Promotional effect of Fe on the performance of supported Cu catalyst for ambient pressure hydrogenation of furfural

Manikandan, Marimuthu; Venugopal, Ashok Kumar; Nagpure, Atul S.; Satyanarayana, C.V.V.; Raja, Thirumalaiswamy

doi:10.1039/c5ra24742j

Cited by 64 publications

(65 citation statements)

References 57 publications

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“…They got 51% of MF yield at 220 • C for 14 h under 90 bar of H 2 pressure (Table 1, entry 26). The promoting effect of Fe on Cu catalyst performance was also studied by Manikandan et al [136]. Cu-Fe/Al 2 O 3 catalyst, with 10 wt% of Fe, exhibited an excellent activity that led to high furfural conversion (>93%) and FA selectivity (>98%) under mild reaction conditions ( Table 1, entry 27).…”

Section: Introductionmentioning

confidence: 84%

Recent Advances in Catalytic Hydrogenation of Furfural

et al. 2019

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Furfural has been considered as one of the most promising platform molecules directly derived from biomass. The hydrogenation of furfural is one of the most versatile reactions to upgrade furanic components to biofuels. For instance, it can lead to plenty of downstream products, such as (tetrahydro)furfuryl alcohol, 2-methyl(tetrahydro)furan, lactones, levulinates, cyclopentanone(l), or diols, etc. The aim of this review is to discuss recent advances in the catalytic hydrogenation of furfural towards (tetrahydro)furfuryl alcohol and 2-methyl(tetrahydro)furan in terms of different non-noble metal and noble metal catalytic systems. Reaction mechanisms that are related to the different catalytic materials and reaction conditions are properly discussed. Selective hydrogenation of furfural could be modified not only by varying the types of catalyst (nature of metal, support, and preparation method) and reaction conditions, but also by altering the reaction regime, namely from batch to continuous flow. In any case, furfural catalytic hydrogenation is an open research line, which represents an attractive option for biomass valorization towards valuable chemicals and fuels.FA is a very important monomer for the synthesis of furan resins, which are widely used in thermoset polymer matrix composites, cements, adhesives, coatings, and casting/foundry resins. This molecule is also used as a non-reactive diluent for epoxy resin, a modifier for phenolic and urea resins, an oil well, and a carbon binder. Furthermore, the salt of FA is used in the synthesis of lysine, vitamin C, lubricants, and plasticizers [22,23]. Moreover, it should be highlighted that FA is also an important intermediate for the production of further hydrogenation products (as shown in Scheme 1), such as 2-methylfuran (MF), a potential alternative fuel with better combustion performance and higher Research Octane Number (RON = 103) than that of gasoline (RON = 96.8) [24]. In other applications, MF is used in perfume intermediates, chloroquine lateral chains in medical intermediates, and as a raw material for the production of chrysanthemate pesticides [25].Moreover, tetrahydrofurfuryl alcohol (THFA) can be used as a green solvent in the pharmaceutical industry and, in addition, it constitutes an outstanding intermediate to produce dihydropyran [26], pyridine [27], tetrahydrofuran, and pentan-1,5-diol [28][29][30]. Particularly, the latest molecule is an important monomer in the plastics industry. Furthermore, 2-methyltetrahydrofuran (MTHF) is quite engaging for its possible applications in organometallic chemistry, as well as in organic reactions that are related to organocatalysis, biotransformations, and biomass processing [31]. Catalysts 2019, 9, 796 3 of 33 Catalysts 2018, 8, x FOR PEER REVIEW 3 of 36 Scheme 1. Illustrative representation of reaction pathways in furfural hydrogenation.Other downstream products of furfural hydrogenation, such as (tetrahydro)furan [32], tetrahydrofurfural [33], lactones [34][35][36][37], levulinates [38,39], cyclopentanone...

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Section: Introductionmentioning

confidence: 84%

Recent Advances in Catalytic Hydrogenation of Furfural

et al. 2019

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“…Recently,F e-Cu/g-Al 2 O 3 was reported to be an effective catalystw ith 93 %f urfural conversion and 98 %s electivity to furfuryl alcohol. [17] Manikandan and coworkers showedt hat Fe and Cu are fully reduced to metal, and bimetallic Fe-Cu was formed at 673 K, which was observedb yu sing in situ powder XRD. They also show that Fe was responsible for the highr eactivity,a nd the selectivity was driven by Cu.…”

Section: Introductionmentioning

confidence: 95%

“…The catalyst was calcined at 1123 K and then added directly into a batch reactor without any prereduction, and it is claimed that the acidic centers in these Cu‐Fe catalysts are the active sites for the dehydration of furfuryl alcohol to 2‐methylfuran. Recently, Fe‐Cu/γ‐Al 2 O 3 was reported to be an effective catalyst with 93 % furfural conversion and 98 % selectivity to furfuryl alcohol . Manikandan and coworkers showed that Fe and Cu are fully reduced to metal, and bimetallic Fe‐Cu was formed at 673 K, which was observed by using in situ powder XRD.…”

