Renewable and Sustainable Energy Reviews 192 (2024) 114243

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Recent progress in deep eutectic solvent(DES) fractionation of

lignocellulosic components ： A review
Tianyuan Xiao a, b, Minjie Hou a, Xu Guo a, Xinyu Cao a, Changgeng Li a, Qi Zhang a, b,
Wenchao Jia a, Yanning Sun a, Yanzhu Guo a, Haiqiang Shi a, *
a
Liaoning Key Lab of Lignocellulose Chemistry and Biomaterialsbo, Liaoning Collaborative Innovation Center for Lignocellulosic Biorefinery, College of Light Industry and
Chemical Engineering, Dalian Polytechnic University, Dalian, Liaoning, 116034, China
b
College of Light Industry and Textile, Qiqihar University, Qiqihar, Heilongjiang, 161000, China

A R T I C L E I N F O A B S T R A C T

Keywords: High-value utilization of plant resources is crucial for achieving carbon neutrality and complete carbon trans­
Deep eutectic solvent (DES) formation. Significant progress has already been made in the comprehensive utilization of plant resources
Lignocellulose through pretreatment methods, particularly the deep eutectic solvent (DES) method for the pretreatment of plant
Pretreatment
fibers. This method enables sustainable development of lignocellulose deconstruction and high-value utilization.
High-value conversion
This paper provided a review of the composition, classification, and properties of different types of DES. It also
Sustainable resources
investigated the effects of stoichiometric ratio, temperature, time, microwave, ultrasonic, hydrothermal, and
emulsification on lignocellulose deconstruction using the DES. Additionally, the study explored the use and
prospects of lignocellulosic fractions in lignin extraction, enzymatic saccharification, and high-value cellulose
production using functional DES systems. The evaluation of the DES functionality is conducted through quantum
chemistry, molecular simulation calculations, and the DES recycling effects (optimum 10 cycles). The mechanism
of DES in lignocellulosic extraction is elucidated, and the prospects for sustainable development are outlined.

eliminated from various fields through industrial wastes and food

byproducts every year. If the resources of the plant can be utilized
1. Introduction comprehensively, its chemical energy can be converted into alternative
fields by various means, this not only saves costs but also maximizes
With the development of science and technology and industrial energy usage. Utilizing plant resources with recycling and low carbon
technology, people’s living standards are changing with each passing emissions is essential to developing modern resources. Moreover, many
day. At the same time, a tremendous amount of fossil energy is simple and well-established plant fiber resource utilization process
consumed each year due to past advances in science and technology, technologies have been applied on a large scale, but still have some
which has created numerous ecological imbalances in people’s living problems of high energy consumption and complex process equipment.
environment [1]. For instance, the greenhouse effect, soil drying up, etc. The plant fiber pre-treatment technology can effectively convert the
Various experts and scholars began to focus on developing clean and individual components of lignocellulose in plant fiber into biomass en­
renewable energy. Biomass energy is the formation of various organ­ ergy production. Destruction of the structure of plant fiber cells by
isms, including plants, animals, and microorganisms, through photo­ physical, chemical, and biological means, so that steam and solvents
synthesis. The form of energy stored in living organisms is chemical dissolve the lignocellulosic chemical components of plant fiber [4,5].
energy by solar energy [2]. Various experts and scholars believe that And then separate and purify each to obtain the main components of
developing biomass energy is an effective way to maintain ecological lignocellulose. The better deconstruction of cellulose, lignin, and
balance. Using biomass for energy development allows carbon energy hemicellulose in lignocellulose is an issue that needs to be addressed
recycling, ecological and environmental stability, and scientific and today. Deep eutectic solvents (DES) are a richly hydrogen-bonded sol­
technological development to move forward together [3]. vent system consisting of a mixture of two or more components in a
Biomass energy refining is the primary means of efficient conversion certain stoichiometric ratio. The formation of hydrogen-bonded solvent
and usage of plant resources. Many plant (tree and grass) resources are

* Corresponding author.
E-mail address: [email protected] (H. Shi).

https://doi.org/10.1016/j.rser.2023.114243
Received 28 May 2023; Received in revised form 30 November 2023; Accepted 16 December 2023
Available online 27 December 2023
1364-0321/© 2023 Elsevier Ltd. All rights reserved.
T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

Nomenclature GA glutaric acid

GPC gel permeation chromatography
Abbreviation Vocabulary Name HBA hydrogen bond acceptor
AA acetic acid HBD hydrogen bond donor
AcChCl acetylcholine chloride K-T Kamlet–Taft
ATR-FTIR Attenuated total reflectance Fourier transform infrared LA lactic acid
BzChCl benzyl dimethyl(2-hydroxyethyl) ammonium chloride MA malonic acid
BTMAC Benzyl trimethylammonium chloride MD molecular dynamics
BTEAC Benzyl triehtylammonium chloride Mn number of average molecular weigh
CEL cellulolytic enzyme lignin Mw weight-average molecular weight
ChCl choline chloride NMR nuclear magnetic resonance
COSMO-RS conductor-like screening models for real solvents OA oxalic acid
DAL dealkaline lignin OL organosolv lignin
DBU 1,5- diazabicyclo[5.4.0]-5-undecane OPEFB oil palm empty fruit bunch
DES deep eutectic solvent PB p-hydroxybenzoic acid
DSC differential scanning calorimetry PBA p-hydroxy benzyl alcohol
EG ethylene glycol PCA p-coumaric acid
EHL enzymatic hydrolysis lignin PDI polydispersity index
EMAL enzymatic/mild acidolysis lignin PEG polyethylene glycol
FA formic acid PHA p-hydroxybenzaldehyde

systems between the chemical components of DES by charge-transfer non-polluting, environmentally friendly, low-toxicity, highly efficient
interactions. It is possible to break the lignocellulose inter-component pre-treatment system for plant fibers, which can be recovered and pu­
barrier in plant fiber. Lignocellulose deconstruction and purification of rified still with recyclable functionality [11].
high-quality biomass chemicals are achieved [6,7]. Due to the low en­ In general, DES is able to reduce the dissociation point of two con­
ergy consumption of the preparation method and the ease of preparation stituent substances according to their different properties and will play a
of the chemical components, it is more suitable for the sustainable specific extraction role with additional substances [12]. And DES can be
development of plant fiber pretreatment on a large scale [8]. Moreover, recycled numerous times after separation and purification. Moreover,
DES can play a unique role in lignocellulose separation processes, such recycling DES several times will not affect the pretreatment effect too
as selectively extracting lignin to prepare lignin nanoparticles, much, and the composition of DES components will have no environ­
increasing the efficiency of cellulose glycosylation, and preserving the mental pollution [13](Fig. 1). It has great potential for the fabrication of
integrity of cellulose crystallinity [9,10]. DES has become a bio-based functional materials with superior properties and the

Fig. 1. The properties of DES and its application fields.

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production of economically superior chemicals [14]. For instance, the 2.1.2. Hemicellulose
biomass nanocomposite produced by DES pretreatment of rice husk is Hemicellulose is a complex mixture of different types of mono­
used as a negative electrode material in lithium batteries. It has cycli­ saccharides, including five-carbon sugars and six-carbon sugars such as
cally stable electrochemical properties and a maximum specific capacity xylose, mannose, and galactose. Unlike cellulose and lignin, hemicel­
of 372.5 mAh/g [15,16]. The composition and classification of DES are lulose is not as thermally or chemically stable. Previous research has
reviewed in this paper. The main factors affecting DES are summarized shown that hemicellulose is primarily located between cellulose and
by the effect of different properties of DES in plant fiber. Together with lignin. Therefore, a significant amount of self-hydrolysis occurs during
the progress in the application of DESs in different fields, the advantages the pretreatment of plant fibers, which results in the hydrolysis of
and future trends of DES are summarized in the work [17]. hemicellulose into oligosaccharides as well as the formation of lignin-
carbohydrate complex (LCC) [27]. By pretreatment of plant fiber with
2. Lignocellulose DES, oligosaccharides with different chemical compositions can be ob­
tained and functional chemicals can be obtained by chemical processing.
With the growing knowledge about the utilization of plant resources, Moreover, oligosaccharides have high yields and excellent effects after
it has become evident that lignocellulose present in plant fibers can enzymatic glycosylation [28].
serve as a valuable renewable energy source for energy recycling. Hence,
we must extract and transform the intrinsic energy within plant fiber 2.1.3. Lignin
cells into raw materials applicable to various industrial sectors [18] During the separation of cellulose, the scientist A. Payen discovered a
(Fig. 2). kind of carbon content higher than that of cellulose, which was later
named lignin [29]. Gradually, through the study of plant cells and
2.1. The components of lignocellulose biomass lignocellulose, it was discovered that the chemical structure of phenyl­
ephrine could have anti-UV and anti-oxidant properties. Moreover, its
The main chemical components of plant fiber cells are distributed in phenol-like structure can be used as a substitute for various chemicals
the intercellular layer, surrounding the primary and secondary walls of [30]. Nowadays, numerous experts and scholars have discovered that
the plant cell. These components are crucial in the processes of lignifi­ DESs form a strong hydrogen bond with the phenylephrine structure of
cation and cationization [19]. lignin. Lignin can not only be removed, it is deconstructed efficiently
[31]. In addition, some DESs form hydrogen bonds with lignin to inhibit
2.1.1. Cellulose the formation of lignin nanoparticles, which opens a new avenue for
In 1938, a French scientist, A. Paen, discovered cellulose after the biomass energy applications [32,33].
pretreatment of wood and verified that it had a polymer and stable
lattice structure [20]. Currently, the crystallinity of cellulose has been
improved by different methods of pretreatment plant fiber [21–23]. In 2.2. lignocellulose originated from different sources
particular, the crystallinity of cellulose obtained after pretreatment with
DES is significantly improved, and the yield of the product in enzymatic 2.2.1. Wood
saccharification products [24], nanoscale cellulose fiber [25], and Lignocellulose is a plant fiber derived mainly from trees, agricultural
nanoscale crystals [26] is enhanced, with pronounced properties and products and industrial waste [34]. Lignocellulose in different plant
heavy yields. fiber, cellulose composition, and plant cell structures are extremely
different(Table 1). Wood can be divided into cork and hardwood based
on differences in plant cell structure and plant growth characteristics

