Phase composition and catalytic properties of ZrO2 and CeO2-ZrO2 in the ketonization of pentanoic acid to 5-nonanone

Шутилов, А. А.; Simonov, Mikhail; Zaytseva, Yu. A.; Зенковец, Г. А.; Simakova, Irina L.

doi:10.1134/s0023158413020134

Cited by 21 publications

(26 citation statements)

References 18 publications

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“…In a related study, Nagashima et al successfully demonstrated ketonic decarboxylation of propanoic acid using CeO x -based composite oxides [12]. Shutilov and co-workers researched the production of 5-nonanone from pentanoic acid using different zirconium catalysts and found that CeO 2 -ZrO 2 yielded maximum conversion and selectivity of 93.2% and 78.7%, respectively [13]. A comprehensive study of ketonic decarboxylation from hexanoic acid mediated by weakly basic ceria/zirconia catalysts was undertaken by Gaertner and colleagues [14].…”

Section: Introductionmentioning

confidence: 99%

Ketone Formation via Decarboxylation Reactions of Fatty Acids Using Solid Hydroxide/Oxide Catalysts

Smith

Perera-Solis

et al. 2018

Inorganics

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A sustainable route to ketones is described where stearone is produced via ketonic decarboxylation of stearic acid mediated by solid base catalysts in yields of up to 97%, at 250 °C. A range of Mg/Al layered double hydroxide (LDH) and mixed metal oxide (MMO) solid base catalysts were prepared with Mg/Al ratios of between 2 and 6 via two synthetic routes, co-precipitation and co-hydration, with each material tested for their catalytic performance. For a given Mg/Al ratio, the LDH and MMO materials showed similar reactivity, with no correlation to the method of preparation. The presence of co-produced oxide phases in the co-hydration catalysts had negligible impact on reactivity.

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Section: Introductionmentioning

confidence: 99%

Ketone Formation via Decarboxylation Reactions of Fatty Acids Using Solid Hydroxide/Oxide Catalysts

Smith

Perera-Solis

et al. 2018

Inorganics

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“…ZrO 2 possessed a mixed phase, with monoclinic and tetragonal; whereas La x Zr y O z displayed a tetragonal phase. This indicated that the improvement of stability was caused by the phase transformation, and the higher activity was due to the greater acetic acid surface concentration.The study of carboxylic acid ketonization over ZrO 2 and the modified ZrO 2 catalysts was also performed in the vapor phase [26,31,34,36,37]. Parida et al studied acetic acid ketonization over alkali-metal cations promoted ZrO 2 at 623-698 K [31].…”

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confidence: 99%

“…They reported that Na was the most effective promoter, probably due to the crystal phase conversion from m-ZrO 2 to t-ZrO 2 through adding Na. Shutilov et al reported that 10 wt% CeO 2 supported on ZrO 2 showed the highest activity of pentanoic acid ketonization at 355 • C among 5-20 wt% CeO 2 / ZrO 2 [36]. The modification by CeO 2 led to the formation of Ce-Zr solid solution based on t-ZrO 2 .…”

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confidence: 99%

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Effect of Zirconia Polymorph on Vapor-Phase Ketonization of Propionic Acid

Ding

Zhao

2019

Catalysts

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Vapor-phase ketonization of propionic acid derived from biomass was studied at 300-375 • C over ZrO 2 with different zirconia polymorph. The tetragonal ZrO 2 (t-ZrO 2 ) are more active than monoclinic ZrO 2 (m-ZrO 2 ). The results of characterizations from X-ray diffraction (XRD) and Raman suggest m-ZrO 2 and t-ZrO 2 are synthesized by the solvothermal method. NH 3 and CO 2 temperature-programmed desorption (NH 3 -TPD and CO 2 -TPD) measurements show that there were more medium-strength Lewis acid base sites with lower coordination exposed on m-ZrO 2 relative to t-ZrO 2 , increasing the adsorption strength of propionic acid. The in situ DRIFTS (Diffuse reflectance infrared Fourier transform spectroscopy) of adsorbed propionic acid under ketonization reaction reveal that as the most abundant surface intermediates, the monodentate propionates are more active than bidentate propionates. In comparison with m-ZrO 2 , the t-ZrO 2 surface favors monodentate adsorption over bidentate adsorption. Additionally, the adsorption strength of monodentate propionate is weaker on t-ZrO 2 . These differences in adsorption configuration and adsorption strength of propionic acid are affected by the zirconia structure. The higher surface concentration and weaker adsorption strength of monodentate propionates contribute to the higher ketonization rate in the steady state.Catalysts 2019, 9, 768 2 of 15 coordination of Ti 4+ cations exposed on the surface. Stubenrauch et al. studied the reaction of formic acid and acetic acid on CeO 2 (111) and (100) surface [24]. On both surfaces, CH 2 CO was produced through acetic acid dehydration near 600 K. However, acetone was detected only on the (111) surface during acetic acid decomposition at 600 K. This result is different from that obtained by Kim et al., since Ce 4+ cations of (111) surface possess one vacancy relative to the Ce 4+ cations in the bulk. Wang et al. carried out ketonization of carboxylic acid on anatase and rutile TiO 2 , monoclinic and tetragonal ZrO 2 at 503-533 K [25,26]. They showed that the reaction activity of acetic acid was higher over anatase TiO 2 than that over rutile TiO 2 , and attributed that to the more reactive monodentate acetate present on anatase TiO 2 , whereas unreactive bidentate acetate was present on rutile TiO 2 . The effect of different nanocrystals (nanocubes, nanorods and nanopolyhedra) of CeO 2 on acetic acid ketonization was studied by Snell et al. at 503 K in the condensed phase and at 623 K in the vapor phase [27]. They found that the crystal of CeO 2 was disrupted in the condensed phase with the formation of metal carboxylate, whereas the bulk structure was maintained during the vapor phase reaction. They suggested that the morphology of CeO 2 did not have a critical influence on the reaction activity in the condensed and vapor phase. Although some work has been done on the influence of the structure, no consensus has been reached. This may be due to the different reaction conditions (condensed phase and vapor phase) via the different reaction...

