The Effect of Ceria Content on the Acid–Base and Catalytic Characteristics of ZrO2–CeO2 Oxide Compositions in the Process of Ethanol to n-Butanol Condensation

Vlasenko, N. A.; Kyriienko, Pavlo I.; Yanushevska, Olena; Valihura, Karina V.; Soloviev, Sergiy O.; Strizhak, P. E.

doi:10.1007/s10562-019-02937-x

Cited by 30 publications

(25 citation statements)

References 51 publications

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“…20 It was also confirmed for the Guerbet coupling over ZrO 2 –CeO 2 compositions, wherein the ceria additive served as a stabilizer for the tetragonal ZrO 2 . 21…”

Section: Introductionmentioning

confidence: 99%

Yttria-Stabilized Zirconia as a High-Performance Catalyst for Ethanol to n-Butanol Guerbet Coupling

et al. 2019

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It has been shown that yttria-stabilized zirconia is an effective catalyst for ethanol to n-butanol Guerbet coupling. The variation of the calcination temperature allows an improvement in the catalytic characteristics of this material via stabilization of the tetragonal phase of zirconia, having higher basicity than the monoclinic one. The treatment of yttria-stabilized zirconia at an optimal calcination temperature of 500 °C induces the increase in surface basicity required for the aldol condensation step, along with a decrease in surface acidity, which is responsible for the side reaction such as ethylene formation. The catalyst obtained significantly exceeds in selectivity and n-butanol yield than individual zirconia and other oxide systems which have been studied in this reaction.

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“…20 It was also confirmed for the Guerbet coupling over ZrO 2 –CeO 2 compositions, wherein the ceria additive served as a stabilizer for the tetragonal ZrO 2 . 21…”

Section: Introductionmentioning

confidence: 99%

Yttria-Stabilized Zirconia as a High-Performance Catalyst for Ethanol to n-Butanol Guerbet Coupling

et al. 2019

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“…The acid-base and redox properties of ceria-based materials have been extensively investigated because the unique catalytic activity enables ceria to catalyze a variety of organic reactions [55][56][57][58]. The surface of ceria is characterized by very low Lewis and Brönsted acid site density and weak acid strength [39], while at the same time extremely high density [59] of strong Lewis-base sites [60], which interact with carboxylic acids to form different types of carboxylates (monodentate, bidentate: chelate and bridge) [40,41,61].…”

Section: Kinetic Studymentioning

confidence: 99%

Catalytic Pyrolysis of Aliphatic Carboxylic Acids into Symmetric Ketones over Ceria-Based Catalysts: Kinetics, Isotope Effect and Mechanism

2020

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Ketonization is a promising way for upgrading bio-derived carboxylic acids from pyrolysis bio-oils, waste oils, and fats to produce high value-added chemicals and biofuels. Therefore, an understanding of its mechanism can help to carry out the catalytic pyrolysis of biomass more efficiently. Here we show that temperature-programmed desorption mass spectrometry (TPD-MS) together with linear free energy relationships (LFERs) can be used to identify catalytic pyrolysis mechanisms. We report the kinetics of the catalytic pyrolysis of deuterated acetic acid and a reaction series of linear and branched fatty acids into symmetric ketones on the surfaces of ceria-based oxides. A structure–reactivity correlation between Taft’s steric substituent constants Es* and activation energies of ketonization indicates that this reaction is the sterically controlled reaction. Surface D3-n-acetates transform into deuterated acetone isotopomers with different yield, rate, E≠, and deuterium kinetic isotope effect (DKIE). The obtained values of inverse DKIE together with the structure–reactivity correlation support a concerted mechanism over ceria-based catalysts. These results demonstrate that analysis of Taft’s correlations and using simple equation for estimation of DKIE from TPD-MS data are promising approaches for the study of catalytic pyrolysis mechanisms on a semi-quantitative level.

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“… 10 − 20 Much effort has been made to improve catalytic performance, through modifying the availability or strength of acid and base sites, geometry and coordination of metal ions, or extent of reduction or through mixing different oxides. 12 , 18 , 21 − 25 The use of different oxides and different reaction conditions, and possibly co-catalysts (e.g., Cu, Pd) 15 , 26 or co-reactants (e.g., H 2 , alcohols), 17 , 26 , 27 complicates a comprehensive understanding of the mechanism of this catalytic reaction and the factors that control its activity and selectivity. Different steps including enolization (C–H bond scission at the α position to the carbonyl group) and C–C coupling have been found to be rate-determining in the literature, with different reaction orders and either the presence or absence of the kinetic isotope effect reported.…”

Section: Introductionmentioning

confidence: 99%

Elucidating the Mechanism of Ambient-Temperature Aldol Condensation of Acetaldehyde on Ceria

et al. 2021

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Using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations, we conclusively demonstrate that acetaldehyde (AcH) undergoes aldol condensation when flown over ceria octahedral nanoparticles, and the reaction is desorption-limited at ambient temperature. trans -Crotonaldehyde (CrH) is the predominant product whose coverage builds up on the catalyst with time on stream. The proposed mechanism on CeO 2 (111) proceeds via AcH enolization (i.e., α C–H bond scission), C–C coupling, and further enolization and dehydroxylation of the aldol adduct, 3-hydroxybutanal, to yield trans -CrH. The mechanism with its DFT-calculated parameters is consistent with reactivity at ambient temperature and with the kinetic behavior of the aldol condensation of AcH reported on other oxides. The slightly less stable cis -CrH can be produced by the same mechanism depending on how the enolate and AcH are positioned with respect to each other in C–C coupling. All vibrational modes in DRIFTS are identified with AcH or trans -CrH, except for a feature at 1620 cm –1 that is more intense relative to the other bands on the partially reduced ceria sample than on the oxidized sample. It is identified to be the C=C stretch mode of CH 3 CHOHCHCHO adsorbed on an oxygen vacancy. It constitutes a deep energy minimum, rendering oxygen vacancies an inactive site for CrH formation under given conditions.

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The Effect of Ceria Content on the Acid–Base and Catalytic Characteristics of ZrO2–CeO2 Oxide Compositions in the Process of Ethanol to n-Butanol Condensation

Cited by 30 publications

References 51 publications

Yttria-Stabilized Zirconia as a High-Performance Catalyst for Ethanol to n-Butanol Guerbet Coupling

Yttria-Stabilized Zirconia as a High-Performance Catalyst for Ethanol to n-Butanol Guerbet Coupling

Catalytic Pyrolysis of Aliphatic Carboxylic Acids into Symmetric Ketones over Ceria-Based Catalysts: Kinetics, Isotope Effect and Mechanism

Elucidating the Mechanism of Ambient-Temperature Aldol Condensation of Acetaldehyde on Ceria

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