See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/350396396

A strong, biodegradable and recyclable lignocellulosic bioplastic

Article  in  Nature Sustainability · July 2021

DOI: 10.1038/s41893-021-00702-w

CITATIONS READS

110 6,231

10 authors, including:

Qinqin Xia Chen Chaoji

Northeast Forestry University Wuhan University
28 PUBLICATIONS   1,203 CITATIONS    168 PUBLICATIONS   16,931 CITATIONS   

SEE PROFILE SEE PROFILE

Shuaiming He Yubing Zhou

South China University of Technology University of Maryland, College Park
10 PUBLICATIONS   181 CITATIONS    22 PUBLICATIONS   2,120 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Towards better Li metal anodes View project

Deep eutectic solvent Biorefinery lignocellulose catalyst View project

All content following this page was uploaded by Chen Chaoji on 27 August 2021.

The user has requested enhancement of the downloaded file.

 Articles
https://doi.org/10.1038/s41893-021-00702-w

A strong, biodegradable and recyclable

lignocellulosic bioplastic
Qinqin Xia   1,6, Chaoji Chen   1,6, Yonggang Yao1, Jianguo Li1, Shuaiming He1, Yubing Zhou1, Teng Li   2,
Xuejun Pan   3, Yuan Yao   4 ✉ and Liangbing Hu   1,5 ✉

Renewable and biodegradable materials derived from biomass are attractive candidates to replace non-biodegradable petro-
chemical plastics. However, the mechanical performance and wet stability of biomass are generally insufficient for practical
applications. Herein, we report a facile in situ lignin regeneration strategy to synthesize a high-performance bioplastic from
lignocellulosic resources (for example, wood). In this process, the porous matrix of natural wood is deconstructed to form a
homogeneous cellulose–lignin slurry that features nanoscale entanglement and hydrogen bonding between the regenerated
lignin and cellulose micro/nanofibrils. The resulting lignocellulosic bioplastic shows high mechanical strength, excellent water
stability, ultraviolet-light resistance and improved thermal stability. Furthermore, the lignocellulosic bioplastic has a lower
environmental impact as it can be easily recycled or safely biodegraded in the natural environment. This in situ lignin regenera-
tion strategy involving only green and recyclable chemicals provides a promising route to producing strong, biodegradable and
sustainable lignocellulosic bioplastic as a promising alternative to petrochemical plastics.

P
etrochemical plastics are inexpensive and durable materials,
widely used in various areas such as packaging1, construction2,
electronics3 and aviation4. However, it takes hundreds or even
thousands of years for most plastics (for example, polyethylene,
polystyrene and polyvinyl chloride) to degrade due to the stable
long polymer chains5. As a result, 11 billion metric tons of plastics
are projected to accumulate in landfills and the natural environment
by 20256, causing severe environmental pollution7.
To address this crisis, researchers have proposed the replace-
ment of conventional petrochemical-based plastics with bio-based
or biodegradable materials that are more environmentally friendly8.
‘Bioplastics’ are a broad class of materials that can include either
bio-based (but not necessarily biodegradable) or petrochemical and
bio-based plastics that are considered biodegradable9. When made
from different biomass feedstock (mainly composed of lignin, cel-
lulose and hemicellulose)10, bioplastics can reduce the reliance on
fossil fuels and diminish greenhouse gas emissions. Such materi-
als can be synthesized using various processes that include delig-
nification11, chemical crosslinking12,13 and modification of natural
fibres11,14. However, these approaches face tremendous obstacles,
including the use of toxic chemicals and complex processing steps
with associated high manufacturing costs. In addition, it remains
challenging to improve the mechanical strength and water stabil-
ity, which are typically limited by the weak interfacial bonding
and hydrophilicity of cellulose and/or hemicellulose in bio-based
bioplastics. Therefore, it is critical to develop a simple and sustain-
able method of fabricating bioplastics from naturally abundant
resources, in which the final product must be biodegradable at its
end-of-life while at the same time being mechanically strong and
robust during service, thus requiring a unique balance between
degradability and durability.
To address these needs, we present an efficient in situ lignin
regeneration approach that can fabricate lignocellulosic bioplastic
demonstrating high mechanical strength, improved water and
thermal stability, excellent recyclability and biodegradability, as
well as low cost (Fig. 1a). The design of this in situ lignin regen-
eration method eliminates the need to separate and isolate lignin
and cellulose from wood, which is a cost- and energy-intensive
process. Instead, in situ lignin regeneration leads to a homogeneous
and highly viscous cellulose–lignin slurry, in which lignin fills the
spaces within the interconnected cellulose micro/nanofibrils net-
work, resulting in a highly dense structure. Lignocellulosic bioplas-
tic can then be easily obtained by casting this cellulose–lignin slurry
(Fig. 1b). Moreover, the lignocellulosic bioplastic can be easily recy-
cled by mechanically disintegrating the product at its end-of-life in
water to reform a uniform cellulose–lignin slurry for reuse. Unlike
most petrochemical plastics, this lignocellulosic bioplastic can be
biodegraded by microorganisms in soil, demonstrating an attractive
closed-loop cycle feature. Additionally, the material is mechanically
strong and robust during service, demonstrating a unique balance
between degradability and durability, which neither conventional
plastics nor hydrophilic cellulose consumer products can provide.
This strong, water-stable, biodegradable and recyclable lignocel-
lulosic bioplastic synthesized by in situ lignin regeneration with a
substantially reduced environmental waste footprint demonstrated
herein is a strong candidate for replacing widely used petrochemical
plastics toward sustainable applications (for example, agricultural
mulching films, construction and automotive parts).
Results
Fabrication of the lignocellulosic bioplastic. We synthesized
the lignocellulosic bioplastic using an in situ lignin regeneration
approach directly from abundant and inexpensive wood powder
(Fig. 2a), a wood processing residue that is generally discarded as
waste. The starting wood material has a mesoporous structure and
lignocellulosic composition made up of cellulose, hemicellulose and

1
Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA. 2Department of Mechanical Engineering, University of
Maryland, College Park, MD, USA. 3Department of Biological Systems Engineering, University of Wisconsin-Madison, Madison, WI, USA. 4Yale School of
the Environment, Yale University, New Haven, CT, USA. 5Center for Materials Innovation, University of Maryland, College Park, MD, USA. 6These authors
contributed equally: Qinqin Xia, Chaoji Chen. ✉e-mail: y.yao@yale.edu; binghu@umd.edu

Nature Sustainability | VOL 4 | July 2021 | 627–635 | www.nature.com/natsustain 627

Articles NaTuRE SusTaInabIlITy

a
Cellulose Deep eutectic solvent
Hemicellulose Lignin Water

Lignin
Lignocellulose dissolution
Lignin Lignocellulosic
Cellulose regeneration bioplastic
fibrillation

Solvent recycle

In situ lignin regeneration

Degradability of
end-of-life waste

Nutrient
(for example, water, CO2, organics)

