Mechanistic insights into the catalytic transfer hydrogenation of furfural with methanol and alkaline earth oxides

Gyngazova, Maria S.; Grazia, Lorenzo; Lolli, Alice; Innocenti, Giada; Tabanelli, Tommaso; Mella, Mariella; Albonetti, Stefania; Cavani, Fabrizio

doi:10.1016/j.jcat.2019.02.020

Cited by 50 publications

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References 80 publications

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“…This strongly indicates that both BaO and SrO oxides have high predominance of the very strong basic sites. This confirms the well-known basicity strength order for alkaline earth oxides: BaO > SrO > CaO > MgO [33]. Code 01-084-1778) [33].…”

Section: Resultssupporting

confidence: 84%

“…This confirms the well-known basicity strength order for alkaline earth oxides: BaO > SrO > CaO > MgO [33]. Code 01-084-1778) [33]. The diffraction patterns of the AU modified material exhibit reflections peaks that originate from strontianite as well as the reflections peaks originated from Sr(OH)2 (Ref.…”

Section: Resultssupporting

confidence: 80%

“…Code 01-084-1778) [33]. The diffraction patterns of the AU modified material exhibit reflections peaks that originate from strontianite as well as the reflections peaks originated from Sr(OH) 2 [33]. The very high reactivity of SrO toward water could explain the presence of these hydrated compounds [33].…”

Section: Resultsmentioning

confidence: 99%

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Efficient Oxidative Esterification of Furfural Using Au Nanoparticles Supported on Group 2 Alkaline Earth Metal Oxides

et al. 2020

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Furfural (FF) is a strategic product for the development of highly valued chemicals from biomass. The oxidation product of FF, furoic acid (FA), is an important precursor for the synthesis of green esters, such as methyl furoate. Taking into account issues with the direct furfural oxidation, furfural derivatives, such as alkyl furoates, can be easily prepared via oxidative esterification.Here, Au nanoparticles that were immobilized on alkaline-earth metal oxide supports were studied for the oxidative esterification of furfural while using alcohol as both reactant and solvent. The formation of esters is favored by the presence of basic sites on catalyst surface, resulting in high selectivity, preventing the formation of the acetal as a by-product. The Au/MgO sample provided up to 95% methyl furoate (MF) yield, a fast reaction rate, and high performance for furfural:Au molar ratios between 50 and 300. Furthermore, this catalyst was stable during reuse, since both the selectivity and the activity were maintained after four cycles. Oxidative esterification products were achieved in the presence of other alcohols, leading to the formation of esters of up to C 5 (isopentyl furoate) with high selectivity (>99%). Linear and branched esters were formed, but the long-chain linear alcohols resulted in higher yields, such as n-butyl furoate in 94% yield.Catalysts 2020, 10, 430 2 of 14 considered to be one of the most important platform compounds in biorefineries of the future [8][9][10]. Several products that are obtained via HMF oxidation are of great interest for the polymer industry because their derivatives can be used as C6 monomers to replace petrochemical monomers [1-10]. For example, 2,5-furandicarboxylic acid (FDCA) is a monomer in the production of polyethylene 2,5-furandicarboxylate (PEF), being a green alternative to polyethylene terephthalate (PET) [11][12][13]. The direct use of FDCA in the industry is difficult due to its low solubility in most commonly used solvents. The furan-2,5-dimethylcarboxylate ester (FDMC) is actually more suitable for the subsequent polymerization reaction, thanks to its better solubility. For this reason, the development of catalytic systems that are capable of producing FDMC directly from the HMF has received much attention today. One alternative is the production of FDCA can be obtained from furoic acid (furfural oxidation product) via the Henkel reaction [13]. However, the use of Au catalysts can also be a viable alternative. FDCA can be obtained from furoic acid (furfural oxidation product) via the Henkel reaction [13]. Recently, Au catalysts have been successfully applied for the oxidative esterification of alcohols [14-17] and they have also been explored for the esterification of furfural and HMF [18][19][20][21][22][23][24][25][26][27][28]. The first example of HMF esterification to produce dimethyl-2-furoate (FDMC) required the use of a base (NaOMe) [29]. Although other catalytic systems have then been reported, there are few examples of successful Au catalytic systems for t...

