Polyoxometalate‐Cyclodextrin‐Based Cluster‐Organic Supramolecular Framework for Polysulfide Conversion and Guest–Host Recognition in Lithium‐sulfur Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(36)

Published: July 19, 2023

Developing polyoxometalate-cyclodextrin cluster-organic supramolecular framework (POM-CD-COSF) still remains challenging due to an extremely difficult task in rationally interconnecting two dissimilar building blocks. Here we report unprecedented POM-CD-COSF crystalline structure produced through the self-assembly process of a Krebs-type POM, [Zn2 (WO2 )2 (SbW9 O33 ]10- , and β-CD units. The as-prepared POM-CD-COSF-based battery separator can be applied as lightweight barrier (approximately 0.3 mg cm-2 ) mitigate polysulfide shuttle effect lithium-sulfur batteries. designed Li-S batteries equipped with modified exhibit remarkable electrochemical performance, attributed fast Li+ diffusion channel β-CD, efficient polysulfide-capture ability by dynamic host-guest interaction improved sulfur redox kinetics bidirectional catalysis POM cluster. This research provides broad perspective for development multifunctional frameworks their applications

Language: Английский

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Two Different Three-Dimensional Uranium-Containing Polymolybdates Based on Zn(II) for the Heterogeneous Catalytic Construction of C–N Bond

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(19), P. 8919 - 8924

Published: May 3, 2024

The introduction of transition metal (TM) ions into polyoxometalates (POMs) cannot only bring about interesting structural diversities but also enable changes in properties. However, TM-containing Silverton-type polyoxomolybdates are still lacking terms diversity and application development. Herein, two Zn(II)-containing {UMo12O42}-based polyoxomolybdates, H1.89Na4.11(H2O)9Zn[UMo12O42]·4.5H2O (Zn-1) H1.8Na4.2(H2O)12Zn[UMo12O42] (Zn-2) were hydrothermally synthesized, demonstrating a practical strategy to assembly POMs. Zn-1 is proven be an excellent recyclable heterogeneous catalyst cross-dehydrogenation coupling 1,4-naphthoquinones with amines reactions, series 2-amino-1,4-naphthoquinones potential medicinal value have been constructed.

Language: Английский

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Highly-stable Silverton-type U^IV-containing polyoxomolybdate frameworks for the heterogeneous catalytic synthesis of quinazolinones

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(11), P. 6454 - 6460

Published: Jan. 1, 2024

The first series of Silverton {UMo 12 O 40 }-based polyoxomolybdates linked by Fe II , Co and Ni were synthesized characterized. They exhibited excellent stabilities used as heterogeneous catalysts for the synthesis quinazolinones.

Language: Английский

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New two fold interpenetrating 3D polyoxovanadate-based metal–organic framework as bifunctional catalyst for the removal of 2-chloroethyl ethyl sulfide and phenolic compounds

Polyoxometalates, Journal Year: 2024, Volume and Issue: 3(3), P. 9140061 - 9140061

Published: Feb. 19, 2024

The design and synthesis of a bifunctional catalyst to tackle environmental pollution caused by 2-chloroethyl ethyl sulfide (CEES) phenolic compounds is meaningful. In this study, new three-dimensional (3D) polyoxovanadate (POV)-based metal–organic framework, [Co(L)(V₄O₁₂)_0.5(H₂O)]·2H₂O (1; L = N,N'-bis(3-methylpyridin-3-yl)-2,6-naphthalenediamide), was synthesized under hydrothermal conditions. 1 characterized using single-crystal X-ray diffraction analysis, infrared spectroscopy, powder diffraction. Structural analysis shows that the [V₄O₁₂]^4– clusters pairs Co²⁺ cations are alternately connected form one-dimensional inorganic chain, eventually generating 3D (4,4)-connected framework through expansion L, which exhibits two fold interpenetration array. As catalyst, satisfactory catalytic properties for selective oxidation corresponding sulfoxide, with an effective conversion > 99% selectivity 97%. Furthermore, excellent photocatalytic degradation activity toward phenol, 2-chlorophenol, m-cresol visible light. efficiencies were above 92.6% 140 min. reaction kinetics, mechanisms photodegradation, recycling capability phenol also investigated in detail.

Language: Английский

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Conjugated organic component-functionalized hourglass-type phosphomolybdates for visible-light photocatalytic Cr(VI) reduction in wide pH range

Rare Metals, Journal Year: 2023, Volume and Issue: 42(11), P. 3638 - 3650

Published: Sept. 29, 2023

Language: Английский

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Polyoxometalate catalysts for the synthesis of N-heterocycles

Polyoxometalates, Journal Year: 2023, Volume and Issue: 3(1), P. 9140048 - 9140048

Published: Nov. 30, 2023

N-heterocycle compounds are the crucial scaffolds present in natural products, synthetic molecules, agricultural chemicals, and pharmaceuticals. Hence, development of green catalytic systems for constructing N-heterocycles has been a focused topic organic synthesis industrial catalysis. Polyoxometalates (POMs) polynuclear metal–oxygen clusters with structural diversity physicochemical properties. POMs possess advantageous properties such as adjustable acidity, redox properties, high thermal stability, non-toxic nature. Therefore, have widely investigated their application hold great potential applications. In this review, we summarized recent progress (mainly from 2010 to 2023) catalyzed by heteropolyacids (HPAs), modified HPA catalysts, transition metal-modified POMs. The synthesized include pyrroles, indoles, pyridines, benzodiazepines, among others. Furthermore, prospects POMs-based were also proposed.

