Chemoselective hydrogenation of carbonyl compounds over heterogeneous catalysts

Mäki‐Arvela, Päivi; Hájek, Jan; Salmi, T.; Murzin, Dmitry Yu.

doi:10.1016/j.apcata.2005.05.045

Cited by 592 publications

(525 citation statements)

References 205 publications

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“…These results are in agreement with numerous literature studies reporting essentially exclusive formation of propanal over Pd nanoparticles in powdered catalysts. [3,12] In contrast to Pd nanoparticles, significant propenol production was observed over Pd(111), and the amount of propenol produced increased from almost zero at 220 K to a maximum at 270 K. The Pd(111) catalyst also produced a small amount of propanal at all three temperatures. The amount of propanal produced over Pd(111) was similar to that of propenol at 220 K. However, the selectivity towards propenol production increased with increasing temperature, and at 270 K, the Pd(111) catalyst was nearly 100% selective towards production of propenol.…”

Section: Influence Of Pd Particle Size and Temperature On Activity Anmentioning

confidence: 97%

Selective Hydrogenation of Acrolein Over Pd Model Catalysts: Temperature and Particle‐Size Effects

O’Brien

Dostert

Schauermann

et al. 2016

Chemistry A European J

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In this work, the selectivity in hydrogenation of acrolein over Fe3O4-supported Pd nanoparticles is investigated as a function of nanoparticle size in the 220-270 K temperature range. While Pd(111) shows nearly 100% selectivity towards the desired hydrogenation of the C=O bond to produce propenol, Pd nanoparticles were found to be much less selective towards this product.In-situ detection of surface species using infrared-reflection absorption spectroscopy shows that the selectivity towards propenol critically depends on the formation of an oxopropyl spectator species. While an overlayer of oxopropyl species is effectively formed on Pd(111) turning the surface highly selective for propenol formation, this process is strongly hindered on Pd nanoparticles by acrolein decomposition resulting in CO formation. We show that the extent of acrolein decomposition can be tuned by varying the particle size and the reaction temperature.As a result, significant production of propenol is observed over 12 nm Pd nanoparticles at 250 K, while smaller (4 and 7 nm) nanoparticles did not produce propenol at any of the temperatures 2 investigated. The possible origin of particle size dependence of propenol formation is discussed.This work demonstrates that the selectivity in hydrogenation of acrolein is controlled by the relative rates of acrolein partial hydrogenation to oxopropyl surface species and of acrolein decomposition, which has significant implications for rational catalyst design.3

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Section: Influence Of Pd Particle Size and Temperature On Activity Anmentioning

confidence: 97%

Selective Hydrogenation of Acrolein Over Pd Model Catalysts: Temperature and Particle‐Size Effects

O’Brien

Dostert

Schauermann

et al. 2016

Chemistry A European J

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“…The main route for their synthesis is the selective hydrogenation of a,b-unsaturated carbonyl compounds. Conventional reduction of these compounds by gaseous dihydrogen over many metal catalysts results in preferable hydrogenation of the C=C bond [1][2][3][4][5]. Recently, metallic gold dispersed on FeOOH or c-Fe 2 O 3 has shown a remarkable chemoselectivity in the reduction of the conjugated C=O bond in the a,b-unsaturated carbonyl compounds [6,7].…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Alcohols in Chemoselective Transfer Hydrogenation of Acrolein over Magnesium Oxide as the Catalyst

Gliński

Ulkowska

2010

Catal Lett

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This paper presents the first full thermodynamic description of the hydrogen transfer between acrolein, the simplest a,b-unsaturated aldehyde, and a set of aliphatic alcohols, both primary and secondary. The vapour phase transfer hydrogenation of acrolein into allyl alcohol with various primary and secondary aliphatic alcohols used as hydrogen donors in the presence of MgO as the catalyst has been studied. Despite differentiated reactivity exhibited by these alcohols, a high chemoselectivity ([80%) to allyl alcohol has been observed for all of them. On the basis of thermodynamic calculations it has been found that secondary alcohols as hydrogen donors are more reactive than primary ones. However, ethanol or butan-1-ol have shown the highest reactivity. In their presence yields of allyl alcohol higher than 60% have been noted, which greatly exceed those predicted by thermodynamic calculations based on the following equation: acrolein ? ethanol (butan-1-ol) ? allyl alcohol ? acetaldehyde (butyraldehyde). Although similar yields have been reported in literature, no subsequent nor side reactions have been discussed even though the attained yield cannot be accounted for by this reaction alone. As a possible explanation of the discrepancy the occurrence of a disregarded reaction, for which DG \ 0, has been considered. It has been shown that aldol condensation fulfills these thermodynamic requirements, however, the products of this reaction are noted only at the beginning of the process and the decrease of their amount does not influence the yield of allyl alcohol.

