Catalytic Performance of Micro-Mesoporous Zirconosilicates Prepared by Non-Hydrolytic Sol-Gel in Ethanol-To-Butadiene Transformation and Related Reactions

Hradsky, Dalibor; Macháč, Petr; Škoda, David; Leonova, Lucie; Sazama, Petr; Pastvová, Jana; Kaucký, Dalibor; Všianský, Dalibor; Moravec, Zdeněk; Stýskalík, Aleš

doi:10.26434/chemrxiv-2022-n5xkb

Cited by 3 publications

(3 citation statements)

References 62 publications

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“…Very similar results were previously obtained via the non-hydrolytic sol-gel (NHSG) process. 14,62 NHSG catalysts displayed higher acidity leading to higher production of ethylene. An important take away message is that AASG represents a reliable method to obtain highly dispersed Ta species in silica matrices.…”

Section: Characterizing the Peculiarities Of Aerosol Made Agta-sio 2 ...mentioning

confidence: 99%

Aerosol-assisted sol–gel synthesis of mesoporous Ag–Ta–SiO₂catalysts for the direct upgrading of ethanol to butadiene

et al. 2023

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Section: Characterizing the Peculiarities Of Aerosol Made Agta-sio 2 ...mentioning

confidence: 99%

Aerosol-assisted sol–gel synthesis of mesoporous Ag–Ta–SiO₂catalysts for the direct upgrading of ethanol to butadiene

et al. 2023

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“…Acetaldehyde might be used as a butadiene precursor in the so-called Lebedev process. [12][13][14][15] New sustainable catalytic pathways need to be developed to produce acetaldehyde and to overcome crude oil resources depletion.…”

Section: Introductionmentioning

confidence: 99%

Ethanol Dehydrogenation over Copper-Silica Catalysts: From Atomic Distribution to 15 nm Large Particles

Pokorny

Vykoukal

Macháč

et al. 2022

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Non-oxidative ethanol dehydrogenation is a renewable source of acetaldehyde and hydrogen. The reaction is often catalyzed by supported copper catalysts with high selectivity. The activity and long-term stability depend on many factors, including particle size, choice of support, doping, etc. Herein we present four different synthetic pathways to prepare Cu/SiO2 catalysts (~2.5 wt% Cu) with varying copper distribution: hydrolytic sol-gel (mostly atomic dispersion), dry impregnation (Ā = 3.9 nm; σ = 1.4 nm and particles up to 22 nm), strong electrostatic adsorption (Ā = 2.6 nm; σ = 1.0 nm) and solvothermal hot injection followed by Cu particles deposition (Ā = 14.7 nm; σ = 3.1 nm). All materials were characterized by ICP-OES, XPS, N2 physisorption, STEM-EDS, XRD, and H2-TPR, and tested in ethanol dehydrogenation from 185 to 325 °C. The sample prepared by hydrolytic sol-gel exhibited mostly atomic Cu dispersion and, accordingly, the highest catalytic activity. Its acetaldehyde productivity (2.79 g g−1 h−1 at 255 °C) outperforms most of the Cu-based catalysts reported in the literature, but it lacks stability and tends to deactivate over time. On the other hand, the sample prepared by simple and cost-effective dry impregnation, despite having Cu particles of various sizes, was still highly active (2.42 g g−1 h−1 acetaldehyde at 255 °C) and it was the most stable sample out of the studied materials. The characterization of the spent catalyst confirmed its exceptional properties: it showed the lowest extent of both coking and particle sintering.