Close loop cycle

Microorganisms

b
• Low cost

• Mechanically strong

• Water stable
m
10 c

• Thermally stable

• Recyclable

45 cm • Biodegradable

Fig. 1 | The preparation of high-performance lignocellulosic bioplastic. a, Schematic demonstrating the preparation and degradability of the
lignocellulosic bioplastic. First, the porous matrix of natural wood is deconstructed using DES, which dissolves the natural lignin and fibrillates the
cellulose of the wood cell walls into micro/nanofibrils. Then we in situ regenerate the lignin by adding water, which causes it to deposit and bind to
the interconnected cellulose micro/nanofibrils network through the formation of hydrogen bonding. The cellulose and lignin after DES treatment are
recombined in the in situ lignin regeneration process to prepare a cellulose–lignin slurry. The lignocellulosic bioplastic obtained from this slurry can be
naturally degraded by microorganisms in the soil. b, Photograph of the lignocellulosic bioplastic.

lignin15–17, the last of which serves as a binder that helps adhere the
cellulose fibres that form the wood cell walls. To deconstruct the
loose and porous structure of the wood powder, we turned to bio-
degradable and recyclable deep eutectic solvent (DES)—a family of
green solvents that feature characteristics of both ionic liquids and
organic solvents. DES can efficiently deconstruct wood by disrupt-
ing the hydrogen bonding between cellulose fibres as well as dem-
onstrating the ability to dissolve lignin18–23. In our system, the DES
consisted of choline chloride (ChCl) and oxalic acid, which serve as
the hydrogen bond acceptor and donor, respectively. The solution
was prepared by simply heating ChCl and oxalic acid (1:1 molar
ratio) at 80 °C to form a transparent solution (Fig. 2b). ChCl and
oxalic acid form hydrogen bonding interactions (OH···Cl), which
reduces the ability of the compounds to crystallize and keeps DES
in a stable liquid state (Fig. 2c). Additionally, this configuration
facilitates the delocalization of the hydrogen protons in oxalic acid,
which increases the acidity of the DES, thus improving the treat-
ment efficiency of wood24,25. The rich hydrogen bonding and acidity
of the DES allows for both the rapid dissolution of the native lignin
and defibrillation of the wood (Extended Data Fig. 1). We then add
water, a green and highly polar solvent26, to the solution of dissolved
lignin and fibrillated cellulose fibres. As lignin is hydrophobic, this
process leads to its rapid regeneration from the DES. After filtering
and washing this mixture using water to remove residual DES, we can
obtain a stable cellulose–lignin slurry in large quantities (Fig. 2d),
featuring a high solid content (up to 20 wt%) and high viscosity
(Supplementary Fig. 1).
With this high solid-content slurry, we can fabricate lignocellu-
losic bioplastic films via a simple casting process that can be con-
ducted at large scale (Fig. 2e). After evaporating the water at room
temperature, we obtained lignocellulosic bioplastic films with sizes
of up to 100 × 15 × 0.1 cm (Fig. 2f and Supplementary Fig. 2). The
resulting lignocellulosic bioplastic exhibits excellent mechanical
robustness and flexibility. It can be easily rolled without break-
ing due to the entangled cellulose fibrils and regenerated lignin
binder (Supplementary Figs. 3 and 4). Different from traditional
manufacturing processes of cellulose-reinforced composite bioplas-
tics and cellulose films, which delignify the material and treat the
extracted lignin as manufacturing waste, our in situ lignin regenera-
tion method fully uses the lignocellulosic components of the bio-
mass without tedious separation steps, providing a more efficient
approach to lignocellulosic biomass use.

628 Nature Sustainability | VOL 4 | July 2021 | 627–635 | www.nature.com/natsustain

NaTuRE SusTaInabIlITy Articles
a b

80 °C

2,000 ml per bottle

Choline chloride Oxalic acid DES

c OH + O
OH + –

O
–
OH 80 °C

H
Cl HO
∆ Cl
N
O N

H
O
H-bond acceptor H-bond donor Intermolecular H-bond

d e

1,000 ml per bottle

Fig. 2 | The fabrication process of the lignocellulosic bioplastic by the in situ lignin regeneration method. a, Wood powder, a waste byproduct from wood
processing. b, The formulation process of the DES used in this work, which is composed of ChCl and oxalic acid. c, The formation of hydrogen bonding
between ChCl and oxalic acid. d, Large-volume cellulose–lignin slurries can be produced. e, Experimental demonstration of the preparation process of the
lignocellulosic bioplastic by casting with a glass rod. f, A large-scale sheet of lignocellulosic bioplastic (100 × 15 × 0.1 cm).

Structure and composition of the lignocellulosic bioplastic. The
lignocellulosic bioplastic exhibits a homogeneous and dense struc-
ture with a relatively flat surface (Fig. 3a,b and Supplementary Fig. 5).
As shown in Fig. 3c and Supplementary Fig. 6, the starting cellulose
material is defibrillated into micro/nanofibrils that are surrounded
by lignin, which functions as a natural and biodegradable binder
that tightly holds the micro/nanofibrils together, enhancing the
interactions between them. A dense, laminated structure is formed
in the lignocellulosic bioplastic, in which each layer is made of the
intertwined, lignin-adhered cellulose fibrils (Fig. 3d,e). This struc-
ture is substantially different from the loosely packed macro-sized
fibres (50–100 μm) of the natural wood powder starting material
(Extended Data Fig. 2). At higher resolution, transmission electron
microscopy (TEM) images show the diameters of the fibrillated
cellulose micro/nanofibrils of the lignocellulosic bioplastic ranged
from 10 to 300 nm (Fig. 3f and Supplementary Fig. 7) and featured
the deposition of regenerated lignin (Fig. 3g and Supplementary
Fig. 8). Note the fibrillated cellulose is densely functionalized with
hydroxyl groups, which strengthens the absorption of lignin by
hydrogen bonding, thus facilitating the structural self-assembly of
the regenerated lignin on the surface of the cellulose micro/nano-
fibrils. Compared to the natural wood powder (Extended Data
Fig. 2), small angle X-ray scattering (SAXS) verified the more iso-
tropic structure of the lignocellulosic bioplastic (Fig. 3h).
We also conducted Fourier transform infrared (FTIR) spectros-
copy of the natural wood powder, pure cellulose (that is, removing
lignin and hemicellulose from wood powder) and the lignocellulosic
bioplastic (Fig. 3i) to further investigate the chemical evolution dur-
ing the lignin regeneration process. The lignocellulosic bioplastic
features absorption peaks at 1,602, 1,508 and 1,456 cm−1 in the FTIR
spectrum, which are attributed to the vibrations of the aromatic
skeleton of lignin27. Additionally, these peaks do not appear in the
pure cellulose control, further suggesting the presence of lignin in
the lignocellulosic bioplastic. A new absorption peak in the ligno-
cellulosic bioplastic also appears at 1,726 cm−1, which corresponds
to the C=O stretching of a carbonyl group, indicating the partial
esterification of the cellulose hydroxyl groups by oxalic acid dur-
ing the DES treatment28. Due to the introduced carbonyl groups on
cellulose, the lignocellulosic bioplastic has a more negative charge
(zeta potential −28.2 mV) than the natural wood powder and pure
cellulose samples in neutral aqueous solution (pH 7) (Fig. 3j and
Supplementary Fig. 9). The repulsive force of the negatively charged
functional groups of the lignocellulosic bioplastic contributes to the
excellent dispersion of its slurry, enabling good processability via
casting. Meanwhile, X-ray diffraction (XRD) patterns of the wood
powder, cellulose and lignocellulosic bioplastic (Fig. 3k) exhibited
similar diffraction peaks (2θ = 14.6°, 16.6° and 22.6°) indicative of
the cellulose I crystalline structure29,30, confirming its preservation

