Enhancing hydrophobicity and catalytic activity of nano-Sn-Beta for alcohol ring opening of epoxides through post-synthetic treatment with fluoride

Spanos, Alexander; Parulkar, Aamena; Brunelli, Nicholas A.

doi:10.1016/j.jcat.2021.10.023

Cited by 9 publications

(30 citation statements)

References 43 publications

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“…Both reactants are nonpolar [40,41] and therefore have been chosen as they can interact differently with hydrophilic and hydrophobic catalyst surfaces. [17] Metallosilicate catalysts during the ring opening of epoxides by amines yield two products. The higher selectivity is usually observed towards Markovnikov product (less substituted amino alcohol).…”

Section: Chemcatchemmentioning

confidence: 99%

“…The differences in activity were more pronounced with bulky substrates such as 1,2epoxyhexane and ethanol compared to smaller reactants like epichlorohydrin and methanol. [17] Moreover, other tin beta zeolites demonstrated a tenfold increase in the Meerwein-Ponndorf-Verley (MPV) reduction rate of cyclohexanone, attrib-uted to their enhanced hydrophobicity. [18] Similarly, partially crystalline zirconosilicates were tested in the MPV reduction of cyclohexanone, revealing three key factors contributing to this reaction: the number of Lewis acid sites, mesopore volumes, and once again, the surface hydrophobicity of the catalysts.…”

Section: Introductionmentioning

confidence: 99%

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Hydrophobicity Boosts Catalytic Activity: The Tailoring of Aluminosilicates with Trimethylsilyl Groups**

et al. 2023

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Introducing organic groups into metal silicate catalysts and thus supposedly changing the surface hydrophobicity has been shown to enhance the catalyst performance in various reactions. However, the organic groups introduction does not unambiguously guarantee hydrophobicity control. Therefore, a thorough characterization is necessary to provide a complete view of the interaction between the catalyst surface, reactants, and products. Herein, an aluminosilicate catalyst with welldispersed Al atoms was prepared via the non-hydrolytic sol-gel method. This material was post-synthetically modified with trimethylsilyl groups; their number on the catalyst surface was controlled via a temperature-vacuum pretreatment. In such a way, aluminosilicate materials with similar porosity, structure, and acid site strength and quality were obtained. Notably, the water sorption measurements showed that trimethylsilylated aluminosilicates adsorb 2.5-3 times less water than the parent material (p/p 0 = 0.3). The turn-over-frequency in epoxide ring opening and ethanol dehydration scaled up with the number of trimethylsilyl groups grafted on the catalyst surface. Particularly, the heavily trimethylsilylated sample achieved three to five times higher turnover-frequency in styrene oxide aminolysis than the parent aluminosilicate material. To the best of the authors' knowledge, it exhibited the most active Al sites for epoxide aminolysis in the present literature.

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Section: Chemcatchemmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Hydrophobicity Boosts Catalytic Activity: The Tailoring of Aluminosilicates with Trimethylsilyl Groups**

et al. 2023

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“…Therefore, the severe hydrophilicity drop might explain the substantial effect on catalytic properties. The beneficial effect of hydrophobicity was also observed during the ring opening of epoxides over nano-Sn-Beta zeolites 17 and indirectly displayed over hydrophobic Ti-SBA-16 and less hydrophobic Ti-SBA-12. 70 The aluminosilicate catalysts prepared by non-hydrolytic sol-gel applying organosilane precursors in one-pot did not exceed the TOF numbers presented herein.…”

Section: II (6)mentioning

confidence: 85%

“…More distinct differences in activity were observed with bulky substrates (1,2-epoxyhexane and ethanol) compared to smaller reactants (epichlorohydrin and methanol). 17 Furthermore, other tin beta zeolites made Meerwein-Ponndorf-Verley (MPV) reduction of cyclohexanone ten times faster thanks to their increasing hydrophobicity. 18 Similarly, partially crystalline zirconosilicates were also tested in MPV reduction of cyclohexanone, and three pivotal factors were revealed to contribute to this reaction, namely Lewis acid site numbers, mesopore volumes, and here again, surface hydrophobicity of catalysts.…”

Section: Introductionmentioning

confidence: 99%

Hybrid Acid Catalysts Prepared via Grafting Trimethylsilyl Groups onto Aluminosilicates Synthesized by Non-Hydrolytic Sol-Gel

Leonova

Moravec

Sazama

et al. 2023

Preprint

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Hybrid materials based on metallosilicates are extensively studied for their enhanced catalytic performance. Introducing organic groups into metal silicate catalysts and thus supposedly change the surface hydrophilicity and hydrophobicity has been shown to have an appreciable effect on the catalyst performance in various reactions, including epoxide ring opening reactions and alcohol dehydration. However, the sole organic groups introduction does not unambiguously guarantee hydrophilicity control and might lead to porosity drop, acidity modulation, structural changes, etc. Therefore, a thorough and complex characterization is necessary to provide a complete view of the interaction between the catalyst surface, reactants, and products. Herein, we have prepared aluminosilicate catalyst with well-dispersed Al atoms in silica-based matrices via the non-hydrolytic sol-gel (NHSG) method. This material was post-synthetically modified with trimethylsilyl groups; their number on the catalyst surface was controlled via a temperature vacuum pretreatment. In such a way, we have obtained aluminosilicate materials with similar porosity, structure, and acid site strength and quality. Notably, the water sorption measurements showed that trimethylsilylated aluminosilicates adsorb 2.5−3 times less water (p/p0 = 0.3) than the parent aluminosilicate catalyst. The turn over frequency in epoxide ring opening and ethanol dehydration scaled up with the number of trimethylsilyl groups grafted on the catalyst surface. Particularly, the heavily trimethylsilylated sample achieved three to five times higher turnover frequency in styrene oxide aminolysis with aniline than the parent aluminosilicate material. To the best of our knowledge, it exhibited the most active Al sites for epoxide aminolysis in the present literature.

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“…The study of the surface properties of a catalyst, in particular the wettability, becomes mandatory in order to modulate the stability of the system on one hand and preferential adsorption or desorption of the organic biomass-derived molecules on the other. [12][13][14][15] In the recent literature, several examples are reported relying on the capacity of a more hydrophobic surface to boost catalyst resistance towards water, poisoning of the active sites, especially acidic ones, thus allowing long-life and good recyclability of the system. [16][17][18][19] Therefore, a low hydrophilic surface is a good tool to improve dehydration of bio-based molecules (such as sorbitol to give isosorbide 20,21 ), but also in the case of condensation like esterification of fatty acids [22][23][24] or biobased acids 25,26 and etherification.…”

Section: Introductionmentioning

confidence: 99%

Tuning the Cu/SiO2 wettability features for bio-derived platform molecules valorization

Cavuoto

Ravasio²,

Zaccheria³

et al. 2022

Molecular Catalysis

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Enhancing hydrophobicity and catalytic activity of nano-Sn-Beta for alcohol ring opening of epoxides through post-synthetic treatment with fluoride

Cited by 9 publications

References 43 publications

Hydrophobicity Boosts Catalytic Activity: The Tailoring of Aluminosilicates with Trimethylsilyl Groups**

Hydrophobicity Boosts Catalytic Activity: The Tailoring of Aluminosilicates with Trimethylsilyl Groups**

Hybrid Acid Catalysts Prepared via Grafting Trimethylsilyl Groups onto Aluminosilicates Synthesized by Non-Hydrolytic Sol-Gel

Tuning the Cu/SiO2 wettability features for bio-derived platform molecules valorization

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