Dissolution of cellulose in ionic liquids: an ab initio molecular dynamics simulation study

Payal, Rajdeep Singh; Balasubramanian, Sundaram

doi:10.1039/c4cp02219j

Cited by 48 publications

(40 citation statements)

References 57 publications

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“…This means the H‐bonds and π‐π stacking in VG‐[Amim] + both play an important role for lignin dissolution. This situation is very different from the cellulose dissolution in imidazolium‐based ILs, where only H‐bonding interaction occurs between the cation and cellulose and the anion plays a decisive role . The important contribution from the π‐π interaction for the lignin dissolution is in good agreement with the experimental observation that the imidazolium cations with π‐conjugated substituents result in improved lignin solubility .…”

Section: Resultssupporting

confidence: 72%

Modeling interactions between a β‐O‐4 type lignin model compound and 1‐allyl‐3‐methylimidazolium chloride ionic liquid

2017

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Aiming at understanding the molecular mechanism of the lignin dissolution in imidazolium-based ionic liquids (ILs), this work presents a combined quantum chemistry (QC) calculation and molecular dynamics (MD) simulation study on the interaction of the lignin model compound, veratrylglycerol-β-guaiacyl ether (VG) with 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The monomer of VG is shown to feature a strong intramolecular hydrogen bond, and its dimer is indicated to present important π-π stacking and intermolecular hydrogen bonding interactions. The interactions of both the cation and anion of [Amim]Cl with VG are shown to be stronger than that between the two monomers, indicating that [Amim]Cl is capable of dissolving lignin. While Cl anion forms a hydrogen-bonded complex with VG, the imidazolium cation interacts with VG via both the π-π stacking and intermolecular hydrogen bonding. The calculated interaction energies between VG and the IL or its components (the cation, anion, and ion pair) indicate the anion plays a more important role than the cation for the dissolution of lignin in the IL. Theoretical results provide help for understanding the molecular mechanism of lignin dissolution in imidazolium-based IL. The theoretical calculations on the interaction between the lignin model compound and [Amim]Cl ionic liquid indicate that the anion of [Amim]Cl plays a more important role for lignin dissolution although the cation also makes a substantial contribution.

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Section: Resultssupporting

confidence: 72%

Modeling interactions between a β‐O‐4 type lignin model compound and 1‐allyl‐3‐methylimidazolium chloride ionic liquid

2017

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“…[35][36][37][38][39][40][41][42][43] Various simulation methods are available at different length and time scales depending on the specific targets requested from the studied IL systems. 44,[52][53][54] Molecular simulations at an atomistic level are widely used in predicting thermodynamic, structural, and dynamic properties of various IL systems. 35,[44][45][46][47][48][49][50] However, due to their computationally demanding nature, these methods are usually adopted to derive effective interactions of ion pairs, 35,46,50,51 and to determine delicate interactions with solute molecules in small systems and short time scales.…”

Section: Introductionmentioning

confidence: 99%

Multiscale modeling of the trihexyltetradecylphosphonium chloride ionic liquid

Wang

Sarman

et al. 2015

Phys. Chem. Chem. Phys.

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A multiscale modeling protocol was sketched for the trihexyltetradecylphosphonium chloride ([P6,6,6,14]Cl) ionic liquid (IL). The optimized molecular geometries of an isolated [P6,6,6,14] cation and a tightly bound [P6,6,6,14]Cl ion pair structure were obtained from quantum chemistry ab initio calculations. A cost-effective united-atom model was proposed for the [P6,6,6,14] cation based on the corresponding atomistic model. Atomistic and coarse-grained molecular dynamics simulations were performed over a wide temperature range to validate the proposed united-atom [P6,6,6,14] model against the available experimental data. Through a systemic analysis of volumetric quantities, microscopic structures, and transport properties of the bulk [P6,6,6,14]Cl IL under varied thermodynamic conditions, it was identified that the proposed united-atom [P6,6,6,14] cationic model could essentially capture the local intermolecular structures and the nonlocal experimental thermodynamics, including liquid density, volume expansivity and isothermal compressibility, and transport properties, such as zero-shear viscosity, of the bulk [P6,6,6,14]Cl IL within a wide temperature range.

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“…1575 cm À1 is assigned to the antisymmetric stretching vibration of the COO À group of the anion. [17][18][19][20] In the past, most of studies on ionic liquid/cellulose mixtures focused on the contributions from anion-cellulose interactions under ambient pressure. 6b).…”

Section: View Article Onlinementioning

confidence: 99%

“…[4][5][6][7][8][9][10] With three hydrogen atoms bound to the imidazolium ring of 1-alkyl-3-methylimidazolium salts, the most acidic proton, i.e., the C 2 proton, may prefer to form hydrogen bonds with anions. [11][12][13][14][15][16][17][18][19][20][21][22] For example, ionic liquids based on the alkylimidazolium cation and the acetate anion (or halide anion) were found to dissolve high amount of cellulose. One of the attractive features of ionic liquids is the higher-order aggregate structure that results from polar/nonpolar phase separation.…”

Section: Introductionmentioning

confidence: 99%

“…One of the attractive features of ionic liquids is the higher-order aggregate structure that results from polar/nonpolar phase separation. [12][13][14][15][16][17][18][19][20] However, some research groups infer that cation-cellulose interactions, such as imidazolium C-HÁ Á ÁO hydrogen bonds, have a non-negligible role in cellulose/ ionic liquid mixtures. For example, Triolo et al proposed that the nano-structural organization may exist in asymmetric imidazolium ions presenting alkyl chains even as short as butyl chains.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The effect of pressure on cation–cellulose interactions in cellulose/ionic liquid mixtures

Chang

Zhang

Hsu

2015

Phys. Chem. Chem. Phys.

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Cation-cellulose interactions in binary mixtures of [EMIM][OAc] and cellulose have been investigated using high-pressure infrared spectroscopy. At low concentrations of cellulose, almost no changes were observed in the imidazolium C(2)-H frequency; on the other hand, at high concentrations of cellulose, increases in the C(2)-H vibration frequency were observed under ambient pressure. As the pressure was elevated, the imidazolium C(2)-H absorption of the [EMIM][OAc]/cellulose mixtures underwent band-narrowing and blue-shifts in the frequency. These observations suggest that high pressures may strengthen the hydrogen bonds formed between C(2)-H and cellulose, possibly forcing the cellulose to dissociate clusters of ionic liquid through enhanced cation-cellulose interactions. In contrast to the cation-cellulose interaction results, the COO(-) absorption of the anion does not show dramatic changes under high pressures. Our results indicate the possibility of enhanced cation-cellulose interactions through pressure elevation, demonstrating that high pressures may have the potential to tune the relative contributions of cation-cellulose and anion-cellulose interactions in cellulose/ionic liquid mixtures.

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Dissolution of cellulose in ionic liquids: an ab initio molecular dynamics simulation study

Cited by 48 publications

References 57 publications

Modeling interactions between a β‐O‐4 type lignin model compound and 1‐allyl‐3‐methylimidazolium chloride ionic liquid

Modeling interactions between a β‐O‐4 type lignin model compound and 1‐allyl‐3‐methylimidazolium chloride ionic liquid

Multiscale modeling of the trihexyltetradecylphosphonium chloride ionic liquid

The effect of pressure on cation–cellulose interactions in cellulose/ionic liquid mixtures

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