Nature Sustainability | VOL 4 | July 2021 | 627–635 | www.nature.com/natsustain 629

 Articles NaTuRE SusTaInabIlITy

a b c

Microfibrils
Nanofibrils

5 µm 5 µm

d e

20 µm 5 µm

f g h
Microfibrils

Nanofibrils

1 µm 200 nm

i j k
–10 Wood powder
C=O Lignocellulosic bioplastic
Lignocellulosic
1,726 Cellulose
bioplastic –15
Transmittance (%)

Zeta potential

Intensity (a.u.)

Cellulose –20

O OH
HO
–25
Wood powder O Esterification O O
1,456
1,602

O O
HO
1,508

–30 OH
O
HO
OH

–35
Wood powder Cellulose Lignocellulosic 10 12 14 16 18 20 22 24
4,000 3,500 3,000 2,500 2,000 1,500 1,000
bioplastic 2θ (°)
Wavelength (cm–1)

Fig. 3 | Structural and compositional characterization of the lignocellulosic bioplastic. a, Photograph of the lignocellulosic bioplastic. b,c, Top-view
SEM images of the lignocellulosic bioplastic. d, Cross-sectional-view SEM image of the lignocellulosic bioplastic. e, Magnified SEM image of the sample
shown in d, revealing the layered structure of the material. f,g, TEM images of the micro/nanofibrils (f) and nanofibrils (g) in the lignocellulosic bioplastic.
h, SAXS pattern of the lignocellulosic bioplastic. i–k, FTIR spectra (i), zeta potential (j) and XRD spectra (k) of the natural wood powder, cellulose and
lignocellulosic bioplastic.

after the in situ lignin regeneration treatment. Additionally, the
crystallinity index of the lignocellulosic bioplastic was ~40.6 ± 4.3%,
showing a 9.4% enhancement compared to the raw wood powder
(~31.2 ± 3.2%), which we attribute to the removal of hemicellulose
and amorphous cellulose (Supplementary Fig. 10).
Molecular structure and interaction of lignin and cellulose. We
collected the 1H-13C nuclear magnetic resonance (NMR) spectra of
the in situ regenerated lignin in lignocellulosic bioplastic to gain
further insights into the transformation of the material and the
bonding mechanism between lignin and cellulose. Milled wood
lignin (MWL), as a representative of native lignin31, was also char-
acterized for comparison. Figure 4a shows the 1H-13C NMR spectra
of the MWL and regenerated lignin samples in the aliphatic region
(δC/δH 50–90/3.0–5.5) and aromatic region (δC/δH 95–135/6.3–8.0).
MWL consists of phenylpropane monomeric units32–34, which are
primarily linked through ether bonds (for example, β-O-4) and
carbon-carbon bonds (for example, β-β, β-5). The β-O-4 ether bond
typically accounts for ~40–65% of the total linkages in lignin34,35. In
the side-chain region, Aα(S) and Aβ(S) present Cα-Hα and Cβ-Hβ in
β-O-4 substructures linked to Syringyl units, respectively. However,
the signals correlating to Aα(S) (δC/δH 71.8/4.83) and Aβ(S) (δC/δH

630 Nature Sustainability | VOL 4 | July 2021 | 627–635 | www.nature.com/natsustain

NaTuRE SusTaInabIlITy Articles
a
S2,6 100 S2,6 100
OMe Cβ Bβ Cβ Bβ MeO γ γ OH
G2 OMe HO HO
G5 110 55 110 55 β β
G5 γ

S/G
MeO α α OMe
G6 120 Aγ Aγ HO
120 α β O O
A’γ 60 60
O O
130 130 OMe
Cγ A’γ Cγ
S/G OMe
65 65 OMe
Est
9

0
3
6

0
9
6
3
7

7
B
7.

7.
7.
7.

7.
A

7.
7.
7.
6.

Bγ

6.
Bγ
70 70 β-aryl ether (β-Ο-4) Tetrahydrofuran(β-β)
Aα(S)

75 75
5 G
β-O-4 HO
β 4 OMe 6 2
80 80 γ 6 2
α O
5
MeO OMe
Aβ(S) OMe
85 85 O
S/G R O
Bα R
13C 13C C S G
ppm ppm Phenylcoumaran(β-5) Syringyl Guaiacyl
1H 1H
5.0 4.6 4.2 3.8 3.4 5.0 4.6 4.2 3.8 3.4
Milled wood lignin In situ regenerated lignin

b The cleavage of β-O-4 of lignin

HO H3CO H3CO
γ H3CO
HO HO
HO Ketone
γ γ γ
HO
β O H3CO
α
β-O-4 α β O α O α β O
OCH3 DES β Hydration
OCH3 OCH3
Acidolysis Deprotonation Deprotonation HO
+
OCH3 OCH3
OCH3 OCH3 OCH3
O Phenolic hydroxyl
O
O O

c The interaction between lignin and cellulose HO

HO H O OH
O H O H
O O
O O O
HO O O
O O
OH O H O
H H
O HO

OH
OH

Lignin
OH

O
O
O O
H
O

Lignin
O
Lig
nin

Lignin
OC

O
O OCH
O
H3

3
H 3CO

Li
O

gn
Lignin

in
Lignin
HO OCH 3
H
OH O CO
CO H3 H3
Cellulose H OC
HO
3
CH O
3
O
O O HO
Regenerated lignin O
O O
HO OH
O H O H
O O
O O O
Lignocellulosic bioplastic O O
HO O OH H O
H O H O
H

Fig. 4 | The structure of the regenerated lignin and the interaction between the regenerated lignin and cellulose. a, 2D-HSQC NMR spectra of MWL and
the regenerated lignin: aliphatic regions (δC/δH 50–90/3.0–5.5), aromatic regions (δC/δH 95–135/6.3–8.0). b, The mechanism of cleaving the lignin β-O-4
bonds during DES treatment, resulting in the formation of a Hibbert’s ketone and phenol hydroxyl group. c, The structural linkages between regenerated
lignin and cellulose.