Fig. 2. Comprehensive utilization of plant resources to achieve carbon cycles.

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Table 1 Moreover, acidic DES disrupts the structure of maize cell walls, further
Lignocellulose content of different lignocellulose sources. promoting enzyme saccharification and energy efficient conversion and
Lignocellulose Lignocellulose content Reference utilization [40,41].
sources Industrial waste also contains large amounts of plant fiber waste in
Cellulose(wt Hemicellulose(wt Lignin(wt
%) %) %) the industrial production process, such as waste coffee beans from the
coffee processing process, and sugar cane slag produced by the process,
Poplar 49 23 27 [59]
Pine 44 26 29 [64]
which can be used for various technological purposes [42,43]. These
Eucalyptus 48 14 29 [77] waste plant fibers come from industrial production processes. Efficient
Beechwood 50 25 20 [68] use of these plant resources can boost the carbon cycle and reduce
Bamboo 40 14 25 [52] carbon emissions [44].
Moso Bamboo 53 23 26 [96]
Corn Stalk 38 24 18 [67]
Corncob 45 35 15 [72] 3. Properties of DES
Bagasse 42 24 19 [63]
Wheat Straw 53 23 21 [67] DES is the preparation of a mixed solution system consisting of a
Rice Straw 35 25 12 [75]
hydrogen bond acceptor (HBA) and a hydrogen bond donor (HBD) by
Cotton 94 2 3 [77]
OPEFB 28 36 35 [91] fully mixing two or more solvents in a certain ratio, with the DES so­
lution point below the solution point of each individual component. This
solvent system was discovered by Abbott et al., in 2003 [45](Fig. 3). It is
[35]. Cork has a lignin content of between 27 % and 33 %. Hardwood only necessary to stir two or more substances with hydrogen bonding
wood has a lignin content between 18 and 25 %. Agricultural biomass capacity to fully mix the two substances into a homogeneous transparent
has low lignin content, ranging from 17 % to 24 % [36]. Lignin in plant liquid at 60 ◦ C or 80 ◦ C. The DES can then be used to separate, extract,
fiber can be better used at elevated masses after removal, and DES can and chemically modify the mixture after it has been kept in dry and
better remove lignin and obtain an efficient conversion product of airtight conditions. In addition, after each extraction, the solute can be
biomass lignocellulose [37]. recycled after removal by rotational evaporation and solvent exchange,
The plant cell structure of cork is complex and not easily eroded by but it can be recycled more than three times under the influence of the
external forces, and the lignin content, elevated plant cellulose, which is solute. Such solvent systems are green, environmentally friendly,
difficult to separate. The plant cells of hardwoods are dense and solid. convenient and efficient. If it is combined with the automation of pro­
DES pretreatment of hardwood plant fiber better dissolves the interlayer duction processes in various industrial sectors in the future, it will have
in the cell wall and increases the release of lignin and hemicellulose. the prospect of economic savings and environmental protection [46].
Especially the acidic DES is better at dissolving bonds in lignocellulose
[38]. 3.1. Composition of DESs

2.2.2. Industrial wastes & farming byproducts DES is essentially composed of two or more substances that can form
In addition to the material cellulose obtained from wood, the pre­ hydrogen bonds with each other. Hydrogen bonding is the main crite­
treatment of plant fiber from agricultural products and industrial waste rion for DES. In addition, the solubility of DES under hydrogen bonding
can also provide excellent integrated utilization of the main components is better than that of any other component [3]. Generally by physical
of lignocellulose. In agricultural production, after harvesting the fruits mixing, two or more substances at atmospheric pressure of 60 ◦ C–80 ◦ C
of agricultural crops, there will be most of the waste such as biomass are sufficiently and uniformly mixed for 4 h to form a clear colorless
straw and biomass husk [39]. The effective composition of lignocellu­ liquid, which is preserved by being placed in a vacuum. During the
lose in these agricultural wastes is less tightly distributed than in woody stirring process, the constituents of the DES are sufficiently mixed so that
plant fiber and can be better separated. The obtained lignocellulose can hydrogen atoms containing firmly electronegative functional groups
be further chemically modified to prepare biomass functional materials form numerous correlated hydrogen bonds between the systems. Single
by pretreatment corn stalks and rice husks with a neutral DES. hydrogen bonding is considerably smaller than chemical bonding, but

Fig. 3. Development of DES solvent in the field of plant fiber pretreatment.

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T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

the formation of clustered hydrogen bonds in the system changes the

properties of the system.
In the DES, Hydrogen bonding is formed due to electrostatic inter­
action between the functional groups of one component and those of the
other component due to charge migration during the mixing process.
Moreover, as the stirring time is extended, the hydrogen bonds formed
by the two components become more homogeneous. It makes the whole
solvent system more homogeneous and stable and becomes a potential
solvent system. This component that can provide Hydrogen bond proton
pairs becomes an HBD (Hydrogen bond donor), commonly a chemical in
which carboxylic acids, amides, and alcohols have strong electronega­
tive active chemical groups. Moreover, hydrogen bond acceptor (HBA)
was a constituent that provided empty hydrogen bond orbitals in this
system, and was commonly composed of quaternary ammonium salt and
quaternary phosphonium salt. Commonly, in the process of most liter­
ature reports, HBAs and HBDs selected as DES systems are shown in the
chart [47](Fig. 1). In addition, the composition of the DES components is
different, the basic characteristics of the DES system are changed, and its
function is different in different fields [48](Fig. 4).
With the discovery of experts and scholars, the DES system is char­
acterized by high efficiency, stability, green, and simple preparation,
which can even be recycled many times. Currently, more than a hundred
kind of DES systems have been developed and thousands of mature DES
application processes have been developed. Faced with a variety of DES
system compositions and classification, the composition of DES system
Fig. 5. Type I-IV Deep eutectic solvents composition.
can usually be summarized by formula(Fig. 5). DES systems can be
classified into four types of hydrogen bonding: 1. Metal salt and organic
salt(Cat+X− ,zMClx; M = Zn, Sn, Fe, Al, Ga, In); 2. Metallic salt hydrate example, through the DES system composed of choline chloride and
and organic salt (Cat + XzMClx.yH2O; M = Cr, Co, Cu, Ni, Fe); 3.HBD and lactic acid, lignin can be degraded simultaneously during the separation
organic salts (Cat+ X-zRZ; Z = CONH2, COOH, OH); 4. Zinc chloride/ process of lignocellulose [49]. the DES system composed of choline
aluminum chloride and HBD (MClx + RZ = McLx− 1 + RZ + MCl-x+1; M chloride, ethylene glycol and glycerol can improve the separation effi­
= Al, Zn & Z = CONH2, OH); 5. Phenolic group aliphatic hydroxyl group ciency of lignin cellulose components [50]. The DES system composed of
(Thymol + Menthol)(Table 2). amino acids, glucose and other components extracted by natural prod­
ucts can have the special function of biomass separation and extraction
[51]. Most people call the DES system of natural product components
3.2. Classification of DESs
natural DES (NADES). Based on the summary and analysis conducted by
experts and scholars regarding the integration of DES systems and their
In the course of DES research, it has been found that the combination
practical outcomes, it can be observed that DES can be classified into
of HBA and HBD can give specific functions to solvent systems, and it
three categories: acid, neutral, and basic techniques, considering the
can also play an attractive role in the field of biomass research. For

Fig. 4. HBAs and HBDs with different functional groups.