Language: Английский

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Atomically precise Au nanoclusters for electrochemical hydrogen evolution catalysis: Progress and perspectives

Polyoxometalates, Journal Year: 2023, Volume and Issue: 2(4), P. 9140031 - 9140031

Published: Aug. 2, 2023

Hydrogen evolution reaction (HER) is a vital step for water electrolysis toward H₂ production, but the conventional nanocatalysts lack uniform size, composition, structure, and chemical coordination environment hence making it extremely challenging to establish unambiguous structure-performance relationship. Owing ultrasmall definitive well-defined at atomic level, atomically precise Au nanoclusters can serve as model catalysts improve knowledge gap between structure catalytic properties. This review first explains significance fundamental mechanism of HER, highlights unique advantages employing catalysts. Subsequently, recent progress including promote catalyze Au-alloy HER discussed, with focus on elaborating With some explicit examples, key factors that affect performance not limited electronic interaction, interfacial effect, size charge state, ligand metal core single atom doping, geometric configuration effect are analyzed. Finally, current critical challenges future perspectives discussed. We hope this shed light designing efficient stable coinage nanocluster-based catalyst electrochemical production beyond.

Language: Английский

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Polyoxometalates based nanocomposites for bioapplications

Rare Metals, Journal Year: 2023, Volume and Issue: 42(11), P. 3570 - 3600

Published: Oct. 3, 2023

Language: Английский

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Reduced phosphomolybdate as photoassisted electrochemical crystalline sensor for trace Cr(VI) detection

Polyoxometalates, Journal Year: 2024, Volume and Issue: 3(4), P. 9140065 - 9140065

Published: April 25, 2024

Sensitive and efficient detection technology for trace toxic hexavalent chromium (Cr(VI)) in water is urgent. Herein, an hourglass-type phosphomolybdate-based metal-organic network was hydrothermally synthesized with formula of [Na_0.5Cu_5.5(H₂O)₂(btmbp)₄][Mn(H₂O)₃]₂{Mn[H₆P₄Mo₆O₃₁]₂}·10H₂O (1, btmbp= 4,4′-bis((1H-1,2,4-triazol-1-yl)methyl)biphenyl). Crystal consists ladder-like two-dimensional layer-like structure constructed by the vertical connections 1-D [Na_0.5Cu_5.5(H₂O)₂(btmbp)₄]⁶⁺ chains inorganic polyanionic chains. Compound 1 exhibits good excellent electrochemical property wide light absorption that can absorb visible to accelerate electron transfer redox process. When serving as a photo-assisted (PAEC) sensor Cr(VI) detection, compound high sensitivity 330.5 μA·μM^-1 low limit 0.95 nM (98.79 ppt) along anti-interference ability PAEC stability. These results are superior most reported POM-based sensors, even comparable noble-metal far satisfying WHO standards concentration drinking water. This work provides new promising photoelectrochemical material actual environmental pollutant monitoring.

Language: Английский

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Tetra-Ln³⁺-Implanted Tellurotungstates Covalently Modified by dl-Malic Acid: Proton Conduction and Photochromic Properties

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(19), P. 8791 - 8798

Published: April 30, 2024

Three unique dl-malic acid covalently modified tetra-Ln3+-implanted tellurotungstates [H2(CH3)2]9NaH9[Ln4(H2O)14W6O13(OH)5(Mal)2(B-α-TeW9O33)4]·48H2O [Ln = La3+ (1), Ce3+ (2), Pr3+ (3); H3Mal acid] were fabricated by reacting Na2TeO3, Na2WO4·2H2O, Mal, and LnCl3·6H2O with dimethylamine hydrochloride in an aqueous solution. The most prominent architectural feature of these compounds is the covalent connection mode organic ligand a polyoxometallate backbone, which relatively rare realm polyoxotungstates. tetrameric polyanion can be deemed as four [TeW9O33]8– fragments fused together via intriguing hexanuclearity [W6O13(OH)5(Mal)2Ln4(H2O)14]13+ cluster. Impedance measurements manifest that all three complexes display splendid proton conduction properties, exceptional conductivity for 2 up to 2.48 × 10–2 S·cm–1 under 85 °C 95% relative humidity. Moreover, 1 3 exhibited fast reversible photochromic properties allochroic half-life periods t1/2 1.046 0.544 min, respectively.

Language: Английский

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