Ligand-Induced Activation of Single-Atom Palladium Heterogeneous Catalysts for Cross-Coupling Reactions

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Single-atom heterogeneous catalysts (SACs) are potential, recoverable alternatives to soluble organometallic complexes for cross-coupling reactions in fine-chemical synthesis. When developing SACs these applications, it is often expected that the need ligands, which essential catalysts, can be bypassed. Contrary that, ligands remain almost always required palladium atoms stabilized on commonly used functionalized carbon and nitride supports, as otherwise show limited activity. Despite this, ligand optimization has received little attention, their role activating poorly understood. Here, we explore impact of structurally diverse phosphine performance nitrogen-doped supported single-atoms (Pd1@NC) Sonogashira–Hagihara (SH) reaction, using X-ray absorption spectroscopy density functional theory simulations rationalize observed trends. Compared ligand-free SAC, SH activity enhanced all ligand-assisted systems, with reactivity varying by up 8 orders magnitude depending choice. Distinct trends emerge based free volume class. Unlike molecular electronic effects less significant due modulating influence support. Instead, SAC-ligand systems governed a balance between deformation energy during coordination metal centers, resulting accessibility reagents. These findings offer key insights into optimizing Pd-SACs leveraging activate centers tailor 3D environment.

Language: Английский

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Alginate-aminoclay/CuO nanocomposite beads: A sustainable and green approach for catalytic reduction of toxic nitroaromatic compounds

Journal of environmental chemical engineering, Journal Year: 2025, Volume and Issue: unknown, P. 115398 - 115398

Published: Jan. 1, 2025

Language: Английский

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Processing Techniques for Bio-based Products in the Global South

Published: Jan. 1, 2025

Language: Английский

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Bio‐Inspired Synthesis and Photocatalytic Applications of α‐Fe₂O₃@ZnO Nanobinary Using Laurus nobilis Leaf Extract: Efficient for Anionic and Cationic Dye Degradation With Reusability Studies

Applied Organometallic Chemistry, Journal Year: 2025, Volume and Issue: 39(4)

Published: March 11, 2025

ABSTRACT This study investigates the sustainable synthesis and applications of α‐Fe₂O₃@ZnO nanocomposites derived using Laurus nobilis leaf extract as a natural reducing agent, promoting eco‐friendly material development for environmental remediation. XRD analysis confirmed formation nanocomposite with crystallite size 21.48 nm, while SEM revealed porous structure uniformly distributed particles ranging from 20 to 50 nm. FTIR spectroscopy identified characteristic Fe‐O Zn‐O bonds, ensuring nanocomposite's purity. Optical showed direct indirect bandgap energies 2.80 1.16 eV, respectively, highlighting its excellent optical properties. The demonstrated remarkable photocatalytic efficiency, achieving 96.3% degradation Brilliant Cresyl Blue (BCB) dye 95.88% Rose Bengal (RB) within 120 min under sunlight irradiation. followed first‐order kinetics, rate constants 0.0241 −1 BCB 0.01875 RB. exhibited reusability, maintaining 93.5% efficiency after five cycles, structural stability throughout repeated use. These results underscore multifunctional potential green‐synthesized dye‐contaminated wastewater treatment, contributing technologies.

Language: Английский

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Micelle-Enabled In Situ Surface Modification of Porous Organic Polymers: Formation of Heterogeneous Microcolony for Efficient Suzuki–Miyaura Coupling in Water

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

Synthesis of water-stable and dispersible heterogeneous catalysts having high catalytic efficiency is more challenging compared with homogeneous due to their low dispersity, activity, spatial confinement active centers in bulk water. Herein, we are describing systematic studies for the development microconfinement participation aqueous micelles via temporal surface modification porous organic polymer derived from phosphine ligands. Detailed investigations using various techniques such as transmission electron microscopy (TEM), scanning (SEM), tensiometry, confocal laser (CLSM), fluorescence lifetime imaging (FLIM) have been used understand role micelles, reagents, materials generation microcolonies Two-color crossover experiments also performed exchange reagents or vice versa, materials. The surfactant-modified ligation stabilization palladium, which was evidenced by high-resolution (HR-TEM), high-angle annular dark-field (HAADF-STEM), X-ray photoelectron spectroscopy (XPS) analysis. act confined space catalysis water showcasing Suzuki-Miyaura cross-coupling reaction a ppm level Pd loading under mild conditions. catalyst found be recyclable five cycles; easy scale-up C-C couplings additional features. Moreover, these data provide an opportunity revising models micellar systems that underpin sustainable

Language: Английский

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Ionic Liquid-Assisted Approaches in the Synthesis of Nitrogen-Containing Heterocycles: A Focus on 3- to 6-Membered Rings

Journal of Ionic Liquids, Journal Year: 2025, Volume and Issue: unknown, P. 100146 - 100146

Published: March 1, 2025

Language: Английский

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Green Approach for Pd-Catalyzed C–N Bond Formation with Weak Nitrogen Nucleophiles Using Saponin-Based Micellar Catalysis: Arylation of Anilines, Amides, Carbamates, Ureas, and Sulfonamides

ACS Sustainable Chemistry & Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: April 11, 2025

Language: Английский

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Palladium Complex Grafted on PEG-Based Amphiphilic Polymers as ppm Level Micellar Catalysts for Suzuki–Miyaura Coupling in Water

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

A series of bisphosphine-grafted amphiphilic polymers based on polyethylene glycol-poly(vinylethylene glycol) (PEG-PVEG) copolymers have been synthesized by using allylic etherification polymerization as a pivotal step. Self-assembling the palladium complexes obtained into spherical micelles has investigated UV-vis, DLS and TEM analysis. The outstanding catalytic performance present micellar catalyst evidenced in aqueous Suzuki-Miyaura coupling reaction, achieving remarkable efficiency even at low loading 100 ppm within 2 h.

Language: Английский

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Sustainable and Scalable Amidations in Water Using Continuous Slurry-Flow Technology

ACS Sustainable Chemistry & Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Language: Английский

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N‐Halosuccinimide‐CeCl3 Transient Charge‐Transfer Complexes as Semi Heterogeneous Photocatalyst in Cyclization of N‐Propargylamides

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(57)

Published: Aug. 1, 2024

In this work, we used photoinert anhydrous cerium(III) chloride, to form a transient charge-transfer (CT) complex with NXS (N-bromosuccinimide or NBS and N-iodosuccinimide NIS) in acetonitrile. These CT complexes acted as semi-heterogeneous photocatalyst. allowed the Ce(III) ions absorb light, turning them into strong electron donors that transferred electrons NXS. This created halide radicals from radical anions, helping turn N-propargylamides oxazole aldehydes. Experiments DMPO spin-trapping showed radical-based mechanism followed single transfer (SET) pathway. Notably, CeCl

Language: Английский

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