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“…It has been suggested that the addition of Ru helps to enhance the reducibility of TiO 2 and that this should result in the easier formation of coordinatively unsaturated Ti 3+ sites [14]. A similar effect has been suggested for ZrO 2 due to the presence of Zr 3+ ions [44,45]. The problem has been investigated by studying the adsorption of Ru 1 (atoms) and Ru 10 (clusters) on the most stable (101) surfaces of both TiO 2 and ZrO 2 oxides to identify the nature of the interaction of the metal with the support and to compare the behaviour of the two oxides [27].…”

Section: (A) Deposition Of Ru Clustersmentioning

confidence: 73%

TiO ₂ and ZrO ₂ in biomass conversion: why catalyst reduction helps

Tosoni

Chen

Puigdollers

et al. 2017

Phil. Trans. R. Soc. A.

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Biomass refers to plant-based materials that are not used for food or feed. As an energy source, lignocellulosic biomass (lignin, cellulose and hemicellulose) can be converted into various forms of biofuel using thermal, chemical and biochemical methods. Chemical conversion implies the use of solid catalysts, usually oxide materials. In this context, reducible oxides are considered to be more active than non-reducible oxides. But why? Using density functional theory DFT + U calculations with the inclusion of dispersion forces, we describe the properties of anatase TiO, a reducible oxide, and tetragonal ZrO, a non-reducible oxide, the (101) surfaces in this context. In particular, we focus on the role of surface reduction, either by direct creation of oxygen vacancies via O desorption, or by treatment in hydrogen. We show that the presence of reduced centres on the surface of titania or zirconia (either Ti or Zr ions, or oxygen vacancies) results in lower barriers and more stable intermediates in two key reactions in biomass catalytic conversion: ketonization of acetic acid (studied on ZrO) and deoxygenation of phenol (studied on TiO). We discuss the role of Ru nanoparticles in these processes, and in particular in favouring H dissociation and hydrogen spillover, which results in hydroxylated surfaces. We suggest that HO desorption from the hydroxylated surfaces may be a relevant mechanism for the regeneration of oxygen vacancies, in particular on low-coordinated sites of oxide nanoparticles. Finally, we discuss the role of nanostructuring in favouring oxide reduction, by discussing the properties of ZrO nanoparticles of diameter of about 2 nm.This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'.

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Phase composition and catalytic properties of ZrO2 and CeO2-ZrO2 in the ketonization of pentanoic acid to 5-nonanone

Cited by 21 publications

References 18 publications

Ketone Formation via Decarboxylation Reactions of Fatty Acids Using Solid Hydroxide/Oxide Catalysts

Ketone Formation via Decarboxylation Reactions of Fatty Acids Using Solid Hydroxide/Oxide Catalysts

Effect of Zirconia Polymorph on Vapor-Phase Ketonization of Propionic Acid

TiO ₂ and ZrO ₂ in biomass conversion: why catalyst reduction helps

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Phase composition and catalytic properties of ZrO2 and CeO2-ZrO2 in the ketonization of pentanoic acid to 5-nonanone

Cited by 21 publications

References 18 publications

Ketone Formation via Decarboxylation Reactions of Fatty Acids Using Solid Hydroxide/Oxide Catalysts

Ketone Formation via Decarboxylation Reactions of Fatty Acids Using Solid Hydroxide/Oxide Catalysts

Effect of Zirconia Polymorph on Vapor-Phase Ketonization of Propionic Acid

TiO 2 and ZrO 2 in biomass conversion: why catalyst reduction helps

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TiO ₂ and ZrO ₂ in biomass conversion: why catalyst reduction helps