Ketones from monocarboxylic acids: Catalytic ketonization over oxide systems

Gliński, Marek; Kijeński, J.; Jakubowski, A.

doi:10.1016/0926-860x(95)00082-8

Cited by 170 publications

(153 citation statements)

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“…Since previously reported research examining the stability of ceria in the ketonization reaction was performed at temperatures at or greater than 300°C, the lack of bulk transformation would be expected. 9,13 From the results in the current work, it is apparent that the lack of carboxylate formation in the bulk at high temperatures is not the result of metal−oxygen bond strength differences. Therefore, this material property alone does not dictate the route for the ketonization reaction pathway.…”

Section: Resultsmentioning

confidence: 67%

“…Given these results, the authors proposed that the reaction mechanism was different for low-temperature ketonization, which purportedly progressed through the pyrolytic route, from that at high temperatures, which catalyzed the reaction through the use of both acid and base surface sites. 7 In a large screening study of metal oxides in the ketonization reaction, ceria was found to be a ketonization catalyst superior to MgO, 9 and ceria has been the focus of a number of studies.…”

Section: Introductionmentioning

confidence: 99%

“…9 In particular, we examined the question of bulk transformation versus surface adsorption for ceria.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Insights into the Ceria-Catalyzed Ketonization Reaction for Biofuels Applications

Snell¹,

Shanks

2013

ACS Catal.

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The ketonization of small organic acids is a valuable reaction for biorenewable applications. Ceria has long been used as a catalyst for this reaction; however, under both liquid and vapor phase conditions, it was found that given the right temperature regime of about 150-300 °C, cerium oxide, which was previously believed to be a stable catalyst for ketonization, can undergo bulk transformations. This result, along with other literature reports, suggest that the long held belief of two separate reaction pathways for either bulk or surface ketonization reactions are not required to explain the interaction of cerium oxide with organic acids. X-ray photon spectroscopy, scanning electron microscopy, and temperature programmed decomposition results supported the formation of metal acetates and explained the occurrence of cerium reduction as well as the formation of cerium oxide/acetate whiskers. After thermogravimetry/mass spectrometry and FT-IR experiments, a single reaction sequence is proposed that can be applied to either surface or bulk reactions with ceria. ABSTRACT: The ketonization of small organic acids is a valuable reaction for biorenewable applications. Ceria has long been used as a catalyst for this reaction; however, under both liquid and vapor phase conditions, it was found that given the right temperature regime of about 150−300°C, cerium oxide, which was previously believed to be a stable catalyst for ketonization, can undergo bulk transformations. This result, along with other literature reports, suggest that the long held belief of two separate reaction pathways for either bulk or surface ketonization reactions are not required to explain the interaction of cerium oxide with organic acids. X-ray photon spectroscopy, scanning electron microscopy, and temperature programmed decomposition results supported the formation of metal acetates and explained the occurrence of cerium reduction as well as the formation of cerium oxide/acetate whiskers. After thermogravimetry/mass spectrometry and FT-IR experiments, a single reaction sequence is proposed that can be applied to either surface or bulk reactions with ceria.

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Section: Resultsmentioning

confidence: 67%

Section: Introductionmentioning

confidence: 99%

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Insights into the Ceria-Catalyzed Ketonization Reaction for Biofuels Applications

Snell¹,

Shanks

2013

ACS Catal.

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“…[62][63][64][65][66][67][68][69][70] Symmetrical ketones such as 3-pentanone, 6-undecanone, and 7-tridecanone have been obtained from ketonization of the appropriate acids. [62,65] This method was applied to the synthesis of nonsymmetrical ketones used as raw materials for pesticides and pharmaceutical products. [66][67][68] For example, methylcyclopropylketone and methylnonylketone were produced by the condensation of acetic acid with cyclopropanecarboxilic acid and decanoic acid, respectively.…”