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“…Frequently, the addition of a second metal leads to more efficient systems that allow obtaining the desired product. 6 The liquid-phase hydrogenation of furfural has been studied using catalysts based on Ni, Co, Ru, Pd and, to a much lesser extent, Pt. Sometimes another metal or promoter is added to improve the catalytic performance of the systems.…”

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confidence: 99%

“…Besides, Ni, due to its low cost, is an interesting alternative, especially taking into account that there are numerous papers dealing with the hydrogenation of furfural employing Ni-based catalysts. 6 The monometallic catalysts M/SiO 2 (M = Pt, Rh, Ni) were characterized by atomic absorption spectrometry, temperature programmed reduction, H 2 and CO chemosorption and transmission electron microscopy. The results obtained are shown in Table 1.…”

mentioning

confidence: 99%

Transition metal-based bimetallic catalysts for the chemoselective hydrogenation of furfuraldehyde

Vetere

Merlo

Ruggera

et al. 2010

J. Braz. Chem. Soc.

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Neste trabalho foi estudada a hidrogenação quimiosseletiva em fase líquida do furfural, empregando-se catalisadores baseados em Pt, Rh e Ni. Sistemas bimetálicos, contendo diferentes quantidades de estanho, foram obtidos por meio de reações de superfície controlada entre um catalisador monometálico e Sn(C 4 H 9 ) 4 . Quando foram utilizados catalisadores monometálicos, os resultados obtidos sugerem uma relação entre as propriedades do metal e da atividade e seletividade. Todos os sistemas permitiram a obtenção do álcool furfurílico com alta seletividade (99, 97 e 76% com catalisadores de Pt, Rh e Ni, respectivamente). A adição de estanho tem efeitos diferentes sobre os três sistemas, tanto em termos de conversão quanto na seletividade. Um resultado interessante foi obtido para os catalisadores baseados em Ni, para os quais a adição de estanho levou a um aumento significativo da seletividade do álcool furfurílico e, dependendo da razão Sn/Ni, também há um aumento na atividade catalítica do sistema.In this work, the liquid-phase chemoselective hydrogenation of furfural was studied, employing Pt, Rh and Ni-based catalysts. Bimetallic systems, containing different amounts of tin, were obtained by means of controlled surface reactions between a monometallic catalyst and Sn(C 4 H 9 ) 4 . The results obtained when monometallic catalysts were employed suggest a relationship between metal properties and the activity and selectivity obtained. All systems allowed obtaining furfuryl alcohol with high selectivity (99, 97 and 76% were achieved with Pt, Rh and Ni catalysts, respectively). The addition of tin has different effects on the three systems, both in terms of conversion and selectivity. An interesting result was obtained for the Ni-based catalysts, for which the addition of tin led to a significant increase in furfuryl alcohol selectivity and, depending on the Sn/Ni ratio, also to an increase in the catalytic activity of the system. Keywords: furfural, furfuryl alcohol, hydrogenation, bimetallic catalysts, PtSn IntroductionThe hydrogenation of furfural is an important reaction in the chemical industry as it is the main way of obtaining furfuryl alcohol.1 This product is widely used in the production of resins, as an intermediate in the manufacture of lysine, vitamin C and lubricants, and to obtain tetrahydrofurfuryl alcohol, among other applications. [2][3][4] Due to the large variety of products that can be obtained from the hydrogenation of furfural, this reaction represents a great challenge from the point of view of its chemoselectivity. As shown in Figure 1, in addition to the products coming from the hydrogenation of the C=O bond and/or the furan ring, there are numerous compounds derived from side reactions (hydrogenolysis of the C=O bond, decarbonylation, hydrogenation and ring opening, condensation reactions, etc.). 3,5 In chemoselective hydrogenation reactions using heterogeneous catalysts, the choice of the active metal is a key factor, since its influence on the resulting activity and/or selectivity is wel...

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Chemoselective hydrogenation of carbonyl compounds over heterogeneous catalysts

Cited by 592 publications

References 205 publications

Selective Hydrogenation of Acrolein Over Pd Model Catalysts: Temperature and Particle‐Size Effects

Selective Hydrogenation of Acrolein Over Pd Model Catalysts: Temperature and Particle‐Size Effects

Reactivity of Alcohols in Chemoselective Transfer Hydrogenation of Acrolein over Magnesium Oxide as the Catalyst

Transition metal-based bimetallic catalysts for the chemoselective hydrogenation of furfuraldehyde

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