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WIREs Energy Environ.
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Catalytic transformation of carbohydrates and lignin in ionic liquids

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Ionic liquids with anions of strong hydrogen‐bond basicity have been broadly reported in the literature as effective solvents for the dissolution of the components of lignocellulosic biomass. The key attributes of various ionic liquids are reviewed with a focus on their structural and functional properties related to biomass dissolution capacity. A number of the most studied ionic liquids with high solubility for cellulose and lignin have often been found not suited for catalytic conversions of these biomass components. Metal chlorides in chloride‐based ionic liquids are robust catalyst systems for efficient cellulose and lignin conversions. Emerging leads in the literature related to the use of ionic liquids for catalytic conversions of cellulose, cellulosic carbohydrates, and lignin are discussed. This article is categorized under: Bioenergy > Science and Materials
Mole fraction of the total Cu in the tetrahedral CuCl42− form as a function of the [Cl] lower axis (M) or (upper axis, water mole fraction). (Reproduced with permission from Ref 30. Copyright 2010, American Chemical Society.)
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Structures of typical ionic liquids covered in this chapter.
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Proposed decomposition pathway of GG in [BMIM]Cl and the synthesis of furfural–lignin resin. (Reproduced with permission from Ref 94. Copyright 2012, American Chemical Society.)
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Structures of TBD, MTBD, TMG, DBU and DABCO.
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Pathways of GG and VG degradation in acidic ionic liquids. Analogous chemistry occurs with GG and VG dimers. (Reproduced with permission from Ref 88. Copyright 2011, Elsevier.)
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Conversion (▪) and guaiacol yield (□) after 20 min under 150°C using GG as model compound. (Reproduced with permission from Ref 88. Copyright 2011, Elsevier.)
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Changes in the degree of polymerization (DP) values of cellulose/hydrolyzed cellulose in aqueous 6 mol% H2SO4 (•) and in [EMIM]Cl containing 6 mol% (i.e., 37 mmol/g [EMIM]Cl) total CuCl2 and CrCl2 (χCuCl2 = 0.91) (▪) at 120°C. (Reproduced with permission from Ref 15. Copyright 2009, Elsevier.)
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Hydrolysis product yield from cellulose using single and paired CuCl2/PdCl2 catalysts having χCuCl2 ranginh from 0 to 1 at 120°C for 1h. The cellulose was dissolved in [EMIM]Cl at 100°C for 1h before initiating the reaction by adding water. Total metal chloride loading is 37 mmol/g [EMIM]Cl (6 mol% with respect to the glucose monomer concentration present in the cellulose feed). (Reproduced with permission from Ref 16. Copyright 2011, Elsevier.)
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Thermal decomposition of [EMIM]Ac into methyl acetate and ethylimidazole.
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Common linkages between phenylpropane units in lignin. (Reproduced with permission from Ref 41. Copyright 2004, Elsevier.)
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Two‐dimensional schematic of lignin structure.
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Two‐dimensional schematic of cellulose and hemicellulose structures.
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Schematic of various cation–anion structures in ionic liquid–water mixture for various mole fractions of water as indicated. (Reproduced with permission from Ref 30. Copyright 2010, American Chemical Society.)
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