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Table 2 3.2.1. Acid solvents

Expressions and examples of different composes of DES. If the HBD or HBA components in the DES system are malic acid,
Number Compose Expression formula Example lactate and p-benzoic acid. Then, after forming a stable hydrogen bond
between the HBD and the HBA, the HBD component can generate active
I Metal salt + Organic salt Cat X zMClx;
+ −
ZnCl2 + ChCl
M = Zn, Sn, Fe, Al，Ga, proton pairs [55–57]. The DESs in the application process, the proton to
In advance on the dissolution or extract derivatives to achieve multiple
II Metal salt hydrate + Cat+X− zMClx.yH2O; CoCl2.6H2O + effects(Table 3). In the process of pretreatment of plant fiber, the
organic salt M = Cr, Co, Cu, Ni, Fe ChCl components of HBD and HBA of acidic solvent have carboxylic acid or
III HBD + Organic salt Cat+ X-zRZ; Urea + ChCl
Z = CONH2, COOH, OH
Lewis acid and Brønsted acid. Its structure forms stable hydrogen bonds
IV HBD + Metal salt MClx + RZ = MClx-1+ ZnCl2 + urea in DESs, which enable the solution to hydrolyze and ionized protons
RZ + MCl-x+1; [58]. It main components of cell walls and ether bonds connecting the
M = Al, Zn & Z = structural units of lignin can be better separated from lignocellulose
CONH2, OH
under acidic conditions, which is called the "lignin first" strategy by
V Phenolic group + Thymol + Menthol Thymol +
aliphatic hydroxyl group Menthol numerous experts [59]. The pretreatment of plant fiber by DES not only
dissolves the principal constituents of lignocellulose, also achieves
a Cat+ represents any ammonium, phosphonium, or sulfonium cation; X repre­
destruction of the lignin structure [60]. Lignin with low molecular
sents a Lewis base, generally.
weight and a uniform distribution of molecular weight were obtained.
a halide anion; z: number of y molecules interacting with the anion.
Some solvent systems can also control the mechanism of lignin forma­
tion and form lignin nanoparticles [61,62].
specific characteristics of HBD [52]. Due to the hydrogen bonding action
of the DES system, the accessibility of biomass components in the sol­
3.2.2. Alkaline solvents
vent system can be improved, and the identification of different prop­
If the HBD group in the DES system is split into alkaline substances
erties of HBD components can improve the functionality of the DES
with the structure of urea and ethylenediamine amino acids, or if the
system [53,54].
HBA is composed of strongly alkaline substances. This can then be used
in DES systems to give excellent solubility in alkaline environments, but

Table 3
Composition of acid DES system and pretreatment conditions.
HBA HBD Molar ratios Feedstock Pretreatment tempreture/oC Pretreatmenttime/h Reference

ChCl LA 1:9 Popular 120 6 [60]

ChCl LA 1:2 Wheat straw 120 12 [63]
ChCl LA 1:2 Wheat straw 150 3 [63]
ChCl LA 1:5 Sugarcane crop 80 12 [64]
ChCl MA 1:1 Sugarcane crop 80 12 [64]
ChCl PTSA 1:1 Poplar 140 1 [65]
ChCl PTSA 1:1 Pine 140 1 [65]
ChCl PTSA 1:1 Corn stalk 140 1 [65]
ChCl OA 1:1 Bamboo 90 3 [3]
ChCl Glua 1:1 Wheat straw 100 8/16 [68]
ChCl MA 1:1 Wheat straw 100 8/16 [68]
ChCl Leva 1:2 Wheat straw 100 8/16 [68]
ChCl Glua 1:1 Corn stalk 100 8/16 [68]
ChCl MA 1:1 Corn stalk 100 8/16 [68]
ChCl Leva 1:2 Corn stalk 100 8/16 [68]
ChCl Glua 1:1 Rapeseed stem 100 8/16 [68]
ChCl MA 1:1 Rapeseed stem 100 8/16 [68]
ChCl Leva 1:2 Rapeseed stem 100 8/16 [68]
ChCl Glya 1:2 Beechwood 90/130 2/4/8 [69]
ChCl LA 1:10 Beechwood 90/130 2/4/8 [69]
ChCl MA 1:3 Beechwood 90/130 2/4/8 [69]
ChCl FA 1:2 Akebia, 120 3 [70]
ChCl AA 1:6 Akebia, 100 3 [70]
ChCl Leva 1:4 Akebia, 120 3 [70]
ChCl Lta 1:2 Rhus coriaria 25a 0.5 [71]
ChCl LA 1:2 Rhus coriaria 25a 0.5 [71]
ChCl AA 1:2 Rhus coriaria 25a 0.5 [71]
ChCl LA 1:1 Pomegranate peel 45 1 [72]
ChCl CA 1:1 Pomegranate peel 45 1 [72]
OA EG 1:4 Corncob 60–90 6 [73]
OA GLY 1:4 Corncob 60–90 6 [72]
OA EG 1:4 Corncob 70–90 6 [66]
OA GLY 1:4 Corncob 70–90 6 [66]
CA GLY 1:4 Corncob 60–90 6 [73]
MA EG 1:4 Corncob 60–90 6 [73]
MA GLY 1:4 Corncob 60–90 6 [73]
ZnCl2 LA 1:10 Poplar 100–140 1–5 [67]
AlCl3 LA 1:10 Poplar 100–140 1–5 [67]
FeCl3 LA 1:10 Poplar 100–140 1–5 [67]
CuCl2 LA 1:10 Poplar 100–140 1–5 [67]

ChCl: choline chloride PTSA: p-Toluenesulfonic acid monohydrate; OA: Oxalic acid dihy-drate; EG:ethylene glycol; GLY: glycerol; Glya: glycolic acid; Glua: glutaric
acid; Leva: levulinic acid; FA: Formic acid; AA:Acetic acid; Lta: L(+) tartaric acid; CA: citric acid; LA: lactic acid; MA: malic acid.
a
Under ultrasonic bath.

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also to play additional properties(Table 4). In the process of biomass This combination of solvents can frequently be carboxylic acids,
separation, alkaline solvents can achieve excellent pretreatment of the amides and alcohol with the function of HBDS, or can be a green solvent
biomass, and the alkaline solution system is easier to form the main like γ-valerolactone, which can enhance the hydrogen bond to bring
substance of the plant cell wall so that each component of the lignin solubility, and DES system composed of biphasic system [69,107]. It can
cellulose is efficiently dissolved and separated [74]. It was found that also be through the addition of Brønsted acid and Levis acid as the third
lignin surfaces separated by the alkaline DES and NaOH systems have component of molten salt hydrate, which not only improves the prop­
hydroxyl and carboxyl functional groups. The mechanism of action of erties of DES solvent, but also enhances the function of DES system [108,
the alkaline DES system is similar to that of NaOH pretreatment, which 109]. Lewis acid enhanced the DES pretreatment using choline chlor­
contributes to the elevated value utilization of the lignocellulosic ide/glycerol was developed. AlCl3-aided aqueous DES system toward
component. biohydrogen production from lignocellulosic biomass, which led to the
bio-accessibility of the straw(Fig. 3). A notable enhancement of the
3.2.3. Neutral solvent enzymatic hydrolysis efficiency from 26.3 % to 87.0 % was acquired
The HBD in the DES system has the structure of an alcohol hydroxyl when corn straw was pretreated with using 2.0 wt% aqueous DES at
group, a phenol hydroxyl group and an amide. This functional group can 100 ◦ C for 5 h [108](Fig. 6).
play a strong role in hydrogen bonding when forming neutral DES sys­
tems compared to alternative DES solvents [79–82]. In addition, 4. The main factors affecting the effect of DES
numerous literature have discussed the influence of functional group
concentration containing different hydroxyl or amide structure on the The DES system has excellent fundamental properties over any of its
action ability of DES (Table 5). The results of DES action show that constituents due to the hydrogen-bonded system. After the formation of
hydrogen bonds formed by polyols or various functional groups can a stable DES system with different components, the intermolecular
improve the properties of DES system [50,83,84]. The relationship be­ forces, dipole moments and electron cloud densities are modified by
tween the functional group action and the hydrogen bond capacity and hydrogen bonding. Thus, the different reaction conditions are respon­
number was analyzed using DFT calculations and force field simulations sible for the effect of the DES system on lignocellulose [110].
[85,86]. Neutral solvents are essentially polyols, glucose and amino
acids for HBD substances [87,88]. These substances themselves contain 4.1. Stoichiometric ratios
the main functional groups –C=O, -N-H and -O-H. These functional
groups have lone pair electrons in the outermost orbitals, which can The different stoichiometric ratios of HBA and HBD for DES will also
form strong hydrogen bonds with the lignin-dominated structures in make the solvent system achieve different effects in the pretreatment
plant fiber [89]. These hydrogen bonds are oriented and saturated, process. Numerous experts and scholars have discussed the effect of
holding the active sites of the lignin-like hands in order to better sepa­ pretreatment of plant fiber under the same plant fiber, with different
rate the main components of the lignocellulose under certain conditions stoichiometric ratios, and it has been shown that different measurement
[90]. ratios have different effects. The reason for this is due to the shift of the
hydrogen bond forces by different proportions of the constituents during
3.2.4. Combined solvent (ternary solvent systems) the formation of the solvent system. At the same time, the effect of the
Numerous studies have found that DES systems with a single prop­ pretreatment process of lignocellulose is different from that of plant
erty have advantages and disadvantages [51]. For example, neutral fiber.
systems with more than one functional group can improve the solubility
of matter in DES systems, but with low efficiency. At this time, it was
4.2. Temperature control
discovered that the addition of acids to low eutectic neutral systems
could give DES systems versatility [99–101]. For example, on the basis
In many DES systems, the temperature conditions during biomass
of lignocellulose separation, strong hydrogen bonding can improve the
pretreatment are singularly controlled. It has been shown that the DES
hydrogen bonding of DES systems, leading to excellent separation of
system has different effects on the pretreatment of plant fiber under
lignin, cellulose and hemicellulose [102–104]. The functionality of
different temperature conditions, and the influence of temperature on
lignin extraction in the DES system can be improved if acid is added to
chemical reactions and intermolecular forces in solvent systems can also
the system [105]. Different kinds of methods can enhance the granula­
be seen through the Gibbs free energy equation [111]. Increasing the
tion and fragmentation of lignin nanoparticles, and further promote the
temperature during pretreatment of plant cells promotes lignocellulose
high efficiency separation and high value conversion of lignocellulose
deconstruction, which allows better separation of the main components
through the combination of DES system [106](Fig. 6).
of lignocellulose.

