Ethanol dehydrogenation on copper catalysts with ytterbium stabilized tetragonal ZrO2 support

Chuklina, Sofia G.; Пылинина, А. И.; Подзорова, Л. И.; Mikhailina, N. A.; Михаленко, И. И.

doi:10.1134/s0036024416120074

Cited by 7 publications

(5 citation statements)

References 15 publications

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“…Many research groups have found Cu catalysts to be highly active for ethanol dehydrogenation, revealing selectivities towards acetaldehyde of almost 100% in some cases [16][17][18][19][20][21][22][23][24][25]. A positive effect is reported when the Cu content increased in the range of 1-5 wt % [26]. Hanukovich et al [27] reported that the rate-determining step of ethanol dehydrogenation on Cu can be the fission of the O-H bond or that of the C α -H bond.…”

Section: N2 Sorptionmentioning

confidence: 99%

“…The last set of TAP experiments concerning ethanol dehydrogenation presented in this paper deals with the catalytic behavior of a Cu/C catalyst. Based on literature findings that Cu catalysts are distinguished by high selectivities towards acetaldehyde [16,18,20,22,24,26], it was assumed that using Cu might lead to a divergent reaction scheme. In this respect, Figure 10a presents the Ar-normalized transient responses to pulses of ethanol in Ar at temperatures between 100 • C and 250 • C on the Cu/C catalyst at an m/z-value of 31, representing ethanol.…”

Section: Experiments With Cu/cmentioning

confidence: 99%

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Ethanol Dehydrogenation: A Reaction Path Study by Means of Temporal Analysis of Products

et al. 2020

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Conventional fossil fuels such as gasoline or diesel should be substituted in the future by environmentally-friendly alternatives in order to reduce emissions in the transport sector and thus mitigate global warming. In this regard, iso-butanol is very promising as its chemical and physical properties are very similar to those of gasoline. Therefore, ongoing research deals with the development of catalytically-supported synthesis routes to iso-butanol, starting from renewably-generated methanol. This research has already revealed that the dehydrogenation of ethanol plays an important role in the reaction sequence from methanol to iso-butanol. To improve the fundamental understanding of the ethanol dehydrogenation step, the Temporal Analysis of Products (TAP) methodology was applied to illuminate that the catalysts used, Pt/C, Ir/C and Cu/C, are very active in ethanol adsorption. H2 and acetaldehyde are formed on the catalyst surfaces, with the latter quickly decomposing into CO and CH4 under the given reaction conditions. Based on the TAP results, this paper proposes a reaction scheme for ethanol dehydrogenation and acetaldehyde decomposition on the respective catalysts. The samples are characterized by means of N2 sorption and Scanning Transmission Electron Microscopy (STEM).

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Section: N2 Sorptionmentioning

confidence: 99%

Section: Experiments With Cu/cmentioning

confidence: 99%

Ethanol Dehydrogenation: A Reaction Path Study by Means of Temporal Analysis of Products

et al. 2020

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“…The specific BET surface areas of the A%Z mixed oxides calcined at 500 °C were 170 and 70 m 2 /g for A5CZ and A50CZ, respectively. [3] The specific BET surface area for the fresh AlÀ Zr mixed oxides prepared under a similar condition was reported 69.8-126.3 m 2 /g at 550 °C [5] and 104.2 m 2 /g for samples syn- °C (previous work [36] ). (&) -t-zirconia, (*) -γ-alumina.…”

Section: Resultsmentioning

confidence: 58%

“… XRD patterns of samples from A5CZ to A75CZ heated at 500 °C (a) and A5CZ samples (b) prepared at 180 °C, 500 °C (this study), and 950 °C (previous work [36] ). (▪) – t‐zirconia, (•) – γ‐alumina.…”

Section: Resultsmentioning

confidence: 77%

Selectivity of Ethanol Conversion on Al/Zr/Ce Mixed Oxides: Dehydration and Dehydrogenation Pathways Based on Surface Acidity Properties

et al. 2022

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Zirconia-alumina mixed oxides (Zr + Ce)O 2 À Al 2 O 3 with various mol. ratios (5, 10, 20, 50, and 75 % alumina) were prepared using the sol-gel method. The catalysts were characterised via XRD, SEM, DTA/TG, BET, and FT-IR spectroscopy. The acidities of the catalysts were measured through the absorption of anthraquinone and pyridine probe molecules using EPR and IR spectroscopy, respectively. Catalytic activity and selectivity were investigated for ethanol conversion to acetaldehyde, ethylene, and diethyl ether, which were used as model reactions to identify surface-active sites. The relationship between the surface structure and the dehydration/dehydrogenation activity was evaluated. Diethyl ether formation is promoted by the presence of the ZrO 2 tetragonal phase at a low ZrO 2 /Al 2 O 3 ratio in the sample composition, at which the Lewis acid site has an aluminum-oxygen environment. The reaction mechanism was also discussed. In the low-temperature reaction region, dehydrogenation competes with dehydration; ethylene and acetaldehyde share a common reactive intermediate.

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“…From the Arrhenius plot of the rate constant (calculated from the results of each experiment) at each reaction temperature, the overall activation energy for ethanol conversion is E a = 82 kJ/mol. This value is in the range of activation energies (75–100 kJ/mol) for dehydrogenation reactions of short-chain (C1–C3) alcohols over different metals, − supporting ethanol dehydrogenation as the rate-limiting step in the reaction.…”

Section: Resultsmentioning

confidence: 67%

Condensed-Phase Ethanol Conversion to Higher Alcohols over Bimetallic Catalysts

Nezam

Zak

Miller

2020

Ind. Eng. Chem. Res.

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The catalytic condensation of ethanol to n-butanol and higher alcohols, known collectively as Guerbet reactions, has attracted attention in recent years as ethanol becomes increasingly available as a biorenewable feedstock. Results are presented here for the continuous, condensed-phase conversion of ethanol to higher alcohols using Ni/La2O3/γ-Al2O3 catalysts and for catalysts containing a second metal (Cu, Co, Pd, Pt, Fe, Mo) in addition to nickel. Detailed characterization of the catalyst surface and bulk properties has been carried out and is correlated to catalyst activity and selectivity. The best results obtained for nickel catalysts are a selectivity to higher alcohols of 75–80% and a turnover frequency of 200 mol ethanol/mol Ni site/h at 230 °C. The addition of cobalt nearly doubles the ethanol conversion rate relative to Ni alone, with only a slight reduction in higher alcohol selectivity. Results of catalyst characterization, a simple kinetic model, and experiments with reaction intermediates support the initial dehydrogenation of ethanol as the rate-limiting step of the condensed-phase reaction.

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Ethanol dehydrogenation on copper catalysts with ytterbium stabilized tetragonal ZrO2 support

Cited by 7 publications

References 15 publications

Ethanol Dehydrogenation: A Reaction Path Study by Means of Temporal Analysis of Products

Ethanol Dehydrogenation: A Reaction Path Study by Means of Temporal Analysis of Products

Selectivity of Ethanol Conversion on Al/Zr/Ce Mixed Oxides: Dehydration and Dehydrogenation Pathways Based on Surface Acidity Properties

Condensed-Phase Ethanol Conversion to Higher Alcohols over Bimetallic Catalysts

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