Surface-functionalized mesoporous gallosilicate catalysts for the efficient and sustainable upgrading of glycerol to solketal

Vivian, Alvise; Soumoy, Loraine; Fusaro, Luca; Fiorilli, Sonia Lucia; Debecker, Damien P.; Aprile, Carmela

doi:10.1039/d0gc02562c

Cited by 28 publications

(26 citation statements)

References 44 publications

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“…The rest was probably lost during the calcination step. The nature of the organic groups was identified with the help of 13 C CPMAS NMR experiments (Fig. 3).…”

Section: Resultsmentioning

confidence: 99%

“…following the same synthetic protocol (see 13 C CPMAS NMR in ESI, Fig. 1S) but this sample had poor catalytic activity and is not discussed further in this article.…”

Section: Methodsmentioning

confidence: 99%

“…longer aliphatic chains, aromatic rings, fluorinated organic groups) has been reported much less often. Such a broadening of applied materials however might bring other positive effects: not only hydrophobicity alteration (that may or may not be observed upon methyl groups introduction), 3,[11][12][13] including also selective adsorption of reactants induced by specific non-bonding interactions (e.g. π-π stacking), 14 but also porosity changes, 15,16 hydrothermal stability improvement, 17 or modulation of catalyst sites strength and accessibility.…”

Section: Introductionmentioning

confidence: 99%

“…30 mg of analyzed sample were pressed and evacuated at 350 °C were referenced to the residual proton signals or carbon resonances of benzene-d6 (7.15 and 128.0 ppm, respectively). Solid-state27 Al,29 Si, and13 C solid state magic angle spinning (MAS) NMR spectra were acquired on Bruker Avance-500 NMR spectrometer with a 4 mm CP-MAS Bruker probe at frequencies 99.4 MHz for silicon, 130.3 MHz for aluminum, and 125.8 MHz for carbon. MAS rates were 8 kHz for29 Si and 13 C (CP)MAS and 10 kHz for27 Al MAS spectra.…”

mentioning

confidence: 99%

“…Solution NMR spectra were recorded on a Bruker 300 MHz NMR spectrometer at frequencies 299.8 MHz for proton and 75.4 MHz for carbon with deuterated solvents as the external lock. The proton and carbon NMR spectra Chemical shifts were referenced externally to29 Si δ[3-(trimethylsilyl)-1-propanesulfonic acid sodium salt (DSS)]: 1.53 ppm;13 C δ[adamantane] 38.68 ppm; 27 Al δ [[Al(H2O)6] 3+ (aq. solution)]: 0.0 ppm.…”

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confidence: 99%

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Non-hydrolytic sol–gel route to a family of hybrid mesoporous aluminosilicate ethanol dehydration catalysts

et al. 2021

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Organic-inorganic hybrid materials are nowadays intensely studied for potential applications in heterogeneous catalysis because their properties and catalytic behavior differ from pristine inorganic counterparts. The organic groups at the catalyst surface can modify not only its hydrophilicity, but also acidity, hydrothermal stability, porosity, etc. In some cases, such properties alteration leads to improved catalytic performance in terms of activity, selectivity, or stability. However, the choice of organic groups stays relatively narrow, as most reports focus on pendant methyl groups. Here, a series of mesoporous hybrid aluminosilicate materials containing various organic groups was prepared in one pot by nonhydrolytic sol-gel (NHSG). Both aromatic and aliphatic, pendant and bridging organic groups were incorporated. The presence of the organic groups in the bulk and at the outermost surface of the materials was verified by solid-state NMR and ToF-SIMS, respectively.Aluminum is mostly incorporated in tetrahedral coordination in the hybrid silica matrix. The organically modified mesoporous aluminosilicate samples were tested as catalysts in the gas phase ethanol dehydration (which relies on solid acids) and most of them outperformed the purely inorganic catalyst benchmark. While a direct influence of surface hydrophilicity or hydrophobicity (as probed by water sorption and water contact angle measurements) appeared unlikely, characterization of acidity (IR-pyridine) revealed that the improved performance for hybrid catalysts can be correlated with a modification of the acidic properties. In turn, acidity is determined by the quality of the dispersion of Al centers in the form of isolated sites in the hybrid silica matrix. All in all, this study establishes a "ranking" for a variety of organic groups in terms of their effect on gas-phase ethanol dehydration to ethylene; ethylene yield decreases in this order: bridging xylylene ≈ pendant methyl > pendant benzyl > bridging methylene ≈ inorganic benchmark (no organic groups) > bridging ethylene.

