An efficient Pt nanoparticle–ionic liquid system for the hydrodeoxygenation of bio-derived phenols under mild conditions

Chen, Lu; Fink, Cornel; Fei, Zhaofu; Dyson, Paul J.; Laurenczy, Gábor

doi:10.1039/c7gc01870c

Cited by 27 publications

(18 citation statements)

References 46 publications

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“…Hydrodeoxygenation (HDO) is an important way to catalyze the conversion of lignin and its derivatives into high-calorific alkane. In this process, deoxygenation is crucial as it makes the whole reaction possible (Chen et al, 2016, 2017; Yang et al, 2019). Brønsted acid (like phosphoric acid), as a deoxidizer, is indispensable for facilitating the deoxygenation reaction in most catalytic systems (Güvenatam et al, 2014; Chen et al, 2016).…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, the regularities of physicochemical properties about the PILs are explained through molecular structures and the interactions between cations and anions, which is helpful to predict the change law of similar PILs in the future. Furthermore, the deoxygenation is a very important reaction during lignin hydrodeoxygenation (HDO) processes (Yan et al, 2010; Chen et al, 2016, 2017). These reactions are mostly catalyzed by using noble metal catalysts or protic acids according to the reported methods (Güvenatam et al, 2014).…”

Section: Introductionmentioning

confidence: 99%

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Physicochemical Properties of Various 2-Hydroxyethylammonium Sulfonate -Based Protic Ionic Liquids and Their Potential Application in Hydrodeoxygenation

et al. 2019

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In order to obtain the regularities of physicochemical properties of hydroxy protic ionic liquids (PILs) and broaden their potential application, a series of 2-hydroxyethylammonium sulfonate-based PILs were synthesized through proton transfer reaction and characterized by NMR and FT-IR and elemental analysis. Their phase transfer behavior ( T m ) and initial decomposition point ( T d ) were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. Meanwhile, the regularities of density (ρ), viscosity (η) and electrical conductivity (σ) of synthesized PILs at different temperatures were measured. The results indicated that their physicochemical properties were tightly related with their structures and the interactions between cations and anions. In addition, the dissociation constants (p K a) of synthesized PILs were obtained by acid-base titration, which revealed that all synthesized PILs had p K a exceeding 7 and their cations were the crux of determining the p K a value. Moreover, several synthesized PILs with a low melting temperature also showed potential application in the deoxidation reaction of cyclohexanol, as they had conversion rates approximating 100% and the selectivity of cyclohexane or cyclohexene was about 80%.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Physicochemical Properties of Various 2-Hydroxyethylammonium Sulfonate -Based Protic Ionic Liquids and Their Potential Application in Hydrodeoxygenation

et al. 2019

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“…As the second most abundant biopolymer on earth containing 7 wt % biologically fixed nitrogen, chitin is regarded as a promising feedstock to produce nitrogen-containing chemicals and materials avoiding the involvement of the energy intensive Haber-Bosch process. , Similar to lignocellulosic biomass based biorefinery, − the concept of “Shell Biorefinery” has been proposed, to recognize the significant potentials of crustacean shells, exoskeletons of insects, and the cell walls of fungi to utilize them in various applications. This concept has been currently under intensive development: new protocols for shell fractionation, − improved pretreatment of chitin, − and novel chemical transformations of chitin/chitosan into the desired products , are all emerging.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Conversion of Chitosan to Glucosaminic Acid by Tandem Hydrolysis and Oxidation

Dai

Gözaydın

et al. 2019

ACS Sustainable Chem. Eng.

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Effective conversion of chitin or its derivatives (i.e., chitosan) to value-added organonitrogen compounds is a promising strategy to valorize chitin. Glucosaminic acid (GlcNA) is an important amino acid derived from chitosan. In this work, we demonstrate the feasibility of GlcNA production from chitosan by tandem hydrolysis and oxidation reactions without isolating glucosamine (GlcN) intermediate. The Amberlyst-15 and Au/MgO were identified as suitable catalysts for the hydrolysis and oxidation step, respectively, but the direct employment of hydrolysate from the first step in further oxidation resulted in very low yield of target amino acid. We show that humin-like polymers formed during hydrolysis poisoned Au/MgO, resulting in low GlcNA yield, and subsequently a key detoxication process of the hydrolyzed mixture using activated carbon was developed. It effectively removed the undesired side products that inhibit Au catalyzed oxidation reaction, markedly enhancing the GlcNA yield from 17% for untreated hydrolysate to 63% for preadsorbed sample. As such, a two-step process is developed to produce GlcNA from chitosan with an overall yield of 36%.

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“…However, to cleave the strong sp 2 C-O bonds in DAEs, classic hydrogenation methods commonly run at high pressure (40–65 bar) and temperature (200–300 °C) reaction conditions 38 – 40 . Some milder hydrogenolyses have been developed, mostly requiring precious metals (Pd 41 , Rh 42 , Ru 41 , 42 , Pt 43 ), but improved conditions (120–150 °C; 6–12 bar H 2 ) with Ni nanoparticles have recently been reported 44 , 45 . Nonetheless, two issues remain: (a) these robust but severe heterogeneous catalytic DAE cleavage reactions show low selectivity, with ring saturation of the phenolic products hard to avoid; and (b) most reports have focused on diphenyl ether (DPE) alone, whereas the DAE scaffolds noted above carry various functionalities 25 .…”

Section: Introductionmentioning

confidence: 99%

Skeletal Ni electrode-catalyzed C-O cleavage of diaryl ethers entails direct elimination via benzyne intermediates

et al. 2022

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Diaryl ethers undergo electrocatalytic hydrogenolysis (ECH) over skeletal Ni cathodes in a mild, aqueous process that achieves direct C-O cleavage without initial benzene ring saturation. Mechanistic studies find that aryl phenyl ethers with a single para or meta functional group (methyl, methoxy, or hydroxy) are selectively cleaved to the substituted benzene and phenol, in contrast to recently reported homogeneous catalytic cleavage processes. Ortho positioning of substituents reverses this C-O bond selectivity, except for the 2-phenoxyphenol case. Together with isotope labeling and co-solvent studies, these results point to two distinct cleavage mechanisms: (a) dual-ring coordination and C-H activation, leading to vicinal elimination to form phenol and a surface-bound aryne intermediate which is then hydrogenated and released as the arene; and (b) surface binding in keto form by the phenolic ring of the hydroxy-substituted substrates, followed by direct displacement of the departing phenol. Notably, acetone inhibits the well-known reduction of phenol to cyclohexanol, affording control of product ring saturation. A byproduct of this work is the discovery that the ECH treatment completely defluorinates substrates bearing aromatic C-F and C-CF3 groupings.

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An efficient Pt nanoparticle–ionic liquid system for the hydrodeoxygenation of bio-derived phenols under mild conditions

Abstract: Hydrodeoxygenation of bio-derived phenols under mild conditions with platinum nanoparticles in situ synthesized in an ionic liquid.

Cited by 27 publications

References 46 publications

Physicochemical Properties of Various 2-Hydroxyethylammonium Sulfonate -Based Protic Ionic Liquids and Their Potential Application in Hydrodeoxygenation

Physicochemical Properties of Various 2-Hydroxyethylammonium Sulfonate -Based Protic Ionic Liquids and Their Potential Application in Hydrodeoxygenation

Catalytic Conversion of Chitosan to Glucosaminic Acid by Tandem Hydrolysis and Oxidation

Skeletal Ni electrode-catalyzed C-O cleavage of diaryl ethers entails direct elimination via benzyne intermediates

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