Research progress in preparation and functional application of nanocellulose by the pretreatment of deep eutectic solvent
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摘要: 近年来，环境友好型的绿色溶剂是发展绿色化学的重要研究方向。低共熔溶剂作为具有一定降解性、生物相容性良好的新型绿色溶剂，在纳米纤维素的制备及功能化应用中展现了强大的发展潜力。本文对低共熔溶剂的基本性质和形成机制进行了综述，并介绍了不同低共熔溶剂在纳米纤维素的制备及功能化应用，以实现纳米纤维素的高效制备和改性。未来通过实验与计算模拟技术的结合，可以充分发挥低共熔溶剂的可设计性，揭示其溶解、降解和制备纳米纤维素的规律，为低共熔溶剂预处理制备及改性纳米纤维素提供参考，推动其在生物质预处理中的规模化应用。Abstract: In recent years, environmentally friendly green solvents have become an important research direction in green chemistry. As a new type of green solvent with certain degradability, good biocompatibility and relatively environmental protection, the deep eutectic solvent has preliminarily shown its strong development potential in the preparation and functional modification of nanocellulose. This paper mainly reviews the basic properties and formation mechanism of the deep eutectic solvent, and introduces the application of different deep eutectic solvent in the preparation and functional modification of nanocellulose, so as to achieve efficient preparation and modification of nanocellulose. In the future, the designability of the deep eutectic solvent can be brought into full play through the combination of experiment and computational simulation technology and reveal the law of its dissolution, degradation and functionalization in the preparation of nanocellulose, so as to provide references for the preparation and modification of the pretreatment of the deep eutectic solvent and promote its large-scale application in biomass pretreatment.
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Key words:
- deep eutectic solvents /
- biomass /
- nanocellulose /
- urea /
- choline chloride /
- green solvents
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图 1 (a) 纤维素的化学结构[35]；(b) 从不同生物质中采用不同方法合成纳米纤维素示意图[35]；(c) 纤维素纳米纤维(CNFs)和纤维素纳米晶体(CNCs)的结构[36]；(d) 纤维素纤维结构示意图[37]
Figure 1. (a) Chemical structure of cellulose[35]; (b) Schematic representation for the synthesis of nanocellulose with different approaches from different biomass[35]; (c) Structures of cellulose nanofibers (CNFs) and cellulose nanocrystals (CNCs)[36]; (d) Schematics of the structure of cellulose nanofibers[37]
图 2 (a) 用于低共熔溶剂(DES)合成的卤化物盐和氢键供体的典型结构[18]；(b) 氯化胆碱-尿素与纤维素可能发生的反应[47]；(c) 纤维素、氯离子和尿素分子的相互作用示意图[48]
Figure 2. (a) Typical structure of halide salts and hydrogen bond donors used for deep eutectic solution (DES) synthesis[18]; (b) Possible reactions of cholinine-urea chloride and cellulose[47]; (c) Schematic diagram of the interaction of cellulose, chloride ions and urea molecules[48]
图 3 (a) 小麦、玉米和油菜籽原料；(b) 原料的化学组成[51]；(c) 酸性DES (乳酸-氯化胆碱(5∶1))和碱性DES (甘油-K2CO3 (5∶1))预处理后的纳米悬浮液[51]；(d) DES处理后纳米原纤维的FESEM图像[51]；(e) 酯化反应方程式
Figure 3. (a) Wheat, corn and rapeseed raw materials; (b) Their compositions[51]; (c) Nanofibrillated samples after acidic-DES (Lactic acid-choline chloride (5∶1)) and alkali-DES (Glycerol-K2CO3 (5∶1)) pretreatments[51]; (d) FESEM images of nanofibrils after DES treatment[51]; (e) Reaction equation of esterification
图 4 (a) 盐酸甜菜碱-甘油DES体系制备纳米纤维素的过程[54]；(b) 纳米纤维素的SEM和TEM图像[54]；(c) 初始DES和循环后的DES[57]；(d) 机械解体后的纳米纤维素悬浮液[57]；(e) 纳米纤维素的TEM图像[57]
Figure 4. (a) Preparation of nanocellulose by betaine hydrochloride-glycerol system[54]; (b) SEM and TEM images of nanocelluloses[54]; (c) Original DES, and recycled DES[57]; (d) Nanocellulose suspensions after mechanical disintegration[57]; (e) TEM images of nanocellulose[57]
表 1 酰胺与氯化胆碱混合物(酰胺∶氯化胆碱摩尔比2∶1)的凝固点及纯酰胺的熔点[23]
Table 1. Freezing point of amide and choline chloride mixture (amide∶choline chloride mole ratio 2∶1) and the melting point of pure amide[23]
Amide compound Freezing point/℃ Melting point/℃ Urea 12 134 Methyl urea 29 93 1, 3-dimethyl urea 70 102 1, 1-dimethyl urea 149 180 Sulfur urea 69 175 Acetamide 51 80 Benzamide 92 129 Tetramethyl urea a −1 Note: a represents no homogeneous liquid was formed. 
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表 2 尿素类低共熔溶剂预处理制备纳米纤维素
Table 2. Preparation of nanocellulose by urea pretreatment with low eutectic solvent
DES Mole ratio Raw material Treating temperature/
timeTypes of nanocellulose Yield of nanocellulose Diameter of nanocellulose/
nmCrystallinity Ref. Choline
chloride-urea1∶2 Birch 100℃/2 h CNF 90% 2-200 nm — [38] Choline
chloride-urea1∶2 Microcrystalline cellulose 110℃/48 h CNC — 80-120 nm 79%-85% [39] Choline
chloride-urea1∶4 Cork dissolved cellulose 150℃/30 min CNF — (4.4±1.6) nm — [40] Choline
chloride-urea1∶2 Bleached birch pulp 100℃/2 h CNF — (17±21) nm 66% [41] Sulfamic
acid-urea1∶2 Spruce cellulose pulp 150℃/30 min CNF — — — [42] Urea-ammonium
thiocyanate2∶1 Bleached birch kraft paper 100℃/2 h CNF 87% 13-19 nm — [43] Urea-guanidine
hydrochloride2∶1 Bleached birch kraft paper 100℃/2 h CNF 90% 13-15 nm — [43] Urea-lithium
chloride5∶1 Cork dissolved pulp 90℃/6 h CNF — — — [44] Choline
chloride-urea1∶2 Recycled pulp 100℃/2 h CNF — 1-6 μm — [45] Sulfamic acid-urea-choline chloride 1∶3∶1 Fiber pulp 100℃/2 h CNF — 0.52 mm — [46]
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