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“…The rest was probably lost during the calcination step. The nature of the organic groups was identified with the help of 13 C CPMAS NMR experiments (Fig. 3).…”

Section: Resultsmentioning

confidence: 99%

“…following the same synthetic protocol (see 13 C CPMAS NMR in ESI, Fig. 1S) but this sample had poor catalytic activity and is not discussed further in this article.…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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confidence: 99%

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Non-hydrolytic sol–gel route to a family of hybrid mesoporous aluminosilicate ethanol dehydration catalysts

et al. 2021

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Multifunctional, Hybrid Materials Design via Spray‐Drying: Much more than Just Drying

Wintzheimer,

Luthardt,

Cao

et al. 2023

Advanced Materials

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Spray‐drying is a popular and well‐known “drying tool” for engineers. This perspective highlights that, beyond this application, spray‐drying is a very interesting and powerful tool for materials chemists to enable the design of multifunctional and hybrid materials. Upon spray‐drying, the confined space of a liquid droplet is narrowed down, and its ingredients are forced together upon “falling dry.” As detailed in this article, this enables the following material formation strategies either individually or even in combination: nanoparticles and/or molecules can be assembled; precipitation reactions as well as chemical syntheses can be performed; and templated materials can be designed. Beyond this, fragile moieties can be processed, or “precursor materials” be prepared. Post‐treatment of spray‐dried objects eventually enables the next level in the design of complex materials. Using spray‐drying to design (particulate) materials comes with many advantages—but also with many challenges—all of which are outlined here. It is believed that multifunctional, hybrid materials, made via spray‐drying, enable very unique property combinations that are particularly highly promising in myriad applications—of which catalysis, diagnostics, purification, storage, and information are highlighted.

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Titanosilicate Epoxidation Catalysts: A Review of Challenges and Opportunities

2021

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Epoxidation reactions are tremendously important for modern chemistry, as they lead to series of highly useful bulk and fine chemicals, monomers, and intermediates for organic synthesis. Progress in epoxidation processes goes hand in hand with the advancement made in catalysis science. In this context, heterogeneous catalysts, and particularly Ti‐based formulations, are playing a central role and have seen tremendous developments over the past two decades, leveraging on advanced materials science. The aim of this review is to illustrate the various strategies of titanosilicate catalysts preparation that can lead to more versatile, more performant, and greener epoxidation processes. We successively cover (i) supported catalysts, obtained by the grafting of Ti species onto preformed silica supports, (ii) microporous crystalline titanosilicates (zeolites), and (iii) amorphous titanosilicates obtained by sol‐gel chemistry. For each category, with an emphasis on catalyst preparation, the challenges that have to be tackled to boost catalyst performance are highlighted. From that point, we present a critical review of the different approaches that have been proposed in the primary literature to tailor the properties that govern catalysts performance (activity, selectivity, stability, ease of handling). This is done by better controlling the nature of the active surface species, adapting particles size and shape, optimizing texture, modifying surface chemistry, etc. These lines of attack encompass molecular approaches for the grafting of well‐defined species, top‐down and bottom‐up synthesis of hierarchically porous zeolites, advanced sol‐gel routes potentially performed in non‐conventional media or coupled with original processing, preparation of self‐standing monoliths, etc. Future research directions are discussed with emphasis on the application scope of new catalytic materials and possible approaches to increase catalyst performance.

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Surface-functionalized mesoporous gallosilicate catalysts for the efficient and sustainable upgrading of glycerol to solketal

Abstract: Two series of functionalized mesoporous Ga-silicates were prepared in a straightforward and sustainable one-pot procedure using different alkyl-silanes. The efficacy of the adopted co-synthetic approach based on aerosol processing has...

Cited by 28 publications

References 44 publications

Non-hydrolytic sol–gel route to a family of hybrid mesoporous aluminosilicate ethanol dehydration catalysts

Non-hydrolytic sol–gel route to a family of hybrid mesoporous aluminosilicate ethanol dehydration catalysts

Multifunctional, Hybrid Materials Design via Spray‐Drying: Much more than Just Drying

Titanosilicate Epoxidation Catalysts: A Review of Challenges and Opportunities

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