Enhancement of the 1-butanol productivity in the ethanol condensation catalyzed by noble metal nanoparticles supported on Mg-Al mixed oxide

Quesada, Jorge; Faba, Laura; Dı́az, Eva; Ordóñez, Salvador

doi:10.1016/j.apcata.2018.06.037

“…And intramolecular dehydration of 1-butanol could lead to the formation of 1-butylene, which could be further hydrogenated to produce butane (step (8 and 9)). In addition, ethanol can convert to carbon monoxide, carbon dioxide or C 1 -C 3 products through oxidation or hydration (step (10)) [38][39][40], while carbon monoxide/dioxide can also be formed from acetaldehyde decarbonylation [41,42] or from organic acids (in-situ generated) decarboxylation [43]. Additionally, intermolecular dehydration can undergo at relatively low temperatures (<623 K) to form ethyl ether (step (11)) over zeolite-based catalysts between two molecules of ethanol.…”

Section: C-c Bond Formation Pathwaymentioning

confidence: 99%

Recent advances in selective C-C bond coupling for ethanol upgrading over balanced Lewis acid-base catalysts

Dai

¹

2019

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Ethanol is a considerable platform molecule in biomass conversion, which could be acquired in quantity through acetone-butanol-ethanol (ABE) fermentation. People have been working on the upgrading of ethanol to value added chemicals for decades. In the meantime, 1-butanol and a series of value added products have been selectively generated through CC bond coupling. In this mini-review, we focus on the recent advances in selective CC bond formation over balanced Lewis acid-base catalysts such as modified metal oxide, mixed metal oxide, hydroxyapatite and zeolite confined transition metal oxide catalysts. Among them, Pd-MgAlO x and Sr-based hydroxyapatite exhibit >70% 1-butanol selectivity, while Zn x Zr y O z and Ta-SiBEA zeolite achieve >80% of isobutene and butadiene selectivity respectively. The mechanism and reaction pathway of CC bond formation in each reaction system are described in detail. The correlation between CC bond coupling and the acidity/basicity of the Lewis acid-base pairs from the surface of the catalysts are also discussed.

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“…The Guerbet reaction of alcohols requires the dehydrogenation of the alcohol to the reactive aldehyde [38,39], a reaction that can be viewed as the microscopic reverse of the hydrogenation of an aldehyde to an alcohol. Moreover, one of the main pathways to selectivity losses during the Guerbet reaction is the C-C bond cleavage of acetaldehyde via decarbonylation [40]. Comparison of monometallic and bimetallic Pd-based catalysts showed that adding Cu to Pd significantly altered the product distribution, shifting selectivity to the hydrogenation reaction.…”

Section: Resultsmentioning

confidence: 99%

Oxygenate Reactions over PdCu and PdAg Catalysts: Distinguishing Electronic and Geometric Effects on Reactivity and Selectivity

Bathena¹,

Phung²,

Svadlenak³

et al. 2020

Preprint

0

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We investigate PdCu and PdAg catalysts in the context of oxygenate upgrading for biofuels. To this end, we measure the rates of decarbonylation and hydrogenation of butyraldehyde, the reactive intermediate for the industrially relevant Guerbet condensation, and correlate the selectivity and reactivity with the properties of the catalysts via a range of characterization efforts. Data obtained from EXAFS and XANES show that the bulk of the catalyst metallic nanoparticles is enriched in Pd, while the surface is enriched in Cu and Ag. The data for PdCu show clear dominance of geometric (ensemble) effects on the selectivity. Conversely, the electronic (ligand) effects of alloying dominate over the reaction rate of the catalysts, as electron donation from Cu to Pd promotes the Cu and increases the desired (de)hydrogenation reactions. In contrast, in PdAg catalysts, the weaker electronic exchange, as indicated by Pd L edge XANES and theoretical calculations, is not sufficient to promote Ag, resulting in monotonic loss of activity with increasing Ag content and without selectivity improvement. We use the implications of these findings to provide valuable design principles for oxygenate catalysis and to discover a highly selective bifunctional catalyst system, comprised of a PdCu alloy catalyst and titanium dioxide for the upgrading of ethanol to longer-chain oxygenates.<br>

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“…The Guerbet reaction of alcohols requires the dehydrogenation of the alcohol to the reactive aldehyde [38,39], a reaction that can be viewed as the microscopic reverse of the hydrogenation of an aldehyde to an alcohol. Moreover, one of the main pathways to selectivity losses during the Guerbet reaction is the C-C bond cleavage of acetaldehyde via decarbonylation [40].…”

Section: Resultsmentioning

confidence: 99%

Oxygenate Reactions over PdCu and PdAg Catalysts: Distinguishing Electronic and Geometric Effects on Reactivity and Selectivity

Bathena¹,

Phung²,

Svadlenak³

et al. 2020

Preprint

0

View full text Add to dashboard Cite

We investigate PdCu and PdAg catalysts in the context of oxygenate upgrading for biofuels. To this end, we measure the rates of decarbonylation and hydrogenation of butyraldehyde, the reactive intermediate for the industrially relevant Guerbet condensation, and correlate the selectivity and reactivity with the properties of the catalysts via a range of characterization efforts. Data obtained from EXAFS and XANES show that the bulk of the catalyst metallic nanoparticles is enriched in Pd, while the surface is enriched in Cu and Ag. The data for PdCu show clear dominance of geometric (ensemble) effects on the selectivity. Conversely, the electronic (ligand) effects of alloying dominate over the reaction rate of the catalysts, as electron donation from Cu to Pd promotes the Cu and increases the desired (de)hydrogenation reactions. In contrast, in PdAg catalysts, the weaker electronic exchange, as indicated by Pd L edge XANES and theoretical calculations, is not sufficient to promote Ag, resulting in monotonic loss of activity with increasing Ag content and without selectivity improvement. We use the implications of these findings to provide valuable design principles for oxygenate catalysis and to discover a highly selective bifunctional catalyst system, comprised of a PdCu alloy catalyst and titanium dioxide for the upgrading of ethanol to longer-chain oxygenates.<br>

show abstract

Enhancement of the 1-butanol productivity in the ethanol condensation catalyzed by noble metal nanoparticles supported on Mg-Al mixed oxide

Cited by 23 publications

References 46 publications

Recent advances in selective C-C bond coupling for ethanol upgrading over balanced Lewis acid-base catalysts

Recent advances in selective C-C bond coupling for ethanol upgrading over balanced Lewis acid-base catalysts

Oxygenate Reactions over PdCu and PdAg Catalysts: Distinguishing Electronic and Geometric Effects on Reactivity and Selectivity

Oxygenate Reactions over PdCu and PdAg Catalysts: Distinguishing Electronic and Geometric Effects on Reactivity and Selectivity

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