Ketonic decarboxylation and esterification of propionic acid over beta zeolites

Mitran, Gheorghița; Chen, Shaojiang; Dolge, Kevin; Huang, Wenyu; Seo, Dong Kyun

doi:10.1016/j.micromeso.2020.110628

Cited by 13 publications

(2 citation statements)

References 51 publications

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“…Furthermore, LAS have been shown to promote ketone formation, [1,2,12,21,79,[93][94][95][96][97] while BAS are suggested to play a role in the formation of undesired products, such as light hydrocarbons and short-chain alkanes, through reactant and product cracking. [1,[98][99][100] In-situ DRIFTS analysis of ammonia adsorption (as depicted in Figure 5 and Table 3) revealed that the Wh-TiO x sample exhibited the highest BAS, while the Bl-TiO x sample exhibited the highest LAS.…”

Section: Discussionmentioning

confidence: 99%

The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiO_x Catalysts

Yazdanpanah,

Fereidooni,

Márquez

et al. 2023

ChemSusChem

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Recently, interest in converting bio‐derived fatty acid methyl esters (FAMEs) into added‐value products has significantly increased. The selectivity of ketonization reaction in the conversion of the FAMEs has significantly hampered the efficiency of this process. Herein, we prepared catalysts with different levels of oxygen vacancies while the crystal phase remained unchanged. The catalyst with the highest level of oxygen vacancy exhibited the maximum selectivity. The density functional theory (DFT) simulation showed an increase in interatomic distances leading to the formation of frustrated Lewis pairs (FLPs) upon the creation of oxygen vacancies. The surface measurements, type and density of acid sites of the catalysts, showed that the Lewis acid sites enhanced the selectivity for ketone production; while Bronsted acid sites increased the formation of by‐products. Moreover, the ketone formation rate was directly proportional to acid density. The findings of this research provide a different approach for catalyst design, based on defects engineering and their effect on the surface activity, which could be used for enhancing the catalytic performance of novel metal oxides.

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Section: Discussionmentioning

confidence: 99%

The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiO_x Catalysts

Yazdanpanah,

Fereidooni,

Márquez

et al. 2023

ChemSusChem

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“…Various solid acids such as heteropoly acids, [3][4][5] zeolites, 6-8 clays, [9][10][11][12] and supported molybdena and vanadia 13,14 have been used for heterogeneous esterification. Among the zeolites, H⊎, HY and HZSM5 15,16 have been used as heterogeneous catalysts in the esterification of acetic acid and propionic acid with different alcohols (cyclohexanol, n-propanol, n-butanol, isopropanol, isobutanol). Nb2O5/SBA-15 catalyst has been used for propanoic acid esterification with methanol.…”

Section: Introductionmentioning

confidence: 99%

La‐H‐zeolites: efficient catalysts for acetic acid ketonic decarboxylation and esterification

Mitran

Chen

Huang

et al. 2021

J of Chemical Tech & Biotech

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BACKGROUND: Cyclohexyl acetate and acetone are used as environmentally friendly solvents, while isobutene acts as an intermediate in the production of methacrolein, ethers, plastics and pharmaceuticals. Two La-zeolite catalysts have been studied for converting acetic acid to cyclohexyl acetate, acetone and isobutene. RESULTS: La-based zeolites were synthesized from Na-nFAU zeolites by ammonium ion exchange, followed by lanthanum ion exchange. The influence of Brønsted and Lewis acid sites on the activity in acetic acid esterification with cyclohexanol and in ketonic decarboxylation of acetic acid was studied. Fourier transform infrared (FTIR) spectroscopy of pyridine adsorption has been used for acid site evaluation. The presence of Brønsted acid sites on the surface leads to an increase in cyclohexyl acetate and acetone selectivity, while the presence of Lewis acidity favors further transformation of acetone in isobutene.CONCLUSION: The sample with the highest Brønsted acidity and the highest content in both La and Al, namely La-H-13X, showed the highest activity for both acetic acid esterification and ketonic decarboxylationan indication that Brønsted acidity is very important for the studied reactions.

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Revealing the Mechanism of Ketonization of Acetic Acid on HBEA Zeolite via Metadynamics Simulations

Liu,

Zhao,

Liu

et al. 2024

ChemCatChem

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Ketonization of biomass‐derived carboxylic acids offers a promising approach to remove oxygen and upgrade into valuable chemicals. However, the mechanism on Brønsted acid site (BAS) confined in micropores of zeolite remains elusive, due to the difficulty to observe the reaction intermediates experimentally and to locate the transition state via static density functional theory (DFT) calculations. Herein, ketonization of acetic acid on HBEA at 673 K was studied by metadynamics simulations based on DFT. The first reaction step was the concerted protonation and dehydroxylation of acetic acid, resulting in an electrophilic acylium cation and H2O (ΔG‡ = 1.53 eV). The subsequent likely steps, including C‐C coupling through the nucleophilic attack of acetic acid (path I), ketene (path II), and 1,1‐dihydroxyethene and (path III) toward acylium cation were tracked and compared. The high barriers for formation of more nucleophilic intermediates of ketene and 1,1‐dihydroxyethene made the overall path II and III less favorable than the direct coupling between acetic acid and acylium cation (path I, ΔG‡ = 2.15 eV). These results indicate that acylium cation is a key intermediate, and the C‐C coupling between acetic acid and acylium cation via nucleophilic attach is the most favorable path on BAS confined in zeolite.

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Ketonic decarboxylation and esterification of propionic acid over beta zeolites

Cited by 13 publications

References 51 publications

The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiO_x Catalysts

The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiO_x Catalysts

La‐H‐zeolites: efficient catalysts for acetic acid ketonic decarboxylation and esterification

Revealing the Mechanism of Ketonization of Acetic Acid on HBEA Zeolite via Metadynamics Simulations

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Ketonic decarboxylation and esterification of propionic acid over beta zeolites

Cited by 13 publications

References 51 publications

The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiOx Catalysts

The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiOx Catalysts

La‐H‐zeolites: efficient catalysts for acetic acid ketonic decarboxylation and esterification

Revealing the Mechanism of Ketonization of Acetic Acid on HBEA Zeolite via Metadynamics Simulations

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The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiO_x Catalysts

The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiO_x Catalysts