85.9/4.11) disappear in the regenerated lignin after the DES treat- via hydrogen bonding interactions, enabling the structural assem-
ment, confirming the cleavage of the β-O-4 ether bond, causing bly and highly entangled network found in the lignocellulosic
lignin to dissolve in DES. This process occurs by protonation of bioplastic. Additionally, the C-C signals (for example, Cβ, Bβ) of
the lignin Cα-OH group in acidic DES, followed by dehydration to the regenerated lignin still exist, which implies the C-C bonds of the
form a Cα cation intermediate25. The Cα cation is then transformed non-polar phenylpropanes in the regenerated lignin remain stable
to the Cβ cation via an enol ether intermediate or direct hydride after DES treatment.
shift36. Subsequent hydration and deprotonation then leads to Besides entanglement among the cellulose micro/nanofibrils via
the cleavage of the β-O-4 bond and the formation of a Hibbert’s hydrogen bonding, the interaction of cellulose and lignin is also
ketone and phenol hydroxyl group (Fig. 4b). The formation of these very important for the performance of the lignocellulosic bioplas-
ketone and phenol groups in the regenerated lignin facilitates the tic. Figure 4c schematically illustrates the interaction between the
crosslinking between the lignin and cellulose micro/nanofibrils regenerated lignin and cellulose micro/nanofibrils during in situ

Nature Sustainability | VOL 4 | July 2021 | 627–635 | www.nature.com/natsustain 631

Articles NaTuRE SusTaInabIlITy

a The biodegradability of the lignocellulosic bioplastic b The recyclability of the lignocellulosic bioplastic
10 October 2019 10 December 2019

In situ lignin Filtrating

regeneration DES and
water

PVC Lignocellulosic
Recycle
bioplastic
Casting
Recycle
30 December 2019 14 January 2020

Stirring Cutting

Debris Disappearance

c Environmental impacts of the lignocellulosic bioplastic

40 35 30 80 40

10–5 kg CO2 eq per cm3/MPa

10–7 kg SO2 eq per cm3/MPa

10–7 kg N eq per cm3/MPa

10–12 CTUh per cm3/MPa

10–4 CTUe per cm3/MPa

32 28
60 30
20
24 21
40 20
16 14
10
20 10
8 7

0 0 0 0 0
Acidification Ecotoxicity Eutrophication Global warming Human health-
potential carcinogenics
45 10 100
10–12 kg CFC-11 eq per cm3/MPa

15 80

10–8 kg PM2.5 eq per cm3/MPa

10–4 MJ surplus per cm3/MPa
10–6 kg O3 eq per cm3/MPa
10–11 CTUh per cm3/MPa

36 80
60
10
27 60
40 5
18 40
5
20
9 20

0 0 0 0 0
Human health- Ozone depletion Smog formation Fossil fuel Respiratory effects
non-carcinogenics depletion
This work ABS PVF

Fig. 5 | The biodegradability, recyclability and environmental impacts of the lignocellulosic bioplastic. a, The biodegradability tests of the lignocellulosic
bioplastic and PVC under moist soil. b, The recyclability of the lignocellulosic bioplastic. c, Environmental impacts of the lignocellulosic bioplastic compared
to ABS and PVF. The triangles show the results for the renewable energy scenario (wind) for the lignocellulosic bioplastic. CTUe, comparative toxicity
unit for ecotoxicity; CTUh, comparative toxicity unit for human health; CFC-11 eq, CFC-11 (trichlorofluoromethane) equivalent; PM2.5 eq, particulate matter
2.5 equivalent.

lignin regeneration. The regenerated lignin tightly interacts with lignin-induced adhesion, the lignocellulosic bioplastic demonstrates
the micro/nanofibrils containing hydroxyl and oxalic acid-induced a high tensile strength (~128 MPa; Extended Data Figs. 3 and 4 and
carbonyl groups by hydrogen bonding (OH···HO, COO···HO) and Supplementary Fig. 11) and excellent water stability (Supplementary
van der Waals forces to form strong lignin–cellulose supramolecu- Figs. 12–14 and Extended Data Fig. 5). Additionally, the abundant
lar complexes, which should impart the lignocellulosic bioplas- carbonyl and phenolic hydroxyl groups in the regenerated lignin
tic with high mechanical strength and excellent multifunctional allow the lignocellulosic bioplastic to almost completely absorb
performance. ultraviolet (UV) light from 200–400 nm in the UV–visible spec-
The regenerated lignin displays amphiphilic character due to its trum, suggesting its superior UV-screening ability (Supplementary
both polar hydrophilic side chains (for example, phenolic hydroxyl Fig. 15). Finally, the thermal degradation temperature of the ligno-
groups) and non-polar hydrophobic backbone (for example, hydro- cellulosic bioplastic is 357 °C, demonstrating the excellent thermal
carbon groups and phenylpropane). Such amphiphilic character is stability of the material (Supplementary Figs. 16 and 17).
attractive for achieving both good mechanical strength and water
stability, as the polar hydrophilic side chains can crosslink with Environmental impacts of the lignocellulosic bioplastic. The
the cellulose micro/nanofibrils to provide mechanical strength strong and hydrostable lignocellulosic bioplastic exhibits excel-
whereas the non-polar hydrophobic backbone can prevent water lent biodegradability in the natural environment. For comparison,
permeation. Due to the entanglement of the micro/nanofibrils and we buried sheets of the lignocellulosic bioplastic and polyvinyl

