Hybrid mesoporous aluminosilicate catalysts obtained by non-hydrolytic sol–gel for ethanol dehydration

2020 ◽  
Vol 8 (44) ◽  
pp. 23526-23542
Author(s):  
Ales Styskalik ◽  
Imene Kordoghli ◽  
Claude Poleunis ◽  
Arnaud Delcorte ◽  
Zdenek Moravec ◽  
...  
Keyword(s):  
Sol Gel ◽  
Methyl Groups ◽  
Ethanol Dehydration ◽  
Mesoporous Aluminosilicate ◽  
Highly Porous

Introduction of methyl groups into the highly porous aluminosilicates prepared by non-hydrolytic sol–gel improves the ethylene yields in ethanol dehydration.

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

2021 ◽  
Author(s):  
Ales Styskalik ◽  
Imene Kordoghli ◽  
Claude Poleunis ◽  
Arnaud Delcorte ◽  
Denis D. Dochain ◽  
...  
Keyword(s):  
Sol Gel ◽  
Ethanol Dehydration ◽  
Mesoporous Aluminosilicate

scholarly journals Non-Hydrolytic Sol-Gel Route to a Family of Hybrid Mesoporous Aluminosilicate Ethanol Dehydration Catalysts

2020 ◽  
Author(s):  
Ales Styskalik ◽  
Imène Kordoghli ◽  
Claude Poleunis ◽  
Arnaud Delcorte ◽  
Denis Dochain ◽  
...  
Keyword(s):  
Gas Phase ◽  
Sol Gel ◽  
Catalytic Performance ◽  
Silica Matrix ◽  
Ethanol Dehydration ◽  
One Pot ◽  
Water Contact ◽  
Hybrid Silica ◽  
Mesoporous Aluminosilicate ◽  
Improved Performance

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 non-hydrolytic 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.<br>

scholarly journals Ethanol Dehydration over Hybrid Mesoporous Aluminosilicate Catalysts Obtained in One Pot by Non-Hydrolytic Sol-Gel

2020 ◽  
Author(s):  
Ales Styskalik ◽  
Imène Kordoghli ◽  
Claude Poleunis ◽  
Arnaud Delcorte ◽  
Zdenek Moravec ◽  
...  
Keyword(s):  
Catalyst Activity ◽  
Sol Gel ◽  
Acid Sites ◽  
Silica Matrix ◽  
Methyl Groups ◽  
Ethanol Dehydration ◽  
Alcohol Dehydration ◽  
One Pot ◽  
Surface Hydrophilicity ◽  
Silica Alumina

<p>Ethanol dehydration is effectively catalyzed by solid acids, such as HZSM-5, alumina, or silica-alumina. In these catalysts, the amount, nature, and strength of acid sites is believed to determine catalyst activity and stability. However, surface hydrophilicity or hydrophobicity can be suggested as another decisive catalyst property that can directly influence performance. For example, a more hydrophobic surface might be beneficial in repelling the co-product of the reaction, water. However, these aspects have been studied only scarcely in the context of alcohol dehydration. Here, a series of mesoporous hybrid aluminosilicate catalysts containing CH<sub>3</sub>Si groups was prepared in one pot by non-hydrolytic sol-gel (NHSG). The presence of the methyl groups was verified by IR, solid-state NMR, and ToF-SIMS. Aluminum is mostly incorporated in tetrahedral coordination in the hybrid silica matrix. Two parameters were varied: (i) the Si:Al ratio and (ii) the Si:MeSi ratio. On the one hand, changing the Si:Al ratio had a marked impact on hydrophilicity, as attested by water sorption measurements. On the other hand, unexpectedly, the introduction of methyl groups had no clear influence on sample hydrophilicity. Nevertheless, some of the methylated aluminosilicate catalysts markedly outperformed the purely inorganic catalysts and a commercial silica-alumina benchmark. While a direct influence of surface hydrophilicity or hydrophobicity could be excluded, characterization of acidity (IR-pyridine) revealed that these improved performances are correlated with a modification of the acidic properties in the hybrid catalysts caused by the presence of methyl groups. A decisive role of acidity in ethanol dehydration was confirmed by an experiment with delayed addition of the Al precursor in the NHSG synthesis. This led to a higher Al surface concentration, marked acid sites number increase, and better catalytic performance, even competing with HZSM-5 in terms of activity.</p>

scholarly journals Ethanol Dehydration over Hybrid Mesoporous Aluminosilicate Catalysts Obtained in One Pot by Non-Hydrolytic Sol-Gel

2020 ◽  
Author(s):  
Ales Styskalik ◽  
Imène Kordoghli ◽  
Claude Poleunis ◽  
Arnaud Delcorte ◽  
Zdenek Moravec ◽  
...  
Keyword(s):  
Catalyst Activity ◽  
Sol Gel ◽  
Acid Sites ◽  
Silica Matrix ◽  
Methyl Groups ◽  
Ethanol Dehydration ◽  
Alcohol Dehydration ◽  
One Pot ◽  
Surface Hydrophilicity ◽  
Silica Alumina