Table 4
Composition of alkaline DES system and pretreatment conditions.
HBA HBD Molar ratios Feedstock Pretreatment tempreture/oC Pretreatment time/h References

K2CO3 GLY 1:5 Wheat straw 100 16 [75]

K2CO3 GLY 1:4 Rice straw 110/150 0.6–2 [76]
K2CO3 GLY 1:5 Rice straw 110/150 0.6–2 [76]
K2CO3 GLY 1:6 Rice straw 110/150 0.6–2 [76]
K2CO3 GLY 1:7 Rice straw 110/150 0.6–2 [76]
K2CO3 GLY 1:5 Corn straw 100 8/16 [68]
K2CO3 GLY 1:5 Rapeseed 100 8/16 [68]
K2CO3 GLY 1:5 Wheat straw 80 24 [68]
K2CO3 GLY 1:5 Corn straw 80 24 [68]
K2CO3 GLY 1:5 Rapeseed 80 24 [68]
K2CO3 GLY 1:6 Bamboo 130 6 [53]
ChCl MEA 1:6 Bamboo 130 6 [53]
ChCl Urea 1:2 Populus 115/150 15 [77]
ChCl MEA 1:6 Eucalyptus 100 1/4 [78]
ChCl MEA 1:6 Cotton 100 1/4 [78]

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Table 5
Composition of Neutral DES solution and pretreatment conditions.
HBA HBD Molar ratios Feedstock Pretreatment temperature/oC Pretreatment time/h References

ChCl Glycerol 1:2 Sugarcane crop 80 12 [64]

ChCl Glycerol 1:2 Miscanthus Gigantus 90–130 12 [91]
ChCl EG 1:2 Miscanthus Gigantus 90–130 12 [91]
ChCl Glycerol 1:3 OPEFB 100 2 [92]
ChCl Glycerol 1:5 OPEFB 100 2 [92]
ChCl Gluc 1:1 pomegranate peel 45 1 [72]
ChCl Suc 1:1 pomegranate peel 45 1 [72]
ChCl GLY 1:1 pomegranate peel 45 1 [72]
ChCl GLY 1:2 Borage 90 8 [93]
ChCl GLY 1:2 lettuce leaves 80–150 3–16 [95]
ChCl GLY 1:5 Wheat Bran 80 2 [96]
ChCl EG 1:2 Moso bamboo 90–130 3 [97]
ChCl GLY 1:2 Moso bamboo 90–130 3 [97]
ChCl Xyl 1:2 Moso bamboo 90–130 3 [97]
ChCl Sorb 1:2 Moso bamboo 90–130 3 [97]
ChCl EG 2:1 Rice straw 80–150 3–24 [98]
ChCl GLY 1:1 Rice straw 80–150 3–24 [98]
ChCl Xyl 1:2 Rice straw 80–150 3–24 [98]
ChCl Sorb 1:2 Rice straw 80–150 3–24 [98]
Sua GLY 1:3 Poplar 90 2 [94]

OPEFB:Oil palm empty fruit bunches; EG:Ethylene Glycol; Gluc: glucose; Suc: sucrose; Xyl:Xylitol; Sorb:Sorbitol; Sua: Sulfamic acid.

Fig. 6. (A) Action mechanism diagram of ternary DES system on biomass resources. (B) The mass balance of the ternary DES pretreatment. Reproduced with
permission from Ref. [108] copyright Elsevier(2022).

Increasing temperature can cause breaking of the hydrogen bond of EG-OA and GLY-OA pretreatment was increased from 37.5 % to 31.8 %–
between LCC and lignin molecules [112]Two DES solvent systems are 78.4 % and 59.5 %. In addition, through the 2D-HSQC results, it was
formed during the pretreatment of corncob plant fiber by oxalic acid, additionally found that increasing the pretreatment temperature en­
ethylene glycol and glycerol, respectively. The pretreatment tempera­ hances the solvent accessibility to LCC and lignin molecules [113]The
ture was increased from 70 to 90 ◦ C, and the lignin yield obtained by alcohol-based lignin derivative obtained from the DES action

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T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