632 Nature Sustainability | VOL 4 | July 2021 | 627–635 | www.nature.com/natsustain

NaTuRE SusTaInabIlITy
chloride (PVC, a common plastic applied in a wide variety of con-
sumer products and the construction industry) in soil at a depth of
5 cm and monitored their morphology over time to determine their
degradability (Fig. 5a). The lignocellulosic bioplastic underwent a
swelling process and then became fractured after 2 months of burial
in the soil, probably due to the presence of microorganisms (for
example, bacteria and fungi). Microorganisms can directly attack
and digest the cellulose and lignin macromolecules of bioplastic37,38.
Eventually, it became completely biodegraded after being buried for
3 months. In contrast, the PVC retained its original shape without
any change after the same burial time, reflecting the long-lasting
burden of such non-biodegradable plastics on the environment.
Additionally, we placed lignocellulosic bioplastic in the grass where
it was exposed to sun, wind and rain for several months, resulting in
the complete degradation of its original structure as well (Extended
Data Fig. 6). This good balance between stability and biodegradabil-
ity (that is, the bioplastic is both stable and durable under working
conditions yet easily degraded under natural soil or outdoor condi-
tions) is appealing for designing next-generation sustainable, bio-
degradable and high-performance plastics that are not persistent in
the environment after their end-of-use.
The lignocellulosic bioplastic also demonstrates good recy-
clability. The end-of-life lignocellulosic bioplastic can be broken
back down into the uniform cellulose–lignin slurry by mechanical
stirring, allowing it to be reapplied as a recycled material (Fig. 5b).
Additionally, we can also recover the DES used in the process by
simply collecting the filtrate during processing and evaporating
the water (Extended Data Fig. 7). Even after recycling, the DES
maintains its excellent reaction efficiency at deconstructing the
lignocellulosic starting material (Supplementary Fig. 18). After
reusing the DES five times, the dissolved native lignin content was
~14.25%, decreased by ~3% compared to when pristine DES was
used (~17.45%), indicating the reactivity of the DES is retained even
after being recycled and reused. We also note the lignocellulosic
bioplastic can be made from various biomass feedstocks, such as
grass, wheat straw and bagasse, suggesting the broad applicability of
the treatment process (Extended Data Fig. 8).
We conducted a cradle-to-gate life-cycle assessment (LCA) to
quantify the environmental impacts of the lignocellulosic bioplastic
and compared the results to two common plastic films, acrylonitrile
butadiene styrene (ABS) and polyvinyl fluoride (PVF) (Fig. 5c and
Supplementary Table 1). In this work, the cellulose–lignin slurry
was fabricated into lignocellulosic bioplastic films by manually cast-
ing with a glass rod in the laboratory. At the industrial scale, we
assumed this casting process will be performed by the calendering
method, which can process paste-like mass into films and sheets39.
Across all the impact categories, the environmental impacts of
the lignocellulosic bioplastic are lower than PVF and close to the
lower bounds of the environmental impacts of ABS films (except
for ozone depletion, where the impact of lignocellulosic bioplastic is
close to the upper bound of ABS result). A contribution analysis was
conducted and the results indicate that the upstream production of
chemicals used in the DES preparation is the major contributor to
impact categories such as fossil fuel depletion, smog formation,
global warming potential and acidification (accounting for 46–87%
of the results in those categories). The results of other environmental
impact categories are driven by electricity used for the wood treat-
ment and DES recycling (49–86%). Note that the DES was assumed
to be reused nine times on the basis of laboratory experiments. We
anticipate that the environmental impacts of the bioplastic could be
even lower if DES was recycled and reused more times.
The electricity in this analysis was assumed to be purchased from
the US average grid. Therefore, the environmental impacts could
be lower if renewable energy were used. To estimate the impacts
of using renewable energy, we evaluated a scenario using electric-
ity generated from wind energy for the lignocellulosic bioplastic
Nature Sustainability | VOL 4 | July 2021 | 627–635 | www.nature.com/natsustain
Articles
production and calendaring process, the results of which are shown
in Fig. 5c as triangles for lignocellulosic bioplastic. Compared with
PVF and ABS, the environmental impacts of the lignocellulosic
bioplastic using wind energy were the lowest across all the impact
categories, except for ozone depletion. This result indicates the need
to use renewable energy to maximize the environmental benefits of
lignocellulosic bioplastics.
The high strength, superior recyclability and degradability of the
lignocellulosic bioplastic could lead to additional environmental
benefits that are not included in this LCA. For example, to fulfil
the same strength requirement, the lignocellulosic bioplastic only
requires 9–30% and 19–38% of the mass of ABS and PVF, respec-
tively. Additional comparisons with other biodegradable plastics
were conducted and the LCA results are shown in Extended Data
Fig. 9. We investigated butylene adipate-co-terephthalate (PBAT),
polyhydroxyalkanoates (PHAs), polylactic acids (PLAs), polybu-
tylene succinate (PBS) and polycaprolactone (PCL). Across most
environmental impact categories, lignocellulosic bioplastic is envi-
ronmentally preferable compared to PHA, PLA, PBS, PCL and
PBAT. In addition, the lignocellulosic bioplastic has much lower
density and higher tensile strength than all the biodegradable plas-
tics investigated (Supplementary Table 2). We also explored the fab-
rication of lignocellulosic bioplastic parts by compression moulding
(Supplementary Fig. 19). Such parts have potential applications in
the automotive manufacturing industry to replace parts made from
traditional fossil-based plastics such as polypropylene (PP), ABS
and polyethylene terephthalate (PET) with lower environmental
impacts (Supplementary Table 3 and Extended Data Fig. 10).
Discussion
In this work, we have demonstrated a simple yet cost-effective
in situ lignin regeneration approach to manufacture a new ligno-
cellulosic bioplastic that is strong, scalable, hydrostable, biode-
gradable and recyclable. Our approach involves the simultaneous
fibrillation of wood and dissolution of lignin in DES. The lignin
is then in situ regenerated on the micro/nanofibril surfaces by
simply adding water, which facilitates the strong contact between
lignin and cellulose through hydrogen bonding interactions.
The in situ regenerated lignin acts as a natural glue to tightly
wrap and link the cellulose micro/nanofibrils together, forming
a homogeneous and high solid-content slurry that can be easily
cast into films. The resulting lignocellulosic bioplastic demon-
strates high performance in various aspects, including a high ten-
