A Bicadmium-Substituted Polyoxometalate Network Based on a Vanadosilicate Cluster for the Selective Oxidation of Styrene to Benzaldehyde

Zhou, Tong; Zhang, Jie; Ma, Yuanyuan; Gao, Xiaoru; Xue, Qihui; Gao, Yuanzhe; Han, Zhangang

doi:10.1021/acs.inorgchem.0c00072

Cited by 16 publications

(6 citation statements)

References 38 publications

(51 reference statements)

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“…Vanadium-based polyoxometalates have been extensively used as green heterogeneous catalysts with high catalytic activity for selective oxidation of styrene to benzaldehyde (Zhou et al, 2020), benzene to PhOH (Li et al, 2020), and mono-substituted benzene to p-PhOH (Kamata et al, 2012). Kirillov and Shul'pin (2013) established a variety of vanadium complexes to catalyze aerobic and/or H 2 O 2 hydroxylation of benzene to phenol and toluene to a mixture of cresols in CH 3 CN.…”

Section: The Mixed Valence Sites Ofmentioning

confidence: 99%

Selective Oxidation of Simple Aromatics Catalyzed by Nano-Biomimetic Metal Oxide Catalysts: A Mini Review

et al. 2020

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The process of selective oxy-functionalization of hydrocarbons using peroxide, O 3 , H 2 O 2 , O 2 , and transition metals can be carried out by the reactive oxygen species such as hydroxyl/hydroperoxyl radical and/or metal oxygenated species generated in the catalytic reaction. Thus, a variety of mechanisms have been proposed for the selective catalytic oxidation of various hydrocarbons including light alkanes, olefins, and simple aromatics by the biological metalloproteins and their biomimetics either in their homogeneous or heterogeneous platforms. Most studies involving these metalloproteins are Fe or Cu monooxygenases. The pathways carried out by these metalloenzymes in the oxidation of C-H bonds invoke either radical reaction mechanisms including Fenton's chemistry and hydrogen atom transfer followed by radical rebound reaction mechanism or electrophilic oxygenation/O-atom transfer by metal-oxygen species. In this review, we discuss the metal oxide nano-catalysts obtained from metal salts/molecular precursors (M = Cu, Fe, and V) that can easily form in situ through the oxidation of substrates using H 2 O 2(aq) in CH 3 CN, and be facilely separated from the reaction mixtures as well as recycled for several times with comparable catalytic efficiency for the highly selective conversion from hydrocarbons including aromatics to oxygenates. The mechanistic insights revealed from the oxy-functionalization of simple aromatics mediated by the novel biomimetic metal oxide materials can pave the way toward developing facile, cost-effective, and highly efficient nano-catalysts for the selective partial oxidation of simple aromatics.

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Section: The Mixed Valence Sites Ofmentioning

confidence: 99%

Selective Oxidation of Simple Aromatics Catalyzed by Nano-Biomimetic Metal Oxide Catalysts: A Mini Review

et al. 2020

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“…Polyoxovanadates (POVs), which are an important branch of the polyoxometallate (POM) family, have received widespread attention in self-assembled synthesis to build multifunctional materials owing to various polyhedral fragments and versatile applications in the fields of supramolecular materials, batteries, catalysis, photooxidation, chiral separation, molecular capsules, biomedical activities, and so forth. − A valid method for the construction of POV-based hybrids is to use POVs as inorganic building blocks and 3d/4f metal–organic complexes as secondary building units to explore functionalized POV-based bimetallic materials through one-pot reaction, − which displays strengths and multifunctionality stemmed from both fragments of POVs and transition metal–organic ligand units. The structure of {V x O y } n − ranges from a simple [VO 4 ] 3– tetrahedron to polymerization units ([V 2 O 7 ] 4– , [V 3 O 9 ] 3– , [V 4 O 12 ] 4– , [V 6 O 18 ] 6– , and [V 10 O 28 ] 6– ) owing to different VO n ( n = 4, 5, 6) polyhedral fragments.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical Studies on Two Dual-Functional Organic–Inorganic Hybrids Based on [V₄O₁₂]^4– Clusters

Zhou,

Zhao,

et al. 2023

Crystal Growth & Design

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Two new bimetallic organic−inorganic hybrids based on [V 4 O 12 ] 4− polyanion, [Cu(dpy)(V 2 O 6 )]•H 2 O (1) and [Cu 2 (tpy) 2 (V 4 O 12 )] (2) [dpy = 2,6-di(pyrazol-1-yl) pyrazine; tpy = 4′-(pyrrol-3-yl)-2,2′:6′,2″-terpyridine], were synthesized under gentle solvothermal conditions. Hybrid 1 has a 1D {−V 4 O 12 − Cu 2 −V 4 O 12 } n circle-connecting-circle chain with [V 4 O 12 ] 4− clusters and [Cu(dpy)] 2+ fragments, and hybrid 2 possesses a discrete structure assembled from [Cu 2 (tpy)] 4+ motifs and [V 4 O 12 ] 4− clusters.We studied dual-functional electrocatalytic activities of the two hybrids for nitrite reduction and oxidation of ascorbic acid. Hybrid 1 shows superior electrocatalytic activity toward oxidation−reduction reactions with electrocatalytic efficiencies of 680 and 128%, respectively. Also, density functional theory calculations including the molecular electrostatic potential and the frontier molecular orbital were adopted to study the electron structure and charge distribution.