additionally stabilizes the lignin derived from lignocellulose [66]. In 4.4.2. Ultrasonication
addition, Miscanthus was found in three different DES systems Ultrasonication can also fulfill an auxiliary role in the fractionation
composed of choline chloride, urea, ethylene glycol, and glycerol. The of lignocellulose in DES systems. Ultrasonication can form microbubble
solubility of the pretreated substrate is also affected to some extent by cavitation to the solvent during the DES reaction and increase the con­
the different temperatures. From the calculation of the solubility of tact area between the solvent and the reaction substrate. At the same
Miscanthus in DES system at 90–130 ◦ C, it was found that temperature time, the lignocellulose barrier is destroyed, and efficient deconstruction
affects the degree of dissociation of the substrate in DES and thus the of lignocellulose is achieved [120–122]. Moreover, some studies have
degree of deconstruction of Miscanthus in DES system [91]. found that increasing ultrasound frequency can enhance the ultrasonic
microbubble effect. It not only enhances the dipolar effect of DES, but
4.3. Processing time also increases the impact of the reaction system and the reaction sub­
strate in the reaction, thus improving the efficiency of the response [123,
In the pretreatment process of DES biomass, it is essentially the 124].
process of forming hydrogen bond molecules and lignocellulose in the
DES system [61]. Moreover, this biomass pretreatment process is based 4.4.3. Hydrothermal
on different reaction efficiencies under fundamental conditions, and the In conventional pretreatment of plant fiber, elevated temperatures
control of reaction time is also a major factor in determining the DES and extreme pressure can break down plant cell walls and promote the
pretreatment process. At the same time, different degrees of reaction dissolution of lignocellulose components. Under such conditions and
effects can also be obtained by controlling the reaction time under temperatures, the dissolution of few substances in plant cells is pro­
certain conditions of fundamental reactivity. Straw was pre-processed moted, reducing the biological barrier between lignin and cellulose. At
using a DESs consisting of choline chloride as the hydrogen bond this point, DES was used in the reaction solvent to further enhance the
acceptor and lignocellulose derived polyols as the HBD. In order to accessibility of DES hydrogen bonds for biomass separation. The pro­
better study the degree of lignocellulosic separation during the pre­ portion of each lignocellulose group is increased in the pretreatment
treatment of the straw. Observing the effects of different reaction times process, which is suitable for the separation of a certain amount of
of 3 h, 6 h, 9 h, 15 h, and 24 h on substrate pretreatment, it was found inferior biomass. Numerous systems of hydrothermal reactions with the
that with the extension of reaction time, the lignin recovery rate in the DES are used, and some pretreatment of hydrolysate with the DES using
substrate increased from 7.8 % to 53.3 %, and the lignin recovery rate of hydrothermal reactions is performed firstly, which varies according to
15h at reaction time increased to 52.2 %. Moreover, the concentration of different plant feedstock and different process conditions for obtaining
oligosaccharides also increased from 5.6 % to 38.5 %. It can be sum­ the production [125].
marized that the control of the reaction time will also exhibit different
biomass fractionation effects under the condition that the DES solvent 4.4.4. Surfactant
has some accessibility to the substrate during the reaction [98]. Surfactants can promote homogeneous reactions in reaction systems.
Meanwhile, under the action of surfactant [126]. It increased the
4.4. Auxiliary method hydrogen bond dispersion in the DES, but it also enhances the accessi­
bility of plant fiber cell walls in eutectic solvents [127,128]. The sur­
Different reaction conditions change the properties and reactivity of factant promotes the complete dissolution of the lignocellulose in the
DES systems, and different methods have their own advantages and plant fiber in the DES, so that the whole solution system reaches a stable
disadvantages. Most lignocellulose fractionation using DES system will phase equilibrium and promotes the dissolution of the lignocellulose
control the ratio of HBA and HBD, pretreatment reaction temperature component in the cell wall. The main surfactants used are Tween 60
and time under the premise of selecting HBA and HBD. However, some [129], polyvinyl alcohol [130], and sodium dodecyl sulfate [126].
auxiliary methods are usually required to make the DES pretreatment
effect more perfect, and enhance the hydrogen bonding ability of the 5. Progress of deep eutectic solvents in lignocellulosic
solvent system or the solvent has good dispersion in the substrate. It will fractionation
be accompanied by some physical and chemical auxiliary conditions in
the pretreatment process. The additional auxiliary methods can not only 5.1. Lignin extraction
cover the weaknesses of the traditional pre-treatment methods, it can
also provide synergistic effects. In traditional processes, plant fiber can be treated with organic sol­
vents. Hemicellulose and lignin were removed to obtain plant fiber with
4.4.1. Microwave elevated cellulose values. It can be seen that lignin has a certain solu­
Microwaves are electromagnetic waves at frequencies between 300 bility in organic solvents [131,132]. The hydrogen bond alkalinity and
MHz and 300 GHz that are deeply directional and propagate linearly lignin removal rate in the solvent can be enhanced by deep eutectic
[114]. Especially, microwaves for DES solvents enhance the dipolar solvents [133–135]. As the utilization of lignin catalytic conversion in­
proton interaction between solvent hydrogen bond donors and acceptors creases, the requirement for lignin removal rate and conversion utili­
[61]. Microwave frequency vibrations can enhance dipole vibrational zation gradually increases. Most of the DES composed of acidic or
conduction in solution, increase the molecular vibrational frequency of neutral organic alcohol were used to extraction and decomposition of
HBA and HBD, and enhance the polarity of hydrogen bonding lignin from lignocellulose(Fig. 7).
[115–117]. Moreover, during the microwave conduction process, DES However, the fundamental difficulty in the utilization of lignin lies in
ionic properties are enhanced so that the microwave energy is converted the fact that lignin is particularly prone to condensation and the for­
into thermal energy, which improves the solvent reaction efficiency, mation of new carbon-carbon bonds in the process of cleavage in the
reduces the reaction cost, and shortens the reaction time, making chemical and biomass chemical industries [44,136,137,138]. These
assisted lignocellulosic fractionation a modern energy-saving and envi­ newly generated intermolecular carbon-carbon bonds, together with the
ronmentally friendly method [118]. Numerous DES systems have been natural intermolecular carbon-carbon bonds, considerably limit the
reacted with substrates using microwave assisted methods [119]. monomer yield of lignin after decomposition [103,139,140]. DES plays
Microwave-assisted action of DES catalyzed production of 5-HMF was an influential role in the extraction of lignin from plant fiber due to its
found to improve the reactivity of the catalytic system. The microwave excellent properties. The strong hydrogen bond alkalinity of DES can act
reaction at 150 ◦ C for 30 min increased the yield of 5-HMF from 5 % to on the active sites of lignin structures. It can not only play the role of
85 % [116]. selective lignin extraction, but also suppress the secondary condensation

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T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

Fig. 7. Bond breaking mechanism of lignin depolymerization by DES.

of lignin after depolymerization in DES for the purpose of depolymer­ acidity condition increases with decreasing pH. During the lignin
ization of lignin molecular weight. Moreover, inhibition of lignin poly­ reformation, the phenol hydroxyl group content increases and the
merization can modulate the reaction conditions to obtain lignin number of ether bonds between the phenylpropane structures decreases,
nanoparticles. The main reasons are that the DES extraction of lignin allowing the formation of lignin nanoparticles (see Fig. 8C).
process, DES causes the chemical structure and size of lignin to be In addition, some studies have found that the traditional hydro­
changed. It is more suitable to become a functional material component thermal pretreatment method is synergic with DES. By setting the hy­
and exerts functional properties such as UV resistance and bacterial drothermal conditions of 130–150 ◦ C, the lignin biomass is pretreated
inhibition in material applications [141–143]. together with DES (CC-EG-AlCl3), and the lignin is further extracted. At
The straw was pretreated by two DES composed of betaine lactate the same time, it was found that the size of the lignin nanoparticles is
(LA/BE) and choline lactate chloride (LA/CC). The results show that the controlled to the lowest 100 nm with a full nanoparticle morphology as
LA/BE and LA/CC systems can separate lignin and cellulose. Lignin is the DES content increases in the pretreatment conditions at elevated
extracted with a high purity of more than 90 %. The total head index of temperatures. HSQC and DPPH were also used to trace the mechanism of
cellulose was almost 60–65 % by quantitative analysis and the lignin lignin depolymerization and renormalization [145,146].(Fig. 8c).
was structure stable [144] (Fig. 8A). Alkaline DES (K2CO3/Gly) was used The process of extracting lignin fractions from lignocellulose using
to dissolve lignocellulose, and with the shift of pH value in the solution DES systems has been developed and matured. In order to develop the
system, the dissolution and reformation behavior of lignin was observed DES lignin extraction process on a commercial scale, many research
under different pH values [75](Fig. 8B). It was concluded that the efforts have focused on the recovery and recycling of DES after lignin

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T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

Fig. 8. (A) The process of extracting lignin from two DES and the relationship diagram of lignin dissolving ability of DES, Reproduced with permission from
Ref. [144]copyright Elsevier (2016), (B) Formation mechanism and molecular weight stability of nanometer lignin particles under different pH conditions,
Reproduced with permission from Ref. [75]copyright Elsevier(2022), (C) Depolymerization mechanism of DES on lignin and size and morphology of lignin nano­
particles, Reproduced with permission from Ref. [143]copyright RSC(2021).

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T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

extraction. Usually, the DES recovery process uses an anti-solvent residues was better than that of the bamboo wall cells [151–153]. Thus,
method and acid precipitation to make the lignin self-assembly and the components of HBD in DES have been explored for enzymatic gly­
finally collect the lignin after the DES further purification. Most DES cation. Poplar fiber were pre-treated with ChCl-PB, ChCl-PCA and
method is the rotary evaporation method; a few research works to ChCl-PHA, respectively. After adjusting the pretreatment process, the
improve the number of cycles of the DES solvent and the effect of using crystallite of ChCl-PB plant fiber residues was significantly improved at
rotary evaporation and reverse osmosis membranes are used to improve 130 ◦ C for 6 h, and the enzymatic glycation conversion rate exceeded 90
the effect of solvent impurity removal. Usually, in some research work % [154–156]. The DES system consists of Brönsted or Lewis acid and an
using DES to extract lignin, the number of cycles of DES can reach 10 additional acidic solvent. The active site of Brønsted-Lewis acid has an
times, and the function is similar. effect on the deconstructing of lignocellulose, which makes lignin
dissociate from hemicellulose and cellulose more efficiently. Using
aluminum chloride, enzymatic saccharification of plant fiber residues
5.2. Enzymatic glycosylation
after deconstruction improves the yield of sugar recovery [67,157,158].
The removal of lignin from lignocellulose by the green method al­
lows better exposure of hemicellulose and cellulose [98]. In other words, 5.3. High-value cellulose
increasing the lignin extraction rate will better increase the high quality
utilization of cellulose and hemicellulose [147,148]. During enzyme The removal of lignin and hemicellulose from lignocellulose is
glycosylation, DES selectively separates the lignin simultaneously. The mentioned in the previous section of discussion [170]. Plant fiber resi­
accessibility of hemicellulose and cellulose in plant fiber residues in­ dues have significant cellulose content. Cellulose contains a large
creases, and the probability of collisions between hemicellulose and number of free alcohol hydroxyl groups, forming a heavy hydrogen bond
cellulose increases. In order to improve the enzymatic glycosylation in network structure [157,171]. It is capable of forming intramolecular
the process of DES pretreatment of plant fiber(Table 6). hydrogen bonds in polymer molecules, which are difficult to dissolve by
Moreover, in the traditional process of enzyme saccharification, the some organic solvents and disrupt polymer structures [172]. Then by
by-products increase with the degree of reaction, which suppresses the regulating the structure, type and proportion of the DES composition,
effect of enzyme activity on hemicellulose and cellulose. DES pretreated DES with strong hydrogen bonds can be prepared to destroy the glyco­
plant fiber and promoted the reaction to enzyme glycosylation [149, sidic bonds in cellulose units [104]. Therefore, cellulose obtained by
150]. The effect of DES (ChCl:MA) on different tissues and cells of DES pretreatment has a high crystallinity and a peculiar lattice
bamboo was studied, and the hydrolysis process of DES was optimized. It morphology [173–175]. X-ray diffraction and Confocal Raman Micro­
was found that the lignin removal force was greatest in potatoes at scopy are commonly used to calculate the crystallinity of cellulose and to
elevated temperatures, and that the crystallinity of the bamboo wall cell observe the microcrystalline structure of cellulose. Determine the value