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Section: Resultssupporting

confidence: 84%

Section: Resultssupporting

confidence: 80%

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Efficient Oxidative Esterification of Furfural Using Au Nanoparticles Supported on Group 2 Alkaline Earth Metal Oxides

et al. 2020

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“…To realize large-scale H 2 generation and achieve anodic chemical upgrade simultaneously,t he search for suitable platform molecules is of paramount importance. [15] The organic substrates mentioned above have ac omplex structure and high cost. However,m ethanol, as as aturated monohydric alcohol with as imple construction, is cheap and abundant.I ndustrially,i ti saraw material for an umber of chemicals such as acetic acid, formate, and formaldehyde.…”

Section: Introductionmentioning

confidence: 99%

Value‐Added Formate Production from Selective Methanol Oxidation as Anodic Reaction to Enhance Electrochemical Hydrogen Cogeneration

et al. 2020

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Electrolytic overall water splitting is a promising approach to produce H2, but its efficiency is severely limited by the sluggish kinetics of the oxygen evolution reaction (OER) and the low activity of current electrocatalysts. To solve these problems, in addition to the development of efficient precious‐metal catalysts, an effective strategy is proposed to replace the OER by the selective methanol oxidation reaction. Ni–Co hydroxide [NixCo1−x(OH)2] nanoarrays were obtained through a facile hydrothermal treatment as the bifunctional electrocatalysts for the co‐electrolysis of methanol/water to produce H2 and value‐added formate simultaneously. The electrocatalyst could catalyze selective methanol oxidation (≈1.32 V) with a significantly lower energy consumption (≈0.2 V less) than OER. Importantly, methanol was transformed exclusively to value‐added formate with a high Faradaic efficiency (selectivity) close to 100 %. Specifically, a cell voltage of only approximately 1.5 V was required to generate a current density of 10 mA cm−2. Furthermore, the Ni0.33Co0.67(OH)2/Ni foam nanoneedle arrays presented an outstanding stability for overall co‐electrolysis.

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“…Indeed, H 2 O is formed along with FDEA. Finally, the band at 1290 cm −1 is characteristic of the O−C‐O stretching vibration in diethyl acetals, which is usually caused by the formation of FDEA in the acetalization of FFR and its absorption onto the surface of the material …”

Section: Resultsmentioning

confidence: 99%

An Efficient Acetalization Method for Biomass‐Derived Furfural with Ethanol Using γ‐Al₂O₃‐Supported Catalysts

2020

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In this paper, the mono and bimetallic catalysts of Rh, Pt and Ni supported on γ‐Al2O3 were tested for the selective acetalization of furfural to produce furfural diethyl acetal in a mixture containing furfural diluted in ethanol. Ni1.5Rh1.5/γ‐Al2O3 exhibited the highest catalytic activity among all the tested catalysts, with an 85% furfural conversion and 100% furfural diethyl acetal selectivity at 100 °C and 30 min of reaction. Catalyst characterization showed that Ni1.5Rh1.5/γ‐Al2O3 presented particle sizes smaller than 1.2 nm, and the active metals were partially oxidized (RhIII and NiII). A direct correlation between conversion and weak acidity of mono and bimetallic catalysts was obtained. Interestingly, despite exhibiting strong acidity, γ‐Al2O3 alone was little active in the process, which evidenced the role of the metal in acetalization of furfural into ethanol. In‐situ DRIFTS experiments indicated that furfural is easily adsorbed onto these small particles as Niδ+‐(η1‐O,C‐FFR) and Rhδ+‐ethoxide species and rapidly transforms into furfural diethyl acetal and water. The catalyst was recycled four times, with a loss in catalytic activity of approximately 19%. The Ni1.5Rh1.5/γ‐Al2O3 catalyst was also successfully applied in the condensation of a variety of biomass derivatives.

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Mechanistic insights into the catalytic transfer hydrogenation of furfural with methanol and alkaline earth oxides

Cited by 50 publications

References 80 publications

Efficient Oxidative Esterification of Furfural Using Au Nanoparticles Supported on Group 2 Alkaline Earth Metal Oxides

Efficient Oxidative Esterification of Furfural Using Au Nanoparticles Supported on Group 2 Alkaline Earth Metal Oxides

Value‐Added Formate Production from Selective Methanol Oxidation as Anodic Reaction to Enhance Electrochemical Hydrogen Cogeneration

An Efficient Acetalization Method for Biomass‐Derived Furfural with Ethanol Using γ‐Al₂O₃‐Supported Catalysts

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Mechanistic insights into the catalytic transfer hydrogenation of furfural with methanol and alkaline earth oxides

Cited by 50 publications

References 80 publications

Efficient Oxidative Esterification of Furfural Using Au Nanoparticles Supported on Group 2 Alkaline Earth Metal Oxides

Efficient Oxidative Esterification of Furfural Using Au Nanoparticles Supported on Group 2 Alkaline Earth Metal Oxides

Value‐Added Formate Production from Selective Methanol Oxidation as Anodic Reaction to Enhance Electrochemical Hydrogen Cogeneration

An Efficient Acetalization Method for Biomass‐Derived Furfural with Ethanol Using γ‐Al2O3‐Supported Catalysts

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An Efficient Acetalization Method for Biomass‐Derived Furfural with Ethanol Using γ‐Al₂O₃‐Supported Catalysts