Selective Ether/Ester C–O Cleavage of an Acetylated Lignin Model via Tandem Catalysis

Lohr, Tracy L.; Li, Zhi; Marks, Tobin J.

doi:10.1021/acscatal.5b01972

Cited by 76 publications

(77 citation statements)

References 64 publications

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“…In another approach, Marks et al . reported the selective C−O hydrogenolysis of an acetylated lignin model compound using a leveraged tandem catalytic strategy.…”

Section: Discussionmentioning

confidence: 76%

“…The role of the type of solvent was also considered in this study.O ther alcohols with similarp hysical and chemical prop- [a] Percentage of formic acid that has decomposed (calculatedb yt itration). www.chemsuschem.org erties to ethanol,s uch as isopropanol andm ethanol, were studied in the formic acid aided lignin decompositioni nt he presenceo ft he NiMo catalyst supported on sulfated alumina (AA) ( Table 1, entries2 and [15][16]. The evolution of the pressure for the three experiments is shown in Figure 8.…”

Section: Effect Of Solventmentioning

confidence: 83%

“…In recent years, different research groups have suggested new reactionp athways that involve lignin modelc ompounds and formic acid [15] or lignin modelc ompounds and similar organic acids, such as acetic acid. [16] Similarb iomass valorization processes (i.e.,f ormic acid mediated liquefaction of chitin) have also been reported. [17] However,t heseh ypotheses have not been demonstrated for the conversion of real lignin.…”

Section: Introductionmentioning

confidence: 99%

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Unraveling the Role of Formic Acid and the Type of Solvent in the Catalytic Conversion of Lignin: A Holistic Approach

et al. 2017

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The role of formic acid together with the effect of the solvent type and their synergic interactions with a NiMo catalyst were studied for the conversion of lignin into bio-oil in an alcohol/formic acid media. The replacement of formic acid with H or isopropanol decreased the oil yield to a considerable degree, increased the solid yield, and altered the nature of the bio-oil. The differences induced by the presence of H were comparable to those observed in the isopropanol system, which suggests similar lignin conversion mechanisms for both systems. Additional semi-batch experiments confirmed that formic acid does not act merely as an in situ hydrogen source or hydrogen donor molecule. Actually, is seems to react with lignin through a formylation-elimination-hydrogenolysis mechanism that leads to the depolymerization of the biopolymer. This reaction competes with formic acid decomposition, which gives mainly H and CO , and forms a complex reaction system. To the best of our knowledge, this is the first time that the distinctive role/mechanism of formic acid has been observed in the conversion of real lignin feedstock. In addition, the solvent, especially ethanol, seems also to play a vital role in the stabilization of the depolymerized monomers and in the elimination/deformylation step.

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“…In another approach, Marks et al . reported the selective C−O hydrogenolysis of an acetylated lignin model compound using a leveraged tandem catalytic strategy.…”

Section: Discussionmentioning

confidence: 76%

Section: Effect Of Solventmentioning

confidence: 83%

Section: Introductionmentioning

confidence: 99%

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Unraveling the Role of Formic Acid and the Type of Solvent in the Catalytic Conversion of Lignin: A Holistic Approach

et al. 2017

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“…10 On the other hand, metal triates, such as those of Eu, Hf and La, have previously been reported to catalyze C-O bond cleavage at elevated temperatures in the presence of Pd/C and at high hydrogen pressures, producing alkanes as products. [13][14][15][16][17][18] In this respect, the use of metal triates in the synthesis of olens is plausible, and ideally the more expensive metals should be replaced with more abundant and inexpensive transition metal-based Lewis acid catalysts in the conversion of biomass-based oxygen containing compounds to olens.…”

Section: Introductionmentioning

confidence: 99%

Transition metal triflate catalyzed conversion of alcohols, ethers and esters to olefins

et al. 2018

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Herein, we report an efficient transition metal triflate catalyzed approach to convert biomass-based compounds, such as monoterpene alcohols, sugar alcohols, octyl acetate and tea tree oil, to their corresponding olefins in high yields. The reaction proceeds through C-O bond cleavage under solventfree conditions, where the catalytic activity is determined by the oxophilicity and the Lewis acidity of the metal catalyst. In addition, we demonstrate how the oxygen containing functionality affects the formation of the olefins. Furthermore, the robustness of the used metal triflate catalysts, Fe(OTf) 3 and Hf(OTf) 4 , is highlighted by their ability to convert an over 2400-fold excess of 2-octanol to octenes in high isolated yields.

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“…A study by Lohr et al. demonstrated that lignin acetylation can increase the solubility in nonpolar solvents and modify the reactivity of pendant hydroxy groups to promote more selective C−O cleavage . In our case, lignin formylation is believed to be beneficial for catalytic conversion into aromatic monomers.…”

Section: Resultsmentioning

confidence: 61%

Rapid Nondestructive Fractionation of Biomass (≤15 min) by using Flow‐Through Recyclable Formic Acid toward Whole Valorization of Carbohydrate and Lignin

Zhou

Tan

et al. 2019

ChemSusChem

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Whole valorization of carbohydrate and lignin from biomass was achieved by rapid flow‐through fractionation (RFF) within 15 min. Wheat straw was effectively deconstructed into its principle components without degradation by using easily recyclable aqueous formic acid (72 wt %) at 130 °C. The obtained cellulose‐rich solid showed a nearly complete glucan recovery and 73.8 % glucose conversion after enzymatic hydrolysis. Xylan also reached full recovery with negligible furfural formation with a sum of 80 % of oligo/mono xylose in spent liquor and 20 % of xylan remaining in the solid. Up to 75.4 % lignin was dissolved in the spent liquor and further fractionated into water‐insoluble (WIL) and water‐soluble lignin (WSL) by dilution with water. WIL showed a non‐condensed and well‐preserved structure with 84.5 % β‐O‐4 remaining, which is believed to be beneficial for catalytic conversion into low‐molecular‐weight chemicals and fuels. The concentration of employed formic acid was below the formic acid/water azeotrope, and therefore the reaction medium could be restored through simple distillation. Together with the joint valorization of lignin and carbohydrates, the presented RFF is a promising process for sustainable biorefinery.

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Selective Ether/Ester C–O Cleavage of an Acetylated Lignin Model via Tandem Catalysis

Cited by 76 publications

References 64 publications

Unraveling the Role of Formic Acid and the Type of Solvent in the Catalytic Conversion of Lignin: A Holistic Approach

Unraveling the Role of Formic Acid and the Type of Solvent in the Catalytic Conversion of Lignin: A Holistic Approach

Transition metal triflate catalyzed conversion of alcohols, ethers and esters to olefins

Rapid Nondestructive Fractionation of Biomass (≤15 min) by using Flow‐Through Recyclable Formic Acid toward Whole Valorization of Carbohydrate and Lignin

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