sile strength of 128 MPa, excellent water stability, UV resistance
and improved thermal stability. Importantly, this lignocellulosic
bioplastic is not only biodegradable by natural microorganisms
but also recyclable by mechanical disintegration, allowing the
material to be reclaimed and used again in the production of lig-
nocellulosic bioplastic. LCA results reveal that the lignocellulosic
bioplastic demonstrates much lower environmental impacts than
petrochemical-based plastics such as PVF and ABS, or other bio-
degradable plastics such as PCL and PBS. This green and recy-
clable manufacturing process and final product demonstrate a
closed-loop cycle providing new opportunities to produce stable,
strong and biodegradable bioplastics from resource-abundant,
renewable and sustainable biomass.
Methods
Materials and chemicals. Poplar wood powder sieved under 60-mesh was selected
as a starting material. Choline chloride (C5H14ClNO, >98%), oxalic acid dihydrate
(H2C2O4 2H2O, >99%), sodium chlorite (NaClO2, >80%), acetic acid (>99%) and
sodium hydroxide (NaOH, >98%) were all of analytical grade and purchased from
Sigma–Aldrich. Cellulose film was purchased from Staples and used as a control to
measure its water stability, optical properties and mechanical strength.
Preparation of DES. A 1:1 molar ratio of ChCl and oxalic acid were mixed and
melted at 80 °C until a homogeneous and transparent liquid was obtained. The DES
mixture was then cooled to room temperature for use.
633
Articles
Fabrication of lignocellulosic bioplastic. Poplar wood and DES at a mass ratio of
1:15 were mixed and heated at 110 °C. Distilled water was added into the obtained
brown liquid (1:10 v/v) and stirred for 2 h. The cellulose and lignin were filtered
and washed using distilled water to remove residual DES. The DES was recycled
by heating the filtered liquid to remove water. After ultrasonic processing (800 W),
the mixture was vacuum-filtered for different amounts of time to obtain different
solid contents of the resulting cellulose–lignin slurry (~15 wt% solid content). The
slurry can be spread on a hydrophobic substrate (to aid in film removal) by a glass
rod to obtain the lignocellulosic bioplastic film after evaporation of water at room
temperature.
Fabrication of pure cellulose. To delignify the wood powder and produce pure
cellulose as a control, NaClO2 was first added to water to prepare a 5 wt% solution,
followed by the addition of acetic acid to change the pH to ~4.6. The 5 g of poplar
wood powder was treated to remove lignin in this NaClO2 (800 ml) solution at
90 °C for 6 h. To obtain highly purified cellulose, the sample was then treated to
remove hemicellulose with 5 wt% NaOH solution (800 ml) at 90 °C for 2 h. After
the chemical treatments, the sample was filtered and rinsed with distilled water
until the residues were neutral. The pure cellulose was used to test FTIR, zeta
potential and XRD.
Characterization. The morphology of the samples was observed with a Hitachi
SU-70 Schottky field-emission gun scanning electron microscope (SEM) (2–5 kV).
TEM images were collected using a field-emission gun JEOL-2100F microscope,
operated at 200 kV and equipped with a Gatan Tridiem 863 GIF (Gatan Imaging
Filter) system. FTIR spectra were recorded using a Nexus 670 FTIR spectrometer
over the range of 650‒4,000 cm−1. XRD patterns were collected using a Rigaku Ultima
III equipped with a curved detector manufactured by Rigaku Americas (operating
tube voltage of 40 kV, tube current at 30 mA, Cu Kα λ = 1.5406 Å). The chemical
composition of the wood powder and lignocellulosic bioplastic was measured
according to the Technical Association of Pulp and Paper Industry (TAPPI T19 m-54
and TAPPI-T222 om-88). SAXS measurements were taken using a Xenocs Xeuss
SAXS/WAXS/GISAXS small angle X-ray scattering system with an X-ray wavelength
of λ = 0.957 Å and sample-to-detector distance of 8.422 mm. The absorption
spectrum was measured by a UV–visible spectrometer Lambda 35 from 200 to
800 nm (PerkinElmer). The thermostability was measured by a thermogravimetric
(TG) analyser (SDT 650) using a heating rate of 10 °C min−1 in air. An integrated
sphere was used to collect the reflected light. Two-dimensional heteronuclear single
quantum coherence (2D-HSQC) NMR spectra were obtained using an Agilent Pro
Pulse 500 MHz spectrometer and recorded in the gradient HSQC adiabatic version.
Note that the lignocellulosic bioplastic samples were pressed (130 °C, 3 h) for the SEM
analysis, FTIR spectra, XRD patterns, TG and UV–visible spectra.
Water stability testing. The water contact angles of the lignocellulosic bioplastic
pressed at 130 °C for 3 h and cellulose film were measured using a OCA20 contact
angle measuring system (Dataphysics) at ambient temperature. To explore the
hydrostability of the materials, the lignocellulosic bioplastic and cellulose film were
submerged in water and the sample weights were measured on a calibrated balance
after removing the excess water on the sample surface using a Kimwipe.
Mechanical tensile test. The tensile properties of the lignocellulosic bioplastic and
cellulose film were measured using a Tinius Olsen H5KT tester. The dimensions of
the samples were ~50 × 5 mm2. The lignocellulosic bioplastic was pressed at 130 °C
for 3 h. The samples were stretched until they fractured at a constant test speed of
5 mm min−1.
Biodegradability test. For the soil biodegradability test, the lignocellulosic
bioplastic and PVC were cut into 5 × 4.5 × 0.025 cm pieces and then buried in
natural soil at a depth of 5 cm to test the biodegradability. Samples were taken out
periodically for observation. For the outdoor exposure test, the lignocellulosic
bioplastic and PVC were cut into 5 × 3 × 0.025 cm pieces. Samples were placed in
the grass and monitored regularly to test the biodegradability.
Life-cycle assessment. The LCA analysis followed the ISO standard series 14040
and was conducted using OpenLCA 1.10.3. Two functional units were used, one
was a constant mass (1 kg) of the bioplastic produced and the other normalized the
environmental impact results by tensile strength, allowing us to compare different
plastic materials in terms of both environmental impacts and material properties.
The system boundaries included wood residues acquisition, transportation
and lignocellulosic bioplastic production. See details in the Supplementary
Information.
Data availability
Data are available on reasonable request from the authors, according to their
contributions.
Received: 29 September 2020; Accepted: 19 February 2021;
Published online: 25 March 2021
634
NaTuRE SusTaInabIlITy
References
1. Yun, X. & Dong, T. in Food Packaging (ed. Grumezescu, A. M.) 147–184
(Academic Press, 2017).
2. Záleská, M. et al. Structural, mechanical and hygrothermal properties of
lightweight concrete based on the application of waste plastics. Constr. Build.
Mater. 180, 1–11 (2018).
3. Someya, T., Bao, Z. & Malliaras, G. G. The rise of plastic bioelectronics.
Nature 540, 379–385 (2016).
4. Kudrin, A. M., Gabriel’s, K. S. & Karaeva, O. A. The temperature effect on
mechanical properties of carbon fiber reinforced plastics for aviation
