Aqueous-phase hydrogenation of furfural over supported palladium catalysts: effect of the support on the reaction routes

Mironenko, Roman M.; Talsi, V. P.; Gulyaeva, T. I.; Тренихин, М. В.; Belskaya, O. B.

doi:10.1007/s11144-018-1505-y

Cited by 41 publications

(19 citation statements)

References 49 publications

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“…Hence, the hydrogenation of furfural in aqueous medium to generate valuable chemicals is an attractive chemical transformation. Although there are precedents for FF hydrogenation in the field of heterogeneous catalysis, [81] processes in water are scarce and they require the use of H 2 under pressure [82,83] . We therefore decided to test the behavior of 1 because it was envisaged that the biphasic medium would allow easy separation and the use of H 2 would not be necessary.…”

Section: Resultsmentioning

confidence: 99%

A Water/Toluene Biphasic Medium Improves Yields and Deuterium Incorporation into Alcohols in the Transfer Hydrogenation of Aldehydes

et al. 2021

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Deuterium labeling is an interesting process that leads to compounds of use in different fields. We describe the transfer hydrogenation of aldehydes and the selective C 1 deuteration of the obtained alcohols in D 2 O, as the only deuterium source. Different aromatic, alkylic and α,β-unsaturated aldehydes were reduced in the presence of [RuCl(p-cymene)(dmbpy)]BF 4 , (dmbpy = 4,4'-dimethyl-2,2'-bipyridine) as the pre-catalyst and HCO 2 Na/HCO 2 H as the hydrogen source. Moreover, furfural and glucose, were selectively reduced to the valuable alcohols, furfuryl alcohol and sorbitol. The processes were carried out in neat water or in a biphasic water/toluene system. The biphasic system allowed easy recycling, higher yields, and higher selective D incorporation (using D 2 O/toluene). The deuteration took place due to an efficient effective M-H/D + exchange from D 2 O that allows the inversion of polarity of D + (umpolung). DFT calculations that explain the catalytic behavior in water are also included.

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Section: Resultsmentioning

confidence: 99%

A Water/Toluene Biphasic Medium Improves Yields and Deuterium Incorporation into Alcohols in the Transfer Hydrogenation of Aldehydes

et al. 2021

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“…In a typical experiment, 1 g of HPS granules (pretreated, dried and crushed to the size <60 μm) were impregnated with 3 mL of THF solution containing 0.071 g of Pd(CH 3 COO) 2 and 0.090 g of Cu(CH 3 COO) 2 ×H 2 O. The product was dried at 70 °C for 1 h and treated with 2.7 mL of the 0.3 M Na 2 CO 3 solution for precipitation of oxides/hydroxide NPs …”

Section: Methodsmentioning

confidence: 99%

“…The most frequently utilized noble metal catalysts in FF hydrogenation are based on Pd nanoparticles (NPs) stabilized by various supports such as carbons (non‐modified and chemically modified) and metal oxides (SiO 2 , Al 2 O 3 , MgAl oxides, etc. ), including mesoporous solids and those modified with transition metals (Ti, Zr, Sn) . The support can control the interactions between the metal surface and the furan ring, thus, controlling selectivity.…”

Section: Introductionmentioning

confidence: 99%

Selective Hydrogenation of Biomass‐Derived Furfural: Enhanced Catalytic Performance of Pd−Cu Alloy Nanoparticles in Porous Polymer

et al. 2020

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Here, the development of a new catalyst is reported for the selective furfural (FF) hydrogenation to furfuryl alcohol (FA) based on about 7 nm sized Pd−Cu alloy nanoparticles (NPs) formed in inexpensive, commercially available micro/mesoporous hypercrosslinked polystyrene (HPS). A comparison of the catalytic properties of as‐synthesized and reduced (denoted “r”) catalysts as well as Pd−Cu alloy and monometallic palladium NPs showed a considerable enhancement of the catalytic performance of Pd−Cu/HPS‐r compared to other catalysts studied, resulting in about 100 % FF conversion, 95.2 % selectivity for FA and a TOF of 1209 h−1. This was attributed to the enrichment of the NP surface with copper atoms, disrupting the furan ring adsorption, and to the presence of both zerovalent and cationic palladium and copper species, resulting in optimal hydrogen and FF adsorption. These factors along with exceptional stability of the catalyst in ten consecutive catalytic cycles make it highly promising in practical applications.

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“…It has been found that metal doping also leads to different adsorption configurations of the reactants determining intensity of hydrodeoxygenation reaction [76]. The influence of support and dispersion of metal on furfural hydrogenation were noticed also for Pd catalysts [77,78]. Silica-supported bimetallic Pd catalyst doped with Co or Cu showed enhanced reactivity compared to pure Pd in furfural hydrogenation due to decreased hydrogen surface coverage on catalyst surface of overlayer as compared to pure Pd [79].…”

Section: Products Of Reduction Of Furfural On 5%pd-1%au/sio 2 Systemsmentioning

confidence: 96%

“…In the pair of tautomers: 5-hydroxy-2-pentanone and 2-methyloxolan-2-ol in aqueous solution, the equilibrium is shifted towards creation of cyclic hemiketal. On the other hand, Mironenko et al [34,77] during research on the reduction of furfural in water over palladium catalysts supported on carbon materials under slightly severe conditions, identified as the main reaction products: hydroxy-2-pentanone and 4-oxopentanal and 5-hydroxy-2-pentanone, indicating the cyclic form 2-methyloxolan-2-ol as an intermediate product in small amount. These papers stated that the main direction of transformations of furfural over palladium catalysts at any pressure is the hydrolytic opening of the furan ring.…”

Section: Products Of Reduction Of Furfural On 5%pd-1%au/sio 2 Systemsmentioning

confidence: 99%

Bimetallic Pd-Au/SiO2 Catalysts for Reduction of Furfural in Water

et al. 2020

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Catalytic systems based on bimetallic Pd-Au particles deposited on SiO2 were prepared by ultrasonically assisted water impregnation and used in the hydrogenation of furfural obtained by the acidic hydrolysis of waste biomass (brewery’s spent grain) in aqueous phase. Pd-Au/SiO2 catalysts containing 50 g of Pd and 2–100 g of Au per 1 kg of catalyst were characterized by high activity in the studied process and, depending on the Pd/Au ratio, selectivity to 2-methyloxolan-2-ol. The modification of 5%Pd/SiO2 by Au leads to the formation of dispersed Au-Pd solid solution phases, which was confirmed by XRD, XPS, ToF-SIMS, SEM-EDS, and H2-TPR techniques. The effect of dilution of surface palladium by gold atoms is probably crucial for modification of the reaction mechanism and formation of 2-methyloxolan-2-ol as the main product.

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Aqueous-phase hydrogenation of furfural over supported palladium catalysts: effect of the support on the reaction routes

Cited by 41 publications

References 49 publications

A Water/Toluene Biphasic Medium Improves Yields and Deuterium Incorporation into Alcohols in the Transfer Hydrogenation of Aldehydes

A Water/Toluene Biphasic Medium Improves Yields and Deuterium Incorporation into Alcohols in the Transfer Hydrogenation of Aldehydes

Selective Hydrogenation of Biomass‐Derived Furfural: Enhanced Catalytic Performance of Pd−Cu Alloy Nanoparticles in Porous Polymer

Bimetallic Pd-Au/SiO2 Catalysts for Reduction of Furfural in Water

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