Unveiling the Active Surface Sites in Heterogeneous Titanium-Based Silicalite Epoxidation Catalysts: Input of Silanol-Functionalized Polyoxotungstates as Soluble Analogues

Zhang, Teng; Mazaud, Louis; Chamoreau, Lise‐Marie; Paris, Céline; Proust, Anna; Guillemot, Geoffroy

doi:10.1021/acscatal.8b00256

Cited by 37 publications

(41 citation statements)

References 86 publications

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“…Furthermore, for this specific compound, prolonging the reaction up to 48 h did not increase significantly the limonene conversion (81 %), probably due to the deactivation/decomposition of the catalyst. This result is not particularly surprising since the {A,α‐PW 9 } scaffold is generally considered to be less stable than the {B,α‐X III W 9 } (X = As, Sb) ones …”

Section: Oxidation Of Limonene In the Presence Of The (Nbu4n)3[nahmentioning

confidence: 95%

Selective Formation of Epoxylimonene Catalyzed by Phosphonyl/Arsonyl Derivatives of Trivacant Polyoxotungstates at Low Temperature

Makrygenni

Vanmairis²,

Taourit³

et al. 2019

Eur J Inorg Chem

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The catalytic performances of three organophosphonyl/arsonyl derivatives of POMs were evaluated for the epoxidation of limonene in acetonitrile, using aqueous H2O2 as the oxidant. All three W‐based POMs catalysts operated without any additional transition‐metal ions and displayed excellent conversion for limonene at temperatures varying from 4 to 50 °C. Furthermore, the use of B,α‐[NaHAsW9O33{P(O)R}2]3– (R = tBu, ‐CH2CH2CO2H) complexes led to the complete conversion of limonene to epoxylimonene at 4 °C. The selectivity of the reaction was modulated by varying the reaction solvent, and it was found that allylic reactions were favored in ethanol. The effect of the catalyst protonation was also investigated by DFT calculations, highlighting the role of protons in the epoxidation process.

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Section: Oxidation Of Limonene In the Presence Of The (Nbu4n)3[nahmentioning

confidence: 95%

Selective Formation of Epoxylimonene Catalyzed by Phosphonyl/Arsonyl Derivatives of Trivacant Polyoxotungstates at Low Temperature

Makrygenni

Vanmairis²,

Taourit³

et al. 2019

Eur J Inorg Chem

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“…4a) and [-B-SbW 9 O 30 ( t BuSiO) 3 Ti(O i Pr)] 3À (2b; Fig. 4b), with siteisolated Ti IV , demonstrated a distinct catalytic behaviour in the epoxidation of allylic alcohol (Zhang et al, 2018a). This resulted from slight conformational differences on the scaffolds.…”

Section: Epoxidation Of Alkenesmentioning

confidence: 97%

“…By means of meticulous mathematical analysis, kinetic investigation gives indirect but useful insights into the relationship between structure and activity (Skobelev et al, 2015(Skobelev et al, , 2017Zhang et al, 2018a). Software, programs and algorithms are also indispensable, for example, the structure refinement program SHELXL for single-crystal X-ray diffraction analysis (Sheldrick, 2015) and PLATON (Spek, 2009) for calculation of the accessible empty space in the framework of a MOFhybrid POM (Han et al, 2015;Shi et al, 2015).…”

Section: Table 13mentioning

confidence: 99%

Recent advances of polyoxometalate-catalyzed selective oxidation based on structural classification

Chen

Shen

2018

Acta Crystallogr C

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The structural diversity and tenability observed in POMs has encouraged extensive investigations into their catalytic activity. Based on the structural classification of POMs, this review summarizes recent advances relating to POM‐catalyzed selective oxidation and places most emphasis on dynamic developments from 2015 onwards. Work which contributes to comparing the catalytic performance of POMs with delicate structural differences (e.g. the same type of POM structure with differences of the heteroatom, addenda, protonated state or counter‐ion) and in elucidating the origin/distinction of catalytic activity, as well as reasonable mechanisms, are especially highlighted.

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“…Polyoxometalates (POMs) are anionic oxide clusters of early transition metals that have strong acidity and good hydrophilicity were widely used in the field of proton conduction due to its fast charge transfer capability and strong protonholding performance. [8,9] Moreover, the structure of POMs and the size of the heteropolyanion are adjustable. The oxygen site on the surface of POMs can form a large number of hydrogen bond networks.…”

Section: Introductionmentioning

confidence: 99%

Construction of Strandberg‐Type Polyoxometalate‐Based Inorganic‐Organic Hybrid Material with Water‐Assisted Proton Conductivity

et al. 2020

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Polyoxometalates (POMs) were widely applied in the field of proton conduction due to their rapid charge transfer capability and large proton capacity. The Strandberg-type POM has small size and large charge density, can form functional organometallic compounds with metal ions. In this study, by using [P 2 Mo 5 O 23 ] 6À coordinate with the cobalt ion with cytosine as the structure-directing agent, a compound of Co 1.5 (C 4 H 6 N 3 O) 3 [P 2 Mo 5 O 23 ]⋅8.5H 2 O was synthesized, which showed one-dimensional chain structure and exhibits proton conductivity of 3.62 × 10 À 4 S cm À 1 at 98°C and 97% RH. The amino group and nitrogen atoms in the cytosine can form hydrogen bond with the coordination water molecules. Meanwhile, the hydrogen bond network can also be formed between the water molecules, which is one of the main factors for proton conduction performance. The compound Co 1.5 (C 4 H 6 N 3 O) 3 [P 2 Mo 5 O 23 ]⋅8.5H 2 O exhibited the corresponding activation energies and conduction mechanisms at different temperature intervals, by analyzing the temperature-dependent PXRD spectrum under high-humidity conditions, which showed the hydrogen bond network of the crystal during the temperature changes affects its proton conduction performance.

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Unveiling the Active Surface Sites in Heterogeneous Titanium-Based Silicalite Epoxidation Catalysts: Input of Silanol-Functionalized Polyoxotungstates as Soluble Analogues

Cited by 37 publications

References 86 publications

Selective Formation of Epoxylimonene Catalyzed by Phosphonyl/Arsonyl Derivatives of Trivacant Polyoxotungstates at Low Temperature

Selective Formation of Epoxylimonene Catalyzed by Phosphonyl/Arsonyl Derivatives of Trivacant Polyoxotungstates at Low Temperature

Recent advances of polyoxometalate-catalyzed selective oxidation based on structural classification

Construction of Strandberg‐Type Polyoxometalate‐Based Inorganic‐Organic Hybrid Material with Water‐Assisted Proton Conductivity

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