purposes. Inorg. Mater. 9, 763–766 (2018).
5. Rochman, C. M. et al. Classify plastic waste as hazardous. Nature 494,
169–171 (2013).
6. Brahney, J., Hallerud, M., Heim, E., Hahnenbergeret, M. & Sukumaran, S.
Plastic rain in protected areas of the United States. Science 368, 1257–1260
(2020).
7. Law, K. L. et al. The United States’ contribution of plastic waste to land and
ocean. Sci. Adv. 6, eabd0288 (2020).
8. Zhu, Y., Romain, C. & Williams, C. K. Sustainable polymers from renewable
resources. Nature 540, 354–362 (2016).
9. Lambert, S. & Wagner, M. Environmental performance of bio-based and
biodegradable plastics: the road ahead. Chem. Soc. Rev. 46, 6855–6871
(2017).
10. Chen, C. et al. Structure–property–function relationships of natural and
engineered wood. Nat. Rev. Mater. 5, 642–666 (2020).
11. Yang, J., Ching, Y. C. & Chuah, C. H. Applications of lignocellulosic fibers
and lignin in bioplastics: a review. Polymers 11, 751 (2019).
12. Balaguer, M. P., Gomez-Estaca, J., Gavara, R. & Hernandez-Munoz, P.
Biochemical properties of bioplastics made from wheat gliadins cross-linked
with cinnamaldehyde. J. Agric. Food Chem. 59, 13212–13220 (2011).
13. Yue, H. B., Cui, Y. D., Shuttleworth, P. S. & Clark, J. H. Preparation and
characterisation of bioplastics made from cottonseed protein. Green. Chem.
14, 2009–2016 (2012).
14. Herres-Pawlis, S. New stereocontrol on the block. Nat. Chem. 12, 107–109
(2020).
15. Venkateshaiah, A. et al. Recycling non-food-grade tree gum wastes into
nanoporous carbon for sustainable energy harvesting. Green. Chem. 22,
1198–1208 (2020).
16. Yang, Y., Tilman, D., Lehman, C. & Trost, J. J. Sustainable intensification of
high-diversity biomass production for optimal biofuel benefits. Nat. Sustain.
1, 686–692 (2018).
17. Isogai, A., Saito, T. & Fukuzumi, H. TEMPO-oxidized cellulose nanofibers.
Nanoscale 3, 71–85 (2011).
18. Arnodo, D., Ghinato, S., Nejrotti, S., Blangetti, M. & Prandi, C. Lateral
lithiation in deep eutectic solvents: regioselective functionalization of
substituted toluene derivatives. Chem. Commun. 56, 2391–2394 (2020).
19. Hong, S. et al. In-depth interpretation of the structural changes of lignin and
formation of diketones during acidic deep eutectic solvent pretreatment.
Green. Chem. 22, 1851–1858 (2020).
20. Hammond, O. S., Edler, K. J., Bowron, D. T. & Torrente-Murciano, L. Deep
eutectic-solvothermal synthesis of nanostructured ceria. Nat. Commun. 8,
14150 (2017).
21. Tan, X., Zhao, W. & Mu, T. Controllable exfoliation of natural silk fibers into
nanofibrils by protein denaturant deep eutectic solvent: nanofibrous strategy
for multifunctional membranes. Green. Chem. 20, 3625–3633 (2018).
22. Sirvio, J. A., Visanko, M. & Liimatainen, H. Acidic deep eutectic solvents as
hydrolytic media for cellulose nanocrystal production. Biomacromolecules 17,
3025–3032 (2016).
23. Wang, M. et al. Highly stretchable, transparent, and conductive wood
fabricated by in situ photopolymerization with polymerizable deep eutectic
solvents. ACS Appl. Mater. Interfaces 11, 14313–14321 (2019).
24. Xia, Q. et al. Multiple hydrogen bond coordination in three-constituent deep
eutectic solvents enhances lignin fractionation from biomass. Green. Chem.
20, 2711–2721 (2018).
25. Liu, Q. et al. Novel deep eutectic solvents with different functional groups
towards highly efficient dissolution of lignin. Green. Chem. 21, 5291–5297
(2019).
26. Zhao, D. et al. A dynamic gel with reversible and tunable topological
networks and performances. Matter 2, 390–403 (2020).
27. Li, Y. et al. Facile extraction of cellulose nanocrystals from wood using
ethanol and peroxide solvothermal pretreatment followed by ultrasonic
nanofibrillation. Green. Chem. 18, 1010–1018 (2016).
28. Wang, H. et al. Extraction of cellulose nanocrystals using a recyclable deep
eutectic solvent. Cellulose 27, 1301–1314 (2019).
29. Zhu, M. et al. Highly anisotropic, highly transparent wood composites.
Adv. Mater. 28, 5181–5187 (2016).
30. Moon, R. J., Martini, A., Nairn, J., Simonsen, J. & Youngblood, J. Cellulose
nanomaterials review: structure, properties and nanocomposites. Chem. Soc.
Rev. 40, 3941–3994 (2011).
Nature Sustainability | VOL 4 | July 2021 | 627–635 | www.nature.com/natsustain
NaTuRE SusTaInabIlITy
31. Alvarez-Vasco, C. et al. Unique low-molecular-weight lignin with high purity
extracted from wood by deep eutectic solvents (DES): a source of lignin for
valorization. Green. Chem. 18, 5133–5141 (2016).
32. Wu, X. et al. Lignin‐derived electrochemical energy materials and systems.
Biofuel. Bioprod. Birefin. 14, 650–672 (2020).
33. Iravani, S. & Varma, R. S. Greener synthesis of lignin nanoparticles and their
applications. Green. Chem. 22, 612–636 (2020).
34. Ragauskas, A. J. et al. Lignin valorization: improving lignin processing in the
biorefinery. Science 344, 1246843 (2014).
35. Wu, X. et al. Solar energy-driven lignin-first approach to full utilization of
lignocellulosic biomass under mild conditions. Nat. Catal. 1, 772–780 (2018).
36. Fraile, JoséM., Zoel Hormigón, J. I. G., Mayoral, J. A., Saavedra, C. J., &
Salvatella, L. Role of substituents in the solid acid-catalyzed cleavage of the
β-O-4 linkage in lignin models. ACS Sustain. Chem. Eng. 6, 1837–1847
(2018).
37. Sanderson, K. Lignocellulose: a chewy problem. Nature 474, S12–S14 (2011).
38. Jung, Y. H. et al. High-performance green flexible electronics based on
biodegradable cellulose nanofibril paper. Nat. Commun. 6, 7170 (2015).
39. Ashter, S. A. in Thermoforming of Single and Multilayer Laminates Ch. 10
(William Andrew, 2013).
Acknowledgements
We acknowledge the support of the Maryland Nanocenter, its Surface Analysis Center
and AIMLab. We acknowledge J. Gao for his experimental suggestions.
Nature Sustainability | VOL 4 | July 2021 | 627–635 | www.nature.com/natsustain
Articles
Author contributions
L.H., Q.X. and C.C. designed the experiments. Q.X. carried out experiments. Y.G.Y.
and S.H. analysed the mechanical data. Y.Z. helped with the preparation of the
large-scale bioplastic film. Q.X. and J.L. fabricated the lignocellulosic bioplastic parts by
compression moulding. T.L. and X.P. provided some useful suggestions. Y.Y. provided
the LCAs. L.H., Q.X. and C.C. collaboratively analysed the data and wrote the paper.
All authors commented on the final manuscript.
Competing interests
The authors declare no competing interests.
Additional information
Extended data is available for this paper at https://doi.org/10.1038/s41893-021-00702-w.
Supplementary information The online version contains supplementary material
available at https://doi.org/10.1038/s41893-021-00702-w.
Correspondence and requests for materials should be addressed to Y.Y. or L.H.
Peer review information Nature Sustainability thanks Robert Allen, Eun Yeol Lee and
Tong-Qi Yuan for their contribution to the peer review of this work.
Reprints and permissions information is available at www.nature.com/reprints.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in
published maps and institutional affiliations.
© The Author(s), under exclusive licence to Springer Nature Limited 2021, corrected
publication 2021
635
Articles NaTuRE SusTaInabIlITy

