Selective transfer hydrogenolysis of glycerol promoted by palladium catalysts in absence of hydrogen

Musolino, Maria Grazia; Scarpino, L.A.; Mauriello, Francesco; Pietropaolo, R.

doi:10.1039/b915745j

Cited by 90 publications

(90 citation statements)

References 14 publications

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“…The dehydration/ hydrogenation route easier occurs at lower temperature since the initial C-OH breaking involves an energy bond as low as ≅ 80 kcal·mol −1 , while the dehydrogenation/decarbonylation preferentially proceeds at higher temperature since the cleavage of the O-H bond implies a much higher energy value (EO-H ≅ 104 kcal·mol −1 ) [230]. The effective feasibility of the selective catalytic transfer hydrogenolysis of glycerol into 1,2-PDO, promoted by the PdFe catalyst, was demonstrated for the first time by Pietropaolo [137]. Reactions were performed under inert atmosphere in absence of added hydrogen and it was ascertained that the transfer of hydrogen occurs from the alcoholic solvent (2-propanol or ethanol) to the glycerol, through the dehydrogenation of the solvent.…”

Section: C-c and C-o Bond Breaking In C2-c6 Polyolsmentioning

confidence: 99%

“…The effective feasibility of the selective catalytic transfer hydrogenolysis of glycerol into 1,2-PDO, promoted by the PdFe catalyst, was demonstrated for the first time by Pietropaolo [137]. Reactions were performed under inert atmosphere in absence of added hydrogen and it was ascertained that the transfer of hydrogen occurs from the alcoholic solvent (2-propanol or ethanol) to the glycerol, through the dehydrogenation of the solvent.…”

Section: C-c and C-o Bond Breaking In C2-c6 Polyolsmentioning

confidence: 99%

“…In general, supported Pd-Fe catalysts with a strong metal-metal and/or metal-support interaction can be prepared through the co-precipitation technique [131][132][133][134][135][136][137][138][139]. As highlighted by Tsang and co-workers [131], it is very important to control pre-reduction treatments, in terms of temperature and duration, because they affect the induction time.…”

Section: Co-precipitation-cpmentioning

confidence: 99%

“…Specifically, results obtained in important "green and sustainable" reactions will be presented including: aqueous-phase reforming [128][129][130], hydrogenolysis [131][132][133][134][135][136] and CTH [137,138] of C6-C2 polyols, hydrogenolysis and transfer hydrogenolysis of furfural [139,140], hydrodeoxygenation of phenol derivatives [141,142], HDO and CTH of aromatic ethers [143][144][145]. All these reactions will be discussed in details with the aim to show the unicity of heterogeneous Pd-Fe catalysts that are suitable for a wide reductive valorization processes of all constituent components of lignocellulosic biomasses having the potential to be successfully used in modern biorefineries to produce simple bulk compounds.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Upgrading Lignocellulosic Biomasses: Hydrogenolysis of Platform Derived Molecules Promoted by Heterogeneous Pd-Fe Catalysts

et al. 2017

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Abstract:This review provides an overview of heterogeneous bimetallic Pd-Fe catalysts in the C-C and C-O cleavage of platform molecules such as C2-C6 polyols, furfural, phenol derivatives and aromatic ethers that are all easily obtainable from renewable cellulose, hemicellulose and lignin (the major components of lignocellulosic biomasses). The interaction between palladium and iron affords bimetallic Pd-Fe sites (ensemble or alloy) that were found to be very active in several sustainable reactions including hydrogenolysis, catalytic transfer hydrogenolysis (CTH) and aqueous phase reforming (APR) that will be highlighted. This contribution concentrates also on the different synthetic strategies (incipient wetness impregnation, deposition-precipitaion, co-precipitaion) adopted for the preparation of heterogeneous Pd-Fe systems as well as on the main characterization techniques used (XRD, TEM, H 2 -TPR, XPS and EXAFS) in order to elucidate the key factors that influence the unique catalytic performances observed.