Section: Introductionmentioning

confidence: 99%

Iron‐Promotion of Silica‐Supported Copper Catalysts for Furfural Hydrodeoxygenation

Sheng

Lobo

2016

ChemCatChem

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The catalytic hydrodeoxygenation of furfural is an important reaction for the production of biofuels because its product, 2‐methylfuran, has excellent fuel properties: it can be added easily to the existing gasoline pool and it is renewable and, therefore, carbon neutral. The reaction network of hydrodeoxygenation is a two‐step reaction from furfural to furfuryl alcohol and then to 2‐methylfuran. Silica‐supported Cu is a mild hydrogenation catalyst that is selective for the hydrogenation of the carbonyl group of furfural to furfuryl alcohol. We have found that Fe‐containing Cu‐based catalysts show much higher reactivity and very high selectivity towards 2‐methylfuran (85 %+). It is of interest to understand the structural and chemical effects of the Fe promotion (0.15 % w/w) over the Cu catalyst (1 % Cu w/w) and characterize the species responsible for the high hydrogenation performance. Our investigations indicate that after the catalyst is pretreated in hydrogen, Cu is reduced fully, whereas Fe is only reduced partially (a mixture of FeIII and FeII is observed). In situ diffuse reflectance infrared Fourier transform spectroscopy suggests that FeII species are present on the catalyst surface, as indicated by the adsorption of NO.

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“…Through DFT and kinetic studies, it was suggested that the oxophilicity of Fe facilitated the adsorption of FA through a η 2 ‐(C,O) surface species, which drove the reaction towards hydrogenolysis of the C=O bond . Additionally, very recent studies conducted with Cu–Fe supported on carbon and silica also demonstrated a synergistic effect between the more oxophilic Fe species and the more reduced Cu species for hydrogenation and hydrogenolysis of FUR . Temperature‐programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS) under ultra‐high vacuum conducted on Pt–Zn catalysts suggested a similar mechanism, in which Zn acted as the oxophilic metal and allowed for a tilted adsorption mode to be more prevalent on the catalyst surface .…”

Section: Introductionmentioning

confidence: 99%

“…[9,10] Additionally, very recents tudies conducted with Cu-Fe supported on carbon and silica also demonstrated as ynergistic effect between the more oxophilic Fe speciesa nd the more reduced Cu speciesf or hydrogenationa nd hydrogenolysis of FUR. [11,12] Te mperature-programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS) under ultrahigh vacuum conducted on Pt-Zn catalysts suggested as imilar mechanism, in which Zn acted as the oxophilicm etal and allowed for at ilted adsorption mode to be more prevalent on the catalyst surface. [13] Other vapor phase reactions have been conducted with multiple metal systemsi ncluding Cu-Zn-Al and Cu-Zn-Al-Ca-Na.…”

Section: Introductionmentioning

confidence: 99%

Vapor Phase Hydrogenolysis of Furanics Utilizing Reduced Cobalt Mixed Metal Oxide Catalysts

Sulmonetti

Ifkovits

et al. 2017

ChemCatChem

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Vapor phase hydrogenolysis of both furfuryl alcohol and furfural are investigated over reduced Co based mixed metal oxides derived from the calcination of a layered double hydroxide precursor. Although a reduced cobalt‐aluminum oxide sample displays promising selectivity towards 2‐methylfuran (2‐MF) production, the addition of an Fe dopant into the oxide matrix significantly enhances the activity and selectivity per gram of catalyst. Approximately 82 % 2‐MF yield is achieved at high conversion if furfuryl alcohol is fed into the reactor at 180 °C over the reduced 3Co‐0.25Fe‐0.75Al catalyst. Based on structural characterization studies including temperature‐programmed reduction (TPR), X‐ray photoelectron spectroscopy (XPS), and in situ X‐ray absorption spectroscopy (XAS) it is suggested that Fe facilitates the reduction of Co, allowing for formation of more metallic species. Overall, this study demonstrates that non‐precious metal catalysts offer promise for the selective conversion of a key biomass oxygenate to a proposed fuel additive.

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Promotional effect of Fe on the performance of supported Cu catalyst for ambient pressure hydrogenation of furfural

Abstract: A noble-metal free FeCu based bimetallic catalyst system prepared by facile co-impregnation method was found to be a highly admirable for vapour phase selective hydrogenation of furfural to furfuryl alcohol at ambient pressure.

Cited by 64 publications

References 57 publications

Recent Advances in Catalytic Hydrogenation of Furfural

Recent Advances in Catalytic Hydrogenation of Furfural

Iron‐Promotion of Silica‐Supported Copper Catalysts for Furfural Hydrodeoxygenation

Vapor Phase Hydrogenolysis of Furanics Utilizing Reduced Cobalt Mixed Metal Oxide Catalysts

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