<p>Ethanol dehydration is effectively catalyzed by solid acids, such as HZSM-5, alumina, or silica-alumina. In these catalysts, the amount, nature, and strength of acid sites is believed to determine catalyst activity and stability. However, surface hydrophilicity or hydrophobicity can be suggested as another decisive catalyst property that can directly influence performance. For example, a more hydrophobic surface might be beneficial in repelling the co-product of the reaction, water. However, these aspects have been studied only scarcely in the context of alcohol dehydration. Here, a series of mesoporous hybrid aluminosilicate catalysts containing CH<sub>3</sub>Si groups was prepared in one pot by non-hydrolytic sol-gel (NHSG). The presence of the methyl groups was verified by IR, solid-state NMR, and ToF-SIMS. Aluminum is mostly incorporated in tetrahedral coordination in the hybrid silica matrix. Two parameters were varied: (i) the Si:Al ratio and (ii) the Si:MeSi ratio. On the one hand, changing the Si:Al ratio had a marked impact on hydrophilicity, as attested by water sorption measurements. On the other hand, unexpectedly, the introduction of methyl groups had no clear influence on sample hydrophilicity. Nevertheless, some of the methylated aluminosilicate catalysts markedly outperformed the purely inorganic catalysts and a commercial silica-alumina benchmark. While a direct influence of surface hydrophilicity or hydrophobicity could be excluded, characterization of acidity (IR-pyridine) revealed that these improved performances are correlated with a modification of the acidic properties in the hybrid catalysts caused by the presence of methyl groups. A decisive role of acidity in ethanol dehydration was confirmed by an experiment with delayed addition of the Al precursor in the NHSG synthesis. This led to a higher Al surface concentration, marked acid sites number increase, and better catalytic performance, even competing with HZSM-5 in terms of activity.</p>

scholarly journals Non-Hydrolytic Sol-Gel Route to a Family of Hybrid Mesoporous Aluminosilicate Ethanol Dehydration Catalysts

2020 ◽  
Author(s):  
Ales Styskalik ◽  
Imène Kordoghli ◽  
Claude Poleunis ◽  
Arnaud Delcorte ◽  
Denis Dochain ◽  
...  
Keyword(s):  
Gas Phase ◽  
Sol Gel ◽  
Catalytic Performance ◽  
Silica Matrix ◽  
Ethanol Dehydration ◽  
One Pot ◽  
Water Contact ◽  
Hybrid Silica ◽  
Mesoporous Aluminosilicate ◽  
Improved Performance

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 non-hydrolytic 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.<br>

Sol-gel and SPS combined synthesis of highly porous wollastonite ceramic materials with immobilized Au-NPs

2017 ◽  
Vol 43 (11) ◽  
pp. 8509-8516 ◽  
Author(s):  
E.K. Papynov ◽  
O.O. Shichalin ◽  
V.Yu. Mayorov ◽  
E.B. Modin ◽  
A.S. Portnyagin ◽  
...  
Keyword(s):  
Sol Gel ◽  
Ceramic Materials ◽  
Au Nps ◽  
Highly Porous

Sol-Gel Derived Silica Layers for Low-k Dielectrics Applications

2000 ◽  
Vol 612 ◽  
Author(s):  
Sylvie Acosta ◽  
André Ayral ◽  
Christian Guizard ◽  
Charles Lecornec ◽  
Gérard Passemard ◽  
...  
Keyword(s):  
Average Pore Size ◽  
Sol Gel ◽  
Porous Silica ◽  
Thin Layers ◽  
Gaseous Ammonia ◽  
Potential Candidate ◽  
Average Pore ◽  
Synthesis Strategy ◽  
Silica Layers ◽  
Highly Porous

AbstractPorous silica exhibits attractive dielectric properties, which make it a potential candidate for use as insulator into interconnect structures. A new way of preparation of highly porous silica layers by the sol-gel route was investigated and is presented. The synthesis strategy was based on the use of common and low toxicity reagents and on the development of a simple process without gaseous ammonia post-treatment or supercritical drying step. Defect free layers were deposited by spin coating on 200 mm silicon wafers and characterized. Thin layers with a total porosity larger than 70% and an average pore size of 5 nm were produced. The dielectric constant measured under nitrogen flow on these highly porous layers is equal to ∼ 2.5, which can be compared to the value calculated from the measured porosity, ∼ 1.9. This difference is explained by the presence of water adsorbed on the hydrophilic surface of the unmodified silica.

scholarly journals Preparation and morphology of porous SiO2 ceramics derived from fir flour templates

2010 ◽  
Vol 75 (3) ◽  
pp. 385-394 ◽  
Author(s):  
Li Zhong ◽  
Tiejun Shi ◽  
Liying Guo
Keyword(s):  
Amorphous Material ◽  
Sol Gel ◽  
Size Distributions ◽  
X Ray Diffraction ◽  
Ordered Structures ◽  
Porous Sio2 ◽  
Pore Size Distributions ◽  
Naoh Solution ◽  
Gel Processing ◽  
Highly Porous

The preparation of SiO2 ceramics with controllable porous structure from fir flour templates via sol-gel processing was investigated. The specific size the fir flour, which was treated with 20 % NaOH solution, was infiltrated with a low viscous silica sol and subsequently calcined in air, which resulted in the formation of highly porous SiO2 ceramics. X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and field emission scanning electron microscopy (FESEM) were employed to investigate the microstructure and phase formation during processing as well as of the SiO2 ceramics. N2 adsorption measurements were used to analyze the pore size distributions (PSD) of the final ceramics. The results indicated that the surface topography was changed and the proportion of the amorphous material was increased in NaOH-treated fir flour. The final oxide products retained ordered structures of the pores and showed unique pore sizes and distributions with hierarchy on the nanoscale derived from the fir flour.

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