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“…Very similar results were previously obtained via the non-hydrolytic sol-gel (NHSG) process. 14,51 NHSG catalysts featured high Ta dispersion and displayed higher acidity leading to high ethylene production. An important take away message is that AASG represents a reliable method to obtain highly dispersed Ta species in silica matrices (even if the resulting acidity would need to be tempered in the context of the ETB reaction).…”

Section: Characterizing the Peculiarities Of Aerosol Made Agta-sio2 C...mentioning

confidence: 99%

Aerosol-assisted sol-gel synthesis of mesoporous Ag-Ta-SiO2 catalysts for the direct upgrading of ethanol to butadiene

Dochain

Daelen

Stýskalík

et al. 2022

Preprint

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The Lebedev process, or the direct catalytic conversion of bioethanol to butadiene, offers an up-and-coming sustainable alternative to the petrochemical route toward this high-demand C4 hydrocarbon. Since the reaction mechanism involves a cascade of dehydrogenation, hydrogen transfer and dehydration steps, a bifunctional catalyst is required, combining both redox (for the dehydrogenation reaction) and acid (for hydrogen transfer and dehydration reactions) functionalities. Multi-step preparation methods are typically implemented to obtain tailored bifunctional catalysts, and a challenge is to balance the two functions to maximize the BD yield. Here, we disclose a straightforward, one-step, and continuous preparation of Ta-doped SiO2 loaded with Ag nanoparticles by coupling sol-gel chemistry with aerosol processing. Combining tantalum ethoxide, silver nitrate, hydrolysed tetraethyl orthosilicate and Pluronic F127 as templating agent in the aerosol process leads to mesoporous bifunctional catalysts featuring a specific surface area between 310–370 m2 g–1, a pore volume of ca. 0.5 mL g–1 and an average pore diameter of 5 nm. As attested by a variety of characterization techniques, the method leads to the homogeneous incorporation of highly dispersed tantalum species in the silica matrix, thereby creating the required acidic sites. These new catalysts have higher dehydration activity, as compared to the corresponding reference catalysts prepared by classical impregnation. Concomitantly, relatively small silver nanoparticles are stabilized (~15 nm). The relative Ta and Ag loading can be tuned easily. In the ethanol to butadiene reaction, these aerosol-made catalysts achieve a butadiene yield of ca. 25 % by optimizing the relative loadings of Ta and Ag, outcompeting the corresponding formulations prepared by impregnation.

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Catalytic Performance of Micro-Mesoporous Zirconosilicates Prepared by Non-Hydrolytic Sol-Gel in Ethanol-To-Butadiene Transformation and Related Reactions

Cited by 3 publications

References 62 publications

Aerosol-assisted sol–gel synthesis of mesoporous Ag–Ta–SiO₂catalysts for the direct upgrading of ethanol to butadiene

Aerosol-assisted sol–gel synthesis of mesoporous Ag–Ta–SiO₂catalysts for the direct upgrading of ethanol to butadiene

Ethanol Dehydrogenation over Copper-Silica Catalysts: From Atomic Distribution to 15 nm Large Particles

Aerosol-assisted sol-gel synthesis of mesoporous Ag-Ta-SiO2 catalysts for the direct upgrading of ethanol to butadiene

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Catalytic Performance of Micro-Mesoporous Zirconosilicates Prepared by Non-Hydrolytic Sol-Gel in Ethanol-To-Butadiene Transformation and Related Reactions

Cited by 3 publications

References 62 publications

Aerosol-assisted sol–gel synthesis of mesoporous Ag–Ta–SiO2catalysts for the direct upgrading of ethanol to butadiene

Aerosol-assisted sol–gel synthesis of mesoporous Ag–Ta–SiO2catalysts for the direct upgrading of ethanol to butadiene

Ethanol Dehydrogenation over Copper-Silica Catalysts: From Atomic Distribution to 15 nm Large Particles

Aerosol-assisted sol-gel synthesis of mesoporous Ag-Ta-SiO2 catalysts for the direct upgrading of ethanol to butadiene

Contact Info

Product

Resources

About

Aerosol-assisted sol–gel synthesis of mesoporous Ag–Ta–SiO₂catalysts for the direct upgrading of ethanol to butadiene

Aerosol-assisted sol–gel synthesis of mesoporous Ag–Ta–SiO₂catalysts for the direct upgrading of ethanol to butadiene