Methanol as a clean and efficient H-transfer reactant for carbonyl reduction: Scope, limitations, and reaction mechanism

Pasini, Thomas; Lolli, Alice; Albonetti, Stefania; Cavani, Fabrizio; Mella, Mariella

doi:10.1016/j.jcat.2014.06.023

Cited by 77 publications

(65 citation statements)

References 144 publications

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“…[29] The reaction (DE) and transition state (TS) energetics for ethanol dehydrogenation with respect to two alternative energy zeros are shown in Table 2; the optimised stationary points are shown in Figure 6.…”

Section: Alcohol Dehydrogenationmentioning

confidence: 99%

On the Chemistry of Ethanol on Basic Oxides: Revising Mechanisms and Intermediates in the Lebedev and Guerbet reactions

et al. 2014

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A common way to convert ethanol into chemicals is by upgrading it over oxide catalysts with basic features; this method makes it possible to obtain important chemicals such as 1-butanol (Guerbet reaction) and 1,3-butadiene (Lebedev reaction). Despite their long history in chemistry, the details of the close inter-relationship of these reactions have yet to be discussed properly. Our present study focuses on reactivity tests, in situ diffuse reflectance infrared Fourier transform spectroscopy, MS analysis, and theoretical modeling. We used MgO as a reference catalyst with pure basic features to explore ethanol conversion from its very early stages. Based on the obtained results, we formulate a new mechanistic theory able to explain not only our results but also most of the scientific literature on Lebedev and Guerbet chemistry. This provides a rational description of the intermediates shared by the two reaction pathways as well as an innovative perspective on the catalyst requirements to direct the reaction pathway toward 1-butanol or butadiene.

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Section: Alcohol Dehydrogenationmentioning

confidence: 99%

On the Chemistry of Ethanol on Basic Oxides: Revising Mechanisms and Intermediates in the Lebedev and Guerbet reactions

et al. 2014

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“…They found that Lewis acid catalysts could hydrogenate FF to FFA, and the combination of Lewis acid and Ru/C catalysts would further upgrade FF to methyl furan.H owever, Lewis acid catalysts were required in large excessc omparedt o FF and that excess was difficult to recover.C avani et al studied the liquid-phaset ransfer hydrogenation of FF and 5-hydroxymethylfurfural over ah igh-surface-area magnesium oxide catalyst. [29] Methanolw as used as both the hydrogen transfer reagent and the reactions olvent. However,i ta lso required al arge excess of catalyst.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol over Nitrogen‐Doped Carbon‐Supported Iron Catalysts

et al. 2016

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Iron-based heterogeneous catalysts, which were generally prepared by pyrolysis of iron complexes on supports at elevated temperature, were found to be capable of catalyzing the transfer hydrogenation of furfural (FF) to furfuryl alcohol (FFA). The effects of metal precursor, nitrogen precursor, pyrolysis temperature, and support on catalytic performance were examined thoroughly, and a comprehensive study of the reaction parameters was also performed. The highest selectivity of FFA reached 83.0 % with a FF conversion of 91.6 % under the optimal reaction condition. Catalyst characterization suggested that iron cations coordinated by pyridinic nitrogen functionalities were responsible for the enhanced catalytic activity. The iron catalyst could be recycled without significant loss of catalytic activity for five runs, and the destruction of the nitrogen-iron species, the presence of crystallized Fe2 O3 phase, and the pore structure change were the main reasons for catalyst deactivation.

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“…The type of solvent is an important parameter of the process. The formation of FA from Fur [107][108][109], and the conversion of LEs to GVL involve reduction chemistry (CTH) [72,110], where the solvent can simultaneously act as H-donor reagent [111,112]. 2BuOH and 2-propanol (2PrOH) are considered favourable H-donor solvents, which may avoid side reactions [110,111].…”

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confidence: 99%

One-pot conversion of furfural to useful bio-products in the presence of a Sn,Al-containing zeolite beta catalyst prepared via post-synthesis routes

Antunes

Lima

Neves

et al. 2015

Journal of Catalysis

133

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Aiming at the valorisation of furfural (Fur) via sustainable routes based on process intensification and heterogeneous catalysis, the one-pot conversion of this renewable platform chemical to useful bio-products, namely furfuryl alkyl ethers (FEs), levulinate esters (LEs), levulinic acid (LA), angelica lactones (AnLs) and -valerolactone (GVL), was investigated using a single heterogeneous catalyst, in 2-butanol, at 120 ºC. Various chemical 2 reactions are involved in this process, which requires catalysts with active sites for acid and reduction chemistry. For this purpose, it was explored for the first time the catalytic potentialities of modified versions of zeolite beta containing Al and Sn sites prepared from commercially available nanocrystaline zeolite beta via post-synthesis partial dealumination followed by solid-state ion-exchange. The post-synthesis conditions influenced considerably the catalytic performances of these types of materials. The best-performing catalyst was (Sn) SSIE -beta1 with Si/(Al+Sn)=19 (Sn/Al=27.6), which led to total yield of bio-products of 83% at 86% Fur conversion, and exhibited steady catalytic performance for six consecutive runs. A systematic catalytic study using the prepared catalysts with different bio-products as substrates, together with the molecular level and microstructural characterisation of the materials, helped understand the effects of different material properties on the specific reaction pathways in the overall system. These studies led to mechanistic insights into the reaction network of Fur to the bio-products in alcohol media, upon which a kinetic model was developed for the first time. The superior performance of (Sn) SSIE -beta1 in various steps was related to the dealumination degree, dispersion and amount of Sn-sites, and acid properties.

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Methanol as a clean and efficient H-transfer reactant for carbonyl reduction: Scope, limitations, and reaction mechanism

Cited by 77 publications

References 144 publications

On the Chemistry of Ethanol on Basic Oxides: Revising Mechanisms and Intermediates in the Lebedev and Guerbet reactions

On the Chemistry of Ethanol on Basic Oxides: Revising Mechanisms and Intermediates in the Lebedev and Guerbet reactions

Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol over Nitrogen‐Doped Carbon‐Supported Iron Catalysts

One-pot conversion of furfural to useful bio-products in the presence of a Sn,Al-containing zeolite beta catalyst prepared via post-synthesis routes

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