Table 6
Biomass enzymatic glycosylation by DES pretreatment.
Feedstocks DES type Pretreatment conditions Enzymatic type/Conditions Saccharification References
performance

Bamboo ChCl:MA = 1:2 130oC-150 ◦ C,10min CTec3andHTec/50 ◦ C 72h Glucose release [159]
103 μg/mg EGY = 87 %
Bamboo ChCl:EG:PTSA = 100 ◦ C, 10 min Ctec 3:15 FPU/g glucan/50 ◦ C, 72 h EGY = 90.2 % [160]
1:0.5:1
Poplar ChCl-PB = 1:2 100 ◦ C–160 ◦ C,1/3/6/ Cellic CTec2/50 ◦ C 72h Glucose release [156]
9h 55 μg/mg EGY = 90 %
Poplar ChCl-PCA = 1:2 100 ◦ C–160 ◦ C,1/3/6/ Cellic CTec2/50 ◦ C 72h Glucose release [156]
9h 45 μg/mg EGY = 85 %
Poplar ChCl-PHA = 1:2 100 ◦ C–160 ◦ C,1/3/6/ Cellic CTec2/50 C 72h
◦
Glucose release [156]
9h 25 μg/mg EGY = 82 %
Poplar CuCl2-Lac = 1:10 100 ◦ C–140 ◦ C,1–5h NS50199, 230.8 FPU/50 ◦ C 72h EGY = 86 % [67]
Poplar FeCl3-Lac = 1:10 100 ◦ C–140 ◦ C,1–5h NS50199, 230.8 FPU/50 ◦ C 72h EGY = 87 % [67]
Poplar AlCl3-Lac = 1:10 100 ◦ C–140 ◦ C,1–5h NS50199, 230.8 FPU/50 ◦ C 72h EGY = 92 % [67]
Poplar ZnCl2-Lac = 1:10 100 ◦ C–140 ◦ C,1–5h NS50199, 230.8 FPU/50 ◦ C 72 h EGY = 85 % [67]
Poplar ChCl-LA = 3:2 160 ◦ C, 3 h Cellic CTec2/50 ◦ C 72h EGY >90 % [161]
Poplar ChCl-LA = 1:2 130 ◦ C, 1.5 h Cellulase:30 EGY = 75.8 % [162]
FPU/50 ◦ C, 108 h
Poplar ChCl-Gly = 1:2s 150 ◦ C, 3 h CTec2:15 mg enzyme/g glucan Amylases:10 U/g pretreatred EGY = 80 % [95]
biomass/50 ◦ C, 60 h
Poplar ChCl:GA = 2:1 140 ◦ C, 3 h Cellulase:30 mg protein/g cellulose/50 ◦ C, 72 h EGY = 69.1 % [95]
Rice straw ChCl:LA = 1:3 120 ◦ C, 3 h 40 FPU/g/50 ◦ C, 144 h TRY = 75.7 % [163]
Rice straw ChCl:LA = 1:5 60 ◦ C, 12 h Cellulase:9 FPU/g 42 ◦ C, 24 h TRY 333 mg/g [144]
Rice straw, ChCl:FA:AA = 1:1:1 130 ◦ C, 2 h Cellulase:50FPU/g substrate 50 ◦ C, 48 h TSC = 42.8 g/L [164]
Wheat ChCl:FA = 1:3 360 W, 8 min (with MV) Ctec2:50 FPU/g pretreated biomass/50 ◦ C, 72 h EGY = 99 % [165]
straw
Wheat CHCl:MEA = 1:6 70 ◦ C, 9 h Cellulase:50 ◦ C/FPU/g substrate/50 ◦ C 72 h EGY = 89 % [166]
straw
Wheat ChCl:PEG-200:BA = 120 ◦ C, 4 h Cellulase:30 ◦ C EGY = 59 % [99]
straw 1:1:1.5 FPU/g/72 h
Wheat TEBAC:LA = 1:9 100 C, 10 h
◦
Cellulase:35 ◦ C EGY = 89 % [167]
straw FPU/g biomass
βglucosidase: 82 ◦ C CBU/g biomass/50 ◦ C, 72 h
Corncob BTMAC:LA = 1:2 140 ◦ C, 2 h 15 FPU/g/48 ◦ C, 72 h EGY = 94 % [168]
Corncob CCl:LA = 1:1 150 ◦ C Cellulase:50 ◦ C/FPU/g substrate/50 ◦ C, 72 h EGY = 98 % [169]

p-hydroxybenzoic acid (PB), p-coumaric acid (PCA), 4-hydroxybenzylaldehyde (PHA); EGY(%) = glucose obtained from enzymatic hydrolysis/theoretical glucose
content available in pretreated biomass*100 %; TRY(%) = total reducing sugar obtained from enzymatic hydrolysis/theoretical reducing sugar content in pretreated
biomass*100 %.

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T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