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Section: C-c and C-o Bond Breaking In C2-c6 Polyolsmentioning

confidence: 99%

Section: C-c and C-o Bond Breaking In C2-c6 Polyolsmentioning

confidence: 99%

Section: Co-precipitation-cpmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Upgrading Lignocellulosic Biomasses: Hydrogenolysis of Platform Derived Molecules Promoted by Heterogeneous Pd-Fe Catalysts

et al. 2017

Self Cite

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“…Within this concept, two different approaches have been investigated: the first one involves the use of aqueous solutions of glycerol, where hydrogen is formed via aqueous phase reforming (APR) of a part of glycerol [20][21][22][23]; and the second, the addition of a hydrogen donor molecule (alcohols, formic acid), through hydrogen transfer reaction. The idea of catalytic transfer hydrogenation (CTH) was firstly realized by Musolino et al [24] for selective transfer hydrogenolysis of glycerol in the presence of palladium catalysts (Pd/Fe2O3) using ethanol and 2-propanol as H2 donor molecules. The pathways proposed include alcohol dehydrogenation, glycerol dehydration to hydroxyacetone and subsequent hydrogenation of the latter, consuming the H2 generated from the alcohols.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Glycerol Hydrodeoxygenation under Inert Atmosphere: Ethanol as a Hydrogen Donor

Vasiliadou

Lemonidou

2014

Catalysts

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Glycerol hydrodeoxygenation to 1,2-propanediol (1,2-PDO) is a reaction of high interest. However, the need for hydrogen supply is a main drawback of the process. According to the concept investigated here, 1,2-propanediol is efficiently formed using bio-glycerol feedstock with H2 formed in situ via ethanol aqueous phase reforming. Ethanol is thought to be a promising H2 source, as it is alcohol that can be used instead of methanol for transesterification of oils and fats. The H2 generated is consumed in the tandem reaction of glycerol hydrodeoxygenation. The reaction cycle proceeds in liquid phase at 220-250 °C and 1.5-3.5 MPa initial N2 pressure for a 2 and 4-h reaction time. Pt-, Ni-and Cu-based catalysts have been synthesized, characterized and evaluated in the reaction. Among the materials tested, Pt/Fe2O3-Al2O3 exhibited the most promising performance in terms of 1,2-propanediol productivity, while reusability tests showed a stable behavior. Structural integrity and no formation of carbonaceous deposits were verified via Temperature Programmed Desorption of hydrogen (TPD-H2) and thermogravimetric analysis of the fresh and used Pt/FeAl catalyst. A study on the effect of various operating conditions (reaction time, temperature and pressure) indicated that in order to maximize 1,2-propanediol productivity and yield, milder reaction conditions should be applied. The highest 1,2-propanediol yield, 53% (1.1 g1,2-PDO gcat −1 ·h −1 ), was achieved at a lower reaction temperature of 220 °C. OPEN ACCESSCatalysts 2014, 4 398

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Actuating Liquid Crystals Rapidly and Reversibly by Using Chemical Catalysis

Yu,

Gold,

Wolter

et al. 2024

Advanced Materials

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Microtubules and catalytic motor proteins underlie the microscale actuation of living materials, and they have been used in reconstituted systems to harness chemical energy to drive new states of organization of soft matter (e.g., liquid crystals (LCs)). Such materials, however, are fragile and challenging to translate to technological contexts. Rapid (sub‐second) and reversible changes in the orientations of LCs at room temperature using reactions between gaseous hydrogen and oxygen that are catalyzed by Pd/Au surfaces are reported. Surface chemical analysis and computational chemistry studies confirm that dissociative adsorption of H2 on the Pd/Au films reduces preadsorbed O and generates 1 ML of adsorbed H, driving nitrile‐containing LCs from a perpendicular to a planar orientation. Subsequent exposure to O2 leads to oxidation of the adsorbed H, reformation of adsorbed O on the Pd/Au surface, and a return of the LC to its initial orientation. The roles of surface composition and reaction kinetics in determining the LC dynamics are described along with a proof‐of‐concept demonstration of microactuation of beads. These results provide fresh ideas for utilizing chemical energy and catalysis to reversibly actuate functional LCs on the microscale.

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Selective transfer hydrogenolysis of glycerol promoted by palladium catalysts in absence of hydrogen

Cited by 90 publications

References 14 publications

Upgrading Lignocellulosic Biomasses: Hydrogenolysis of Platform Derived Molecules Promoted by Heterogeneous Pd-Fe Catalysts

Upgrading Lignocellulosic Biomasses: Hydrogenolysis of Platform Derived Molecules Promoted by Heterogeneous Pd-Fe Catalysts

Catalytic Glycerol Hydrodeoxygenation under Inert Atmosphere: Ethanol as a Hydrogen Donor

Actuating Liquid Crystals Rapidly and Reversibly by Using Chemical Catalysis

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