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“…In compound 1, the Co1 center adopts a hexa-coordinated distorted octahedral geometry, which is defined by three nitrogen donors from three ttb ligands and three oxygen atoms derived from three coordinated water molecules (Figure S1b). The bond lengths of Co−N/O range from 2.007 (13) S3). Compound 2 crystallizes in the monoclinic P2 1 /n space group.…”

Section: Introductionmentioning

confidence: 99%

“…Selective oxidation of organic compounds to produce high value-added products is one of the most essential requirements in the chemical industry. − In this field, the selective oxidation of aryl alkenes to aromatic aldehydes has aroused great attention because the products of oxidation are important and useful intermediates in fine chemical and pharmaceutical production. − For example, the total annual demand for benzaldehyde has exceeded 90,000 tons, becoming the second organic intermediate after vanillin used in cosmetics and perfumes. , Traditionally, aromatic aldehydes are mainly produced via direct oxidation through the chlorohydrin route by using peracid or stoichiometric chemical oxidants, which suffers from certain problems, such as the formation of undesirable wastes, poor conversion, and environmental pollution. − Although some homogeneous molecular catalysts have been found to be active in this transformation, the difficulty in catalyst separation and the high cost still limit their application. − Therefore, developing high-efficient and low-cost heterogeneous catalysts for selective oxidation of aryl alkenes to aldehydes under environmentally friendly conditions is urgent and highly desired.…”

Section: Introductionmentioning

confidence: 99%

Polyoxometalate-Incorporated Metal-Organic Network as a Heterogeneous Catalyst for Selective Oxidation of Aryl Alkenes

Cui

Zhang

et al. 2022

Inorg. Chem.

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Selective oxidation of aryl alkenes is important for chemical synthesis reactions, in which the key lies in the rational design of efficient catalysts. Herein, four polyoxometalate (POM)-incorporated metal-organic networks, with the formulas of [Co(ttb)(H2O)3]2[SiMo12O40]·2H2O (1), [Co(ttb)(H2O)2]2[SiW12O40]·8H2O (2), [Zn(Httb)(H2ttb)][BW12O40]·9H2O (3) and {[Zn(H2O)3(ttb)]4[Zn3(H2O)6]}[H3SiW10.5Zn1.5O40]2·24H2O (4) (ttb = 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene), were hydrothermally synthesized and structurally characterized. Structural analysis showed that compound 1 consists of a POM-encapsulated three-dimensional (3-D) supramolecular framework; compound 2 is composed of a POM-supported 3-D coordination network; and compounds 3–4 show POM-incorporated 3-D supramolecular networks. Using selective catalytic oxidation of styrene as the model reaction, compounds 1–4 as heterogeneous catalysts display excellent performance with the double advantages of high styrene conversion and benzaldehyde selectivity owing to the synergistic effect among POM anions and transition metal (TM) centers. Among them, compound 1 exhibits the highest performance with ca. 96% styrene conversion and ca. 99% benzaldehyde selectivity in 3 h. In addition, compound 1 also displays excellent substrate compatibility, good reusability, and structural stability. Thus, a plausible reaction pathway for the selective oxidation of styrene is proposed. This study on the structure–function relationship paves a way for the rational design of POM-based heterogeneous catalysts for important catalysis applications.

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A Bicadmium-Substituted Polyoxometalate Network Based on a Vanadosilicate Cluster for the Selective Oxidation of Styrene to Benzaldehyde

Cited by 16 publications

References 38 publications

Selective Oxidation of Simple Aromatics Catalyzed by Nano-Biomimetic Metal Oxide Catalysts: A Mini Review

Selective Oxidation of Simple Aromatics Catalyzed by Nano-Biomimetic Metal Oxide Catalysts: A Mini Review

Experimental and Theoretical Studies on Two Dual-Functional Organic–Inorganic Hybrids Based on [V₄O₁₂]^4– Clusters

Polyoxometalate-Incorporated Metal-Organic Network as a Heterogeneous Catalyst for Selective Oxidation of Aryl Alkenes

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A Bicadmium-Substituted Polyoxometalate Network Based on a Vanadosilicate Cluster for the Selective Oxidation of Styrene to Benzaldehyde

Cited by 16 publications

References 38 publications

Selective Oxidation of Simple Aromatics Catalyzed by Nano-Biomimetic Metal Oxide Catalysts: A Mini Review

Selective Oxidation of Simple Aromatics Catalyzed by Nano-Biomimetic Metal Oxide Catalysts: A Mini Review

Experimental and Theoretical Studies on Two Dual-Functional Organic–Inorganic Hybrids Based on [V4O12]4– Clusters

Polyoxometalate-Incorporated Metal-Organic Network as a Heterogeneous Catalyst for Selective Oxidation of Aryl Alkenes

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Experimental and Theoretical Studies on Two Dual-Functional Organic–Inorganic Hybrids Based on [V₄O₁₂]^4– Clusters