potential of cellulose in the applied domain. 6.1. Stoichiometric calculation

Imax × Imin
CrI = × 100% 5-1 There have been numerous reports on DFT calculations of binding
Imax
energies and number of hydrogen bonds between solvents and biomass
where Imax represents the maximum intensity peak for cellulose I at 2θ substrates, discussing the accessibility of solvents and substrates, and
around 25◦ , I min represents the minimum intensity peak for cellulose II optimizing pretreatment conditions for better lignocellulosic composi­
at 2θ around 20◦ based on Bragg’s law conversion from the Cu Ka ra­ tion [185,190]. In addition, due to the wide combination of DES, the
diation source. computational methods for mechanism investigation can be assisted to
Cellulose was dissolved by DES reagent, and the results showed that save labor and increase research efficiency [191]. On the other hand,
choline chloride/imidazole (3:7) had the characteristics of elevated given that biomass complexity and heterogeneity may increase the dif­
hydrogen bond alkalinity and low viscosity [176]. These properties ficulty of uncovering the reaction mechanism, it may be a promising
favor the dissociation of cellulose and allow it to exhibit relatively strategy to first discover the exact mechanism using model compounds
excellent dissociation in the DES system [177]. However, the maximum [192].
dissolution rate of cellulose is only 2.48 % after pretreatment at 110 ◦ C
without cosolvent [178]. On this basis, using allyl functions choline 6.1.1. Hydrogen bond calculation
chloride as HBA to improve DES, the results show that the cellulose Most of the components of lignocellulose have complex chemical
solubility is only slightly improved (up to 6.53 %), and scanning electron structural bonds and hydroxyl groups. During fractionation through the
microscope (SEM) images also showed that the cellulose morphology DES solvent, solvent systems with stable hydrogen bonds are more likely
changed barely before and after pretreatment [179]. It can be seen that to interact with lignocellulose to form stable hydrogen bonds
cellulose is extremely split and DES reagents with smaller cellulose [193–195]. This motivates the deconstruction and separation of lignin,
dissociation rates can be chosen as much as possible [180]. hemicellulose, and cellulose in lignocellulose [196]. The stoichiometric
Among plant fiber, the cotton is a plant that contains significant ratio, type of HBAs and HBDS in the DES system will affect the properties
amounts of cellulose. Superior quality cellulose, normally obtained by of the DES solvent and its effect on lignocellulose [197]. At the same
processing, can be prepared into cellulosic materials with medicinal time, several reports have demonstrated the force of formation of HBAs
properties. DES solvent dissolves cellulose with great strength and gives and HBDS by hydrogen bonding by chemical methods, and additionally
it excellent crystallization properties, forming cellulose crystals and described the force of hydrogen bonding in a solvent environment by
cellulose fiber with proportionate structural integrity [181]. (Fig. 9A) data [198]. The common quantitative description parameter of
DES is easily permeable to plant fiber. It is the cellulose condition, which hydrogen bond alkalinity is Kamlet-Taft solvation color development
expands the cellulose structure and weakens the interactions in the parameterα, β, and δ [199]. The larger the value of α, β, δ, the stronger
hydrogen bond lattice. Moreover, it is pretreated with 1:2 mol at 150 ◦ C. the hydrogen bond alkalinity. Solvents with strong hydrogen bond
The yield of CNF obtained was increased to 72.5 %. The crystallinity alkalinity are hexamethyl phosphamide, alkyl phosphate esters,
(CrI) of cellulose was increased to 67.7–74.4 %, the oxygen ion charge of dimethyl sulfoxide, dimethylformamide, n-methyl pyrrolidone,
fiber was 0.05–0.06, and the diameter was 17~20 nm [182] (Fig. 9B). tert-butanol, isopropyl alcohol, amine compounds, and some ionic liq­
At the same time, the paper fiber toughness can also be improved by uids [200].
DES solvent treatment of plant fiber pulping in the paper industry. And ̂ + aα + bβ + c(̂
XYZ = XY Z0 π ∗ + dδ) (6-1)
nanocellulose was obtained by separation in pulping. The DES system of
K2CO3 and Gly was used to process rice straw fiber pulps, and the OFAT
vmax(RXH) = v0 max (RXH) + kv(RXR′) (6-2)
method was used to optimize the pulps parameters. The optimal pulps
parameters were determined as the temperature of 140 ◦ C and the re­ ̂′ ))
ΔΔv = v max (RXH) − (v0 max (RXH) + kv(RX R (6-3)
action time of 100 min. The cellulose content between basic DES is 73.8
%, and the crystallinity of cellulose is increased from 52.8 % to 60 % where XYZ0 is the value of the property XYZ in a hypothetical solvent
[76] (Fig. 9C). The basic straw fiber pulp is further processed to obtain having α = β = π* = δ = 0 and the coefficients a, b, c and d represent the
nanocellulose crystals. Through the acidic DES composed of OA-ChCl, responses of the particular chemical property to the different solvent
the slurry is processed and compared with sulfuric acid hydrolysis. It parameters. This approach has been widely used but it seems useful to
can be observed that acidic solvent can hydrolyze, and the amorphous consider these parameters in some detail.
region of cellulose in the DES can release nanocellulose crystals at the With the in-depth study of the data modeling in physics, chemistry
same time, which expands the potential of plant fiber [21] (Fig. 9D). and biology, through Gauss 09 and MD software can realize the mode
DES solvent conditions, through the chemical calculation of lignocel­
6. Evaluation method lulosic components and DES at the level of 6–31g(d), calculate the
hydrogen bonding sites and the number of hydrogen bonds formed
The properties and characteristics of the DES system are sufficient to under the action of the field force. In some studies, by comparing the
dissociate the plant fiber cell walls and the DES solvent further de­ number of hydroxyl groups in glycerol, glycol and propylene glycol HBD
constructs the lignocellulose. Different types of DES systems have special in DES system, a variety of DES system was formed with choline chloride
properties that can give particular properties to dissociated lignocellu­ as HBA [201]. The Veratryl glycerol-B-guaiacyl ether model was simu­
losic components in the pretreatment of plant fiber [183–185]. How­ lated using charmn36 and Gaussian09. VG has functional groups char­
ever, due to better determine the function and properties of DES, the acteristic of lignin, such as β-O-4 ether bonds and phenolic hydroxyl
DES solvent system with stronger excellent performance was selected groups. VG is known to be a commonly used model for lignin. Such as
[186,187]. Recently, DES solvent concentrations, viscosities and den­ β-O-4 ether bonds and phenolic hydroxyl groups [202]. VG was
sities have been calculated using software simulations of solvent envi­ considered a commonly used lignin model. In addition, some DES sys­
ronments, with input from interdisciplinary workers, based on tems add PSTA as a third component to provide proton pairs to discuss
fundamental theorems of chemistry [188,189]. Currently, the DES sys­ the effect of hydrogen bond forces and hydrogen bond numbers on
tem has a wide variety, so the DES evaluation method still needs to be lignocellulosic materials. Fig. 10 shows the number and types of
integrated with multiple disciplines to promote the development and hydrogen bonds obtained from the simulations, together with the posi­
enrich the functionality and selectivity of the DES solvent. tions of the hydrogen bonds in the lignin model. The position and
strength of the hydrogen bond with the lignin phenylpropane structure

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T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

Fig. 9. (A) Process flow chart and process ingredient list of DES processing cotton fiber, Reproduced with permission from Ref. [181]copyright Elsevier(2014). (B)
Process flow chart of CNF prepared from wood fiber treated with DES and the crystallinity and morphology of CNF, Reproduced with permission from Ref. [182]
copyright Elsevier(2020). (C) Process flow chart of DES for rice straw pulp and pulp fiber yield, Reproduced with permission from Ref. [76]copyright Elsevier(2018).
(D) Schematic diagram and morphology diagram of CNF formed by acid treatment of rice straw pulping hydrolysate, Reproduced with permission from Ref. [21]
copyright Elsevier(2020).

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T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

Fig. 10. (a) Geometrics and electrostatic potential surfaces of Ch+, CL≺, EG, VG, and PTSA. (b) Types and numbers of hydrogen bonds in different DES systems
under simulated conditions, Reproduced with permission from Ref. [203]copyright Elsevier(2022).

during the interaction of the DES system with the lignin can be accu­ used for biomass pretreatment, the viscosity of the DES system can be
rately derived [178] (Fig. 10). controlled by adjusting the hydroxyl content of the polyols and the
O1 denoted the oxygen atom in the β-O-4 ether bond in the lignin length of the aliphatic chains and functional groups in the HBD to make
model, O2 denoted the two ether-bonded oxygen atoms on the benzene the DES system more functionally specific [210]. The changing viscosity
ring in the lignin model, O3H stood for the aromatic hydroxyl group in of the DES system can be measured to obtain better the effect of
the lignin model and O4H stood for the two aliphatic hydroxyl groups in hydrogen bonding constructed by mixing HBA and HBD, and the
the lignin model. In this case, the hydrogen bonds in the system were accessibility of the DES system to the reaction substrate can be better
divided into hydrogen bonds of the lignin model with CL≺, hydrogen deduced from the experimental results. However, it is more necessary to
bonds of the lignin model with polyols, and hydrogen bonds of the lignin scientifically explain the quantitative relationship between the
model with PTSA [204]. hydrogen bonding of the DES system and the experimental results.
The changes in the DES system during the overall biomass pre­
treatment were determined by calculating and simulating the hydrogen 6.1.3. Quantum-chemical calculations
bond, identifying the fracture and recombination of the hydrogen bond DES has the advantage of being green, stable, and reproducible,
lattice, and its effect on the plant fiber substrate [88]. Further quanti­ which is attributed to the fusion of HBA and HBD under certain condi­
tative analyses of DES pretreatment can be performed by calculating the tions, which increases the probability of molecular collisions between
number of hydrogen bonds and hydrogen bond energies of the reaction HBA and HBD. HBA and HBD form a stable hydrogen bond network in
system via quantum chemical calculation scripts. However, the func­ solution, which gives DES systems numerous properties such as low
tionality of the DES reaction system still needs to be evaluated in melting point and elevated viscosity.
conjunction with experimental results. It commonly judges the relation between hydrogen-bond acceptors
and hydrogen-bond donors based on quantitative calculations of rele­
6.1.2. Viscosity calculation vant theories in inorganic and physical chemistry. By exploring the kind
The viscosity of the DES system is the main factor determining its and nature of HBA and HBD. The binding energies and orbital properties
functional properties [205]. The viscosity parameter of the solution of the different components are also to be judged. It also makes the
system determines the accessibility of the solution to lignocellulose combination of DES prediction and preparation possible. Not only can
during pretreatment; In other words, the magnitude of the viscosity the function of the DES system be analyzed by judging the shift of the
parameter determines the reaction probability of the reactant in solvent system solvent before and after stirring, but also the property shift of the
[206]. Moreover, the viscosity parameter of the solution, which acts as a DES system after binding can be judged by quantitative calculations. The
medium for the reaction process, also affects the heat transfer rate and properties and orbital parameters of HBA or HBD can be obtained by
thus the pretreatment effect of the lignocellulose [207]. Commonly, consulting books and literature, as well as other scientific research
solvent functionality can be summarized by comparing pretreatment works. Computer software such as Gaussian09 (Gaussview), Charm36
lignin removal, crystallinity of plant fiber residues, sugar content after and Materials studio can also be used to assist in analyzing the properties
enzymatic glycation, and viscosity parameters. The effect of viscosity on and spatial configurations of DES systems, intuitively simulating the
the pretreatment of lignocellulose is generally tuned by adding water probability of molecular collision and the size of binding energy
content in the solvent and controlling the HBD type in the DES system required to form DES systems. In addition, the properties of DES systems
[202]. have been simulated and calculated, and the application prospects of
Adding water to the DES system changes the viscosity of the system different types of DES systems have been conjectured.
and therefore affects the solubility of the substrate to solvent [208]. The ideal configuration and actual properties of the de Sitter system
Here, water can be considered as the third component in the DES system, are derived by comparing simulation and actual experimental reaction
which enables the HBD and HBA to reach a steady state with the results with quantitative computational parameters and computer aided
maximum number of hydrogen bonds and solution energy [209]. software. Choline chloride urea, lactate and malate were selected as
Changing the viscosity of the system by water increases the solubility of components of HBA and HBD. Through the EHOMO and ELUMO of different
lignin in solution, increases the lignin removal rate, and suppresses the molecules, the ΔE (Energy gap) of the DES system is calculated, and 3D-
condensation mechanism. It can also increase the dissociation efficiency molecular electrostatic potential (3D-MEP) were evaluated [185]. By
of cellulose, which lead to nanocellulose crystals with enhanced crys­ comparing the simulation type obtained by theoretical calculation with
tallinity. In addition, the solution viscosity can also be tuned by the actual solution parameters of the formation of DES system, the DES
changing the properties of the HBD in the DES system so that the density system with additional strong hydrogen bond activity was selected, and
of the hydrogen bond lattice in the DES system can reach the appropriate the reaction activity of different kinds of DES system could be judged
hydrogen bond alkalinity. Among the numerous neutral DES systems (Fig. 11).