Extended Data Fig. 1 | The fabrication mechanism of the lignocellulosic bioplastic. Loose and porous wood powder, composed of cellulose, lignin and
hemicellulose, serves as the starting material. After DES (ChCl/oxalic acid) treatment, the cellulose fibres are fibrillated into micro/nanofibrils while DES
dissolves the lignin. Water can interact with the hydrophobic DES through hydrogen bonding interactions. Thus, water can be added as a green antisolvent
in the system, causing the hydrophobic lignin to regenerate. After filtering, we obtain a cellulose–lignin slurry, the solid content of which we can control by
varying the water content. The lignocellulosic bioplastic film can then be obtained by casting the slurry at room temperature.

Nature Sustainability | www.nature.com/natsustain

NaTuRE SusTaInabIlITy Articles

Extended Data Fig. 2 | The structure of the wood powder. a-d, Photograph (a), SEM image (b), magnified SEM image (c) and SAXS pattern (d) of the
wood powder. Compared to the isotropic structure of lignocellulosic bioplastic, the wood powder shows more structural inhomogeneity.

Nature Sustainability | www.nature.com/natsustain

Articles NaTuRE SusTaInabIlITy

Extended Data Fig. 3 | The tensile strength and fracture surfaces of the lignocellulosic bioplastic. a, The tensile stress-strain curves of the cellulose film
and lignocellulosic bioplastic. b, The strength and toughness of the cellulose film and lignocellulosic bioplastic. The lignocellulosic bioplastic demonstrates
excellent mechanical properties with a high tensile strength of 128 MPa and toughness of 2.8 MJ·m3, which are 7- and 8-times higher than cellulose film
(18 MPa and 0.35 MJ·m3), respectively. c-d, Digital and SEM images of the fracture surfaces of the (c) lignocellulosic bioplastic and (d) cellulose film
after tensile testing. The samples have ~1 wt.% water content. The cellulose film fractured by macro-fibre slippage from the loose fibre network structure,
in which most fibres were not broken, indicating the binding strength between the cellulose fibres in the film is weaker than the strength of the fibres
themselves. In contrast, broken fibres appear in the fracture zone of the lignocellulosic bioplastic, suggesting its binding strength is greater than the
strength of its constituent fibres due to the intertwining cellulose micro/nanofibrils and lignin network. Such entangled interaction between the micro/
nanofibrils and high adhesion mediated by the in situ regenerated lignin matrix with abundant hydrogen bonding and van der Waals forces contribute to
the outstanding mechanical properties of the lignocellulosic bioplastic.

Nature Sustainability | www.nature.com/natsustain

NaTuRE SusTaInabIlITy Articles

Extended Data Fig. 4 | The excellent mechanical strength of the lignocellulosic bioplastic. a, Photographs of the lignocellulosic bioplastic
(8 cm×3.5 cm×0.1 cm), b, including under a heavy load (200 g). c-d, The excellent foldability of the lignocellulosic bioplastic. e, The unfolded
lignocellulosic bioplastic features a sharp crease. f, Photograph of the unfolded lignocellulosic bioplastic bearing a heavy load (200 g). Although the
lignocellulosic bioplastic had undergone folding, the creased material can still easily bear the applied weight without failing.

Nature Sustainability | www.nature.com/natsustain

Articles NaTuRE SusTaInabIlITy

Extended Data Fig. 5 | The water stability of the lignocellulosic bioplastic. a. Photographs of water droplets on the cellulose film and lignocellulosic
bioplastic surfaces over time (0–10 min). The lignocellulosic bioplastic has a higher water contact angle (90.0 ± 8°) than that of pure cellulose film
(78.7 ± 10°), demonstrating its slightly greater tendency to repel water. After 10 minutes, the water droplet gradually spreads out and adheres to the
cellulose film (28.2 ± 6°), whereas the shape of the droplet on the lignocellulosic bioplastic surface remains relatively stable (71.8 ± 7°). b, Water
absorption of the cellulose film and lignocellulosic bioplastic over 140 min. The inset shows photographs of water droplets on a sloping lignocellulosic
bioplastic surface (right), demonstrating the material’s excellent water stability, while the water is quickly absorbed on the cellulose film (left). The
lignocellulosic bioplastic has exceptionally lower water absorption (~30%) than that of the cellulose film (~100%). In contrast, water droplets easily
permeate into the hydrophilic cellulose film even on inclined surfaces. c, Water stability test of cellulose film and lignocellulosic bioplastic in water for
30 days. The cellulose film disintegrates while the lignocellulosic bioplastic film maintains its shape. We immersed the cellulose film and lignocellulosic
bioplastic in water for thirty days. After this time, we found the cellulose film completely disintegrated into microfibers, while the lignocellulosic bioplastic
showed good stability in the wet environment, retaining its shape without any fractures.

Nature Sustainability | www.nature.com/natsustain

NaTuRE SusTaInabIlITy Articles

Extended Data Fig. 6 | The degradability tests of the lignocellulosic bioplastic and PVC materials. Direct outdoor exposure was carried out to evaluate
the degradability of the lignocellulosic bioplastic, which was placed on grass and exposed to the sun, wind and rain (College Park, Maryland, U.S., from
October 20, 2019 to March 10, 2020). After three months, the dimensions of the lignocellulosic bioplastic increased as it became more swollen. After
~4 months, the lignocellulosic bioplastic became cracked and fragmented and its original structure completely degraded after five months. Meanwhile,
the PVC remained almost the same as on the first day, demonstrating it cannot be degraded under natural conditions.

Nature Sustainability | www.nature.com/natsustain

Articles NaTuRE SusTaInabIlITy

Extended Data Fig. 7 | Flow diagram for continuous in situ lignin regeneration treatment and the recycling of the DES. After mixing and heating of the
wood powder and DES, followed by the addition of water to in situ regenerate the lignin, we can use an in-line filter to separate the cellulose–lignin slurry
and solvent, in which the DES and water make up the filter liquor. DES can then be purified by heating the mixture to remove water. The recovered DES can
be recycled in the system to treat new lignocellulosic starting materials. Water can also be collected using a condenser and recycled again to serve as the
antisolvent for lignin regeneration.

Nature Sustainability | www.nature.com/natsustain

NaTuRE SusTaInabIlITy Articles

Extended Data Fig. 8 | The universality of in situ lignin regeneration approach. The lignocellulosic bioplastic can be derived from various lignocellulosic
biomass sources, including wood, wheat straw, grass and bagasse, demonstrating the strong universality of this approach.

Nature Sustainability | www.nature.com/natsustain

Articles NaTuRE SusTaInabIlITy

Extended Data Fig. 9 | The life cycle impact assessment results of lignocellulosic and other biodegradable plastics per cm3/MPa. Across most
environmental impact categories, the lignocellulosic bioplastic developed in this work is more environmentally favourable than PHA, PLA, PBS, PCL and
PBAT. There are a few exceptions. Compared with PBAT, the lignocellulosic bioplastic has higher impacts in three categories, including eutrophication,
human health - carcinogenics and respiratory effects. For all three categories, the impacts of lignocellulosic bioplastics are driven by electricity
consumption, which accounted for 71–86% of the results based on the contribution analysis. The electricity was assumed to be the U.S. average grid in
this study. The environmental impacts could be lower if renewable energy were used. To estimate the impacts of using renewable energy, a scenario using
electricity generated from wind was evaluated and the results are shown in Extended Data Fig. 9 as triangles. The Life Cycle Inventory (LCI) of wind energy
was obtained from Ecoinvent database for onshore generation in the U.S. The environmental impacts of the lignocellulosic bioplastic using wind energy are
the lowest across all the impact categories except fossil fuel depletion (close to the upper bounds of the results of PLA and PBAT).

Nature Sustainability | www.nature.com/natsustain

NaTuRE SusTaInabIlITy Articles

Extended Data Fig. 10 | Environmental impacts of the moulded lignocellulosic bioplastic compared to PP, PET and ABS. Compared to PP and ABS,
the lignocellulosic bioplastic is at the lower end across all environmental impact categories. Compared to PET, the lignocellulosic bioplastic has lower
environmental impacts in categories such as ecotoxicity, eutrophication and human health. For other categories, the lignocellulosic bioplastic has
comparable results with PET and close to the higher bounds of PET’s impacts in ozone depletion, smog formation and fossil fuel depletion. Similar to the
LCAs for plastic films, we included a renewable energy scenario to investigate the impacts of using wind and the results are shown as triangles (Extended
Data Fig. 10). Compared with PP, PET and ABS, the environmental impacts of the lignocellulosic bioplastic using wind energy were the lowest across all the
impact categories, except for fossil fuel depletion (which was close to the upper bound of PET’s results).

Nature Sustainability | www.nature.com/natsustain

View publication stats