Section: Acid Condensationmentioning

confidence: 99%

Ceria‐Based Solid Catalysts for Organic Chemistry

Vivier¹,

Duprez²

2010

ChemSusChem

357

244

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Ceria has been the subject of thorough investigations, mainly because of its use as an active component of catalytic converters for the treatment of exhaust gases. However, ceria‐based catalysts have also been developed for different applications in organic chemistry. The redox and acid–base properties of ceria, either alone or in the presence of transition metals, are important parameters that allow to activate complex organic molecules and to selectively orient their transformation. Pure ceria is used in several organic reactions, such as the dehydration of alcohols, the alkylation of aromatic compounds, ketone formation, and aldolization, and in redox reactions. Ceria‐supported metal catalysts allow the hydrogenation of many unsaturated compounds. They can also be used for coupling or ring‐opening reactions. Cerium atoms can be added as dopants to catalytic system or impregnated onto zeolites and mesoporous catalyst materials to improve their performances. This Review demonstrates that the exceptional surface (and sometimes bulk) properties of ceria make cerium‐based catalysts very effective for a broad range of organic reactions.

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“…8 However, ceria-based catalysts are commonly believed to be among the best for the reaction. 9,10 Recently, mixed ceria−zirconia materials have found promising application as ketonization catalysts in the upgrading of biomass-derived intermediates to fuels.…”

Section: Introductionmentioning

confidence: 99%

CeMO_x-Promoted Ketonization of Biomass-Derived Carboxylic Acids in the Condensed Phase

Snell

Shanks

2014

ACS Catal.

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Ketonization of the model bio-oil compound acetic acid was performed in a toluene-solvent condensed phase using five different CeMOx catalysts. The catalysts were characterized using a number of different techniques both before and after reaction testing to gain understanding of how material traits influence their catalytic performance. A number of potentially important catalytic properties were found to be of little importance for the respective reaction. For instance, it was discovered that there was no direct correlation between prereaction surface area with activity for ketonization at high or at low temperatures. Furthermore, better reducibility of the oxide did not appear to correlate with improved ketonization rates. XRD of postreaction materials used at different temperatures demonstrated the reaction temperature regime influenced whether the crystal structure of the fresh mixed oxide was disrupted. The precise temperature regimes were different, depending on composition of the catalytic material. Catalytic activity was then found to be maximized when metal carboxylate formation and subsequent decomposition of the carboxylate were appropriately balanced. ABSTRACT: Ketonization of the model bio-oil compound acetic acid was performed in a toluene-solvent condensed phase using five different CeMO x catalysts. The catalysts were characterized using a number of different techniques both before and after reaction testing to gain understanding of how material traits influence their catalytic performance. A number of potentially important catalytic properties were found to be of little importance for the respective reaction. For instance, it was discovered that there was no direct correlation between prereaction surface area with activity for ketonization at high or at low temperatures. Furthermore, better reducibility of the oxide did not appear to correlate with improved ketonization rates. XRD of postreaction materials used at different temperatures demonstrated the reaction temperature regime influenced whether the crystal structure of the fresh mixed oxide was disrupted. The precise temperature regimes were different, depending on composition of the catalytic material. Catalytic activity was then found to be maximized when metal carboxylate formation and subsequent decomposition of the carboxylate were appropriately balanced.

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Ketones from monocarboxylic acids: Catalytic ketonization over oxide systems

Cited by 170 publications

References 4 publications

Insights into the Ceria-Catalyzed Ketonization Reaction for Biofuels Applications

Insights into the Ceria-Catalyzed Ketonization Reaction for Biofuels Applications

Ceria‐Based Solid Catalysts for Organic Chemistry

CeMO_x-Promoted Ketonization of Biomass-Derived Carboxylic Acids in the Condensed Phase

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Ketones from monocarboxylic acids: Catalytic ketonization over oxide systems

Cited by 170 publications

References 4 publications

Insights into the Ceria-Catalyzed Ketonization Reaction for Biofuels Applications

Insights into the Ceria-Catalyzed Ketonization Reaction for Biofuels Applications

Ceria‐Based Solid Catalysts for Organic Chemistry

CeMOx-Promoted Ketonization of Biomass-Derived Carboxylic Acids in the Condensed Phase

Contact Info

Product

Resources

About

CeMO_x-Promoted Ketonization of Biomass-Derived Carboxylic Acids in the Condensed Phase