition of CO 2 to epoxides where catalyst dissolved in water droplets and occurs at aqueous–organic interface allowing easy recycling by decantation.

Язык: 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, Год журнала: 2024, Номер 11(7), С. 2071 - 2080

Опубликована: Янв. 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.

Язык: Английский

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Deep eutectic solvents applications aligned to 2030 United Nations Agenda for Sustainable Development

Chemical Engineering and Processing - Process Intensification, Год журнала: 2024, Номер 199, С. 109751 - 109751

Опубликована: Март 15, 2024

Язык: Английский

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Tuning functional ionic deep eutectic solvents as green sorbents and catalysts for highly efficient capture and transformation of CO2 to quinazoline-2,4(1H,3H)-dione and its derivatives

Chemical Engineering Journal, Год журнала: 2023, Номер 469, С. 143991 - 143991

Опубликована: Июнь 8, 2023

Язык: Английский

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