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T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

Fig. 11. The HOMO and LUMO orbital distribution of the tested molecules in the gas phase. Reproduced with permission from Ref. [185]copyright Elsevier(2023).

Quantitative calculation can simulate the effect of free protons in the filtration of the plant residue after pretreatment and using the anti­
DES system on the biomass lignin (Fig. 12). Based on the ideal simula­ solvent or acid gradient method. The reaction system is further purified
tion calculation of choline chloride DES system in the field of Reaffix, the by rotary evaporation [211], freeze drying [212], electrodialysis [213],
β-O-4 and glycosidic bond of the model were simulated to be destroyed and membrane [214] separation to obtain DES solvent for recycles.
at 373K, to achieve the purpose of lignocellulose delignification [202]. Overall, one method is removing the solute from the reaction system to
Molecular orbital calculations of the reaction system evaluated the get pure reaction solvent; the other is transferring the solvent from the
accessibility of the DES solution to the reaction substrates. Still, due to reaction system. Currently, DES functionality is evaluated by the num­
the specificity and complexity of lignocellulose, the reaction substrates ber of times DES can be recycled and the pretreatment efficiency.
of many of the current research efforts are only represented by repre­ However, the reasons for the reduced effectiveness of some DES when
sentative model species. recycled still need to be made clear.

6.2.1. Recycling times

6.2. DES recycles
Several research works have investigated the effect of DES with
different ratios of choline chloride and oxalic acid on the separation of
Because of the stability of the physicochemical properties of the DES
biomass fractions from maize kernels and enzymatic saccharification
reaction system, many research efforts have been made to isolate and
yields. It was shown that the DES were still functional for biomass after
purify the pretreated DES, which can be recycled many times and ach­
10 cycles [211]. And the lignocellulose in other kinds of DES pretreated
ieve the desired effect. Generally, lignin is removed from the solvent by

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T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

Fig. 12. The LCC-Lignin and DES systems were simulated by quantitative calculation. Reproduced with permission from Ref. [202]copyright Elsevier(2021).

plant fibers can basically be recycled 3–5 times. Recyclability and reaction temperature to 30 ◦ C and increases the reaction efficiency by
reusability of the solvent firmly determine the feasibility of the DES 215 %. The different types of HBA and HBD make the DES system spe­
pretreatment process towards biomass. cific for material cellulose separation. The polyols DES system enhances
the solubility of the plant fiber substrate. The acid DES system was used
6.2.2. Recycling effect to investigate the increase of glycosidic bond breaking rates of lignin-
After the purification process of the DES system, several groups of ether bonds and LCC complexes by 45 % using HSQC-NMR method.
plant fiber will dissolve in the DES system during the reaction, occu­ Therefore, it provides the basis for DES system in the development of
pying a part of the solvent space volume. At the same time, it also affects plant fiber pretreatment. The DES selectively removes lignin, de­
the hydrogen bonding mechanism between the DES components, thus polymerizes lignin, inhibits lignin polymerization, and forms lignin
increasing steric hindrance of the DES system and decreasing the oligomeric nano-lignin particles. Plant fiber residues with elevated
accessibility of the DES and plant fiber biomass components. As the crystallinity of free cellulose and hemicellulose are used to facilitate the
number of uses increases, the effect of the DES also decreases. Some data enzymatic glycation of harvested sugars and catalyze the conversion of
suggest that the above phenomenon occurs in the separation of biomass good chemicals. In addition, special DES systems can dissolve cellulose
components and their applied effects. to produce nanocellulose crystals and nanocellulose fiber.
Currently, lignin removal rate, enzymatic glycation yield, plant fiber
7. Conclusion and outlook residue crystallinity, solvent recovery efficiency can be used as func­
tional evaluation criteria for DES systems. The hydrogen bond alkalinity
As a green, recyclable, pollution-free and easy-to-prepare modern of the DES system can also be inferred through quantitative calculations
solvent, the DES system has the potential for sustainability. The DES of the DES system and physical and chemical yearly calculations,
system differs from conventional organic and acid-based solvents in its allowing the DES system to play a better role. There are still several
treatment of cellulose in plant fiber. The DES system consisting of HBA directions about DES systems to be developed in the lignocellulose field
and HBD has a larger hydrogen bond potential energy, achieved in future, (1) The specific functional DES system was accurately deter­
deconstruction and separation efficiency of lignocellulosic main com­ mined by quantum chemical calculation, (2) The DES system with
ponents of 94 % or more. enzyme activity was developed to facilitate the pure production of sugar,
Temperature, time, and solid-to-liquid ratio are the main factors that (3) Plant fiber chemistry and synthetic chemistry were combined to
affect the reaction rate of the solution system during the pretreatment of realize the one-pot method of using DES system to prepare functional
wood fiber by the DES system. Reaction efficiency can be improved by biomass flexible materials, (4) Strengthen the recycling efficiency and
preprocessing the DES system with microwave, ultrasonic and hydro­ recycling times of the DES system, so that the DES system can serve in
thermal reactions. In particular, the microwave reaction reduces the the cleaning industry.

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T. Xiao et al. Renewable and Sustainable Energy Reviews 192 (2024) 114243

Declaration of competing interest [20] Deng X, Wan L, Sun H, Li C, Liu F, Yan X, et al. Preparation of nanocellulose from
cotton fibers in deep eutectic solvent (DES) and its application in paper.
Bioresources 2022;17:714–24. https://doi.org/10.15376/biores.17.1.714-724.
The authors declare that there is no conflict of interests regarding the [21] Lim W-L, Gunny AAN, Kasim FH, Gopinath SCB, Kamaludin NHI, Arbain D.
publication of this paper. Cellulose nanocrystals from bleached rice straw pulp: acidic deep eutectic solvent
versus sulphuric acid hydrolyses. Cellulose 2021;28:6183–99. https://doi.org/
10.1007/s10570-021-03914-7.
Data availability [22] Smirnov MA, Sokolova MP, Tolmachev DA, Vorobiov VK, Kasatkin IA,
Smirnov NN, et al. Green method for preparation of cellulose nanocrystals using
Data will be made available on request. deep eutectic solvent. Cellulose 2020;27:4305–17. https://doi.org/10.1007/
s10570-020-03100-1.
[23] Mnasri A, Dhaouadi H, Khiari R, Halila S, Mauret E. Effects of Deep Eutectic
Acknowledgments Solvents on cellulosic fibres and paper properties: green “chemical” refining.
Carbohydr Polym 2022;292:119606. https://doi.org/10.1016/j.
carbpol.2022.119606.
This work was financially supported by the Natural Science Foun­ [24] Kuo C-H, Lee C-K. Enhancement of enzymatic saccharification of cellulose by
dation of China (31971608; 22378036), and the⋅Liao Ning⋅Revitaliza­ cellulose dissolution pretreatments. Carbohydr Polym 2009;77:41–6. https://doi.
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