Article https://doi.org/10.

1038/s41467-024-48937-3

Internal water circulation mediated

synergistic co-hydrolysis of PET/cotton
textile blends in gamma-valerolactone
Received: 21 January 2024 Shun Zhang 1, Wenhao Xu1, Rongcheng Du1, Lei Yan1, Xuehui Liu2,
Shimei Xu 1 & Yu-Zhong Wang 1
Accepted: 17 May 2024

Recycling strategies for mixed plastics and textile blends currently aim for
Check for updates recycling only one of the components. Here, we demonstrate a water coupling
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strategy to co-hydrolyze polyester/cotton textile blends into polymer mono-

mers and platform chemicals in gamma-valerolactone. The blends display a
proclivity for achieving an augmented 5-hydroxymethylfurfural yield relative
to the degradation of cotton alone. Controlled experiments and preliminary
mechanistic studies underscore that the primary driver behind this heightened
conversion rate lies in the internal water circulation. The swelling and dissol-
ving effect of gamma-valerolactone on polyester enables a fast hydrolysis of
polyester at much lower concentration of acid than the one in the traditional
hydrolysis methods, effectively mitigating the excessive degradation of
cotton-derived product and undesirable product formation. In addition, the
system is also applicable to different kinds of blends and PET mixed plastics.
This strategy develops an attractive path for managing end-of-life textiles in a
sustainable and efficient way.

In the past two decades, global fiber production has nearly doubled chemcycling, components other than the target components are
and it is forecasted that fiber consumption will reach 160 million tons generally considered to be unfavorable to the reaction. Separation is
in 20501–3. The current fast fashion trend not only leads to increased usually adopted prior to chemical degradation through manual or
demand for new garments but also a significant amount of textile machine sorting17–19, as well as selective dissolution by solvents
waste4,5. The impact of the fashion industry on the environment is (Fig. 1a)20–22. However, It makes the whole process time-consuming and
widespread and thought-provoking, accounting for an estimated energy-extensive. An alternative way is to directly degrade one com-
8–10% of global CO2 emissions6. Meanwhile, the textile wastes are ponent of textile blends while retaining the other intact (Fig. 1b).
predominantly subjected to landfilling or incineration at the end of life, Current research efforts predominantly concentrate on converting
resulting in a depletion of resources and environmental pollution7–9, as easily treated cotton fibers into chemicals, such as sugars or furfural,
well as the potential health threat of microfibers, which have been using acid or ionic liquid, while keeping the polyester unchanged23,24.
found in rivers, oceans, and drinking10–12. To tackle environmental Differently, in our recent work, in-situ alkaline hydrolysis of polyester
concerns, chemcycling is regarded as a promising method to develop into terephthalic acid (TPA) is achieved while cotton fibers remain
sustainable fashion and circular economy13–15. However, textiles fre- intact in CH2Cl2-EtOH solvents25. Generally, these strategies take
quently comprise diverse polymers, of which the polyester/cotton advantage of the differences in solubility or degradation selectivity
textile blends account for the vast majority16. In the process of among the components of the blends to recover a specific component

1
Collaborative Innovation Center for Eco-Friendly and Fire-Safety Polymeric Materials (MoE), State Key Laboratory of Polymer Materials Engineering, National
Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), College of Chemistry, Sichuan University, Chengdu, China. 2Collaborative Innovation
Center for Eco-Friendly and Fire-Safety Polymeric Materials (MoE), State Key Laboratory of Polymer Materials Engineering, National Engineering Laboratory of
Eco-Friendly Polymeric Materials (Sichuan), College of Architecture and Environment, Sichuan University, Chengdu, China. e-mail: [email protected]

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Article https://doi.org/10.1038/s41467-024-48937-3

a. Degradation after Separation Strategy

O
O O O Degradation
O O n Monomers
n O
O polyester
Separation
polyester
OH OH Reuse or
O HO
OH OH degradation Chemicals
O O HO
O O O O O or
HO OH OH n HO OH OH n regenerated cotton
cotton cotton

· Tedious separation steps

· Harsh degradation conditions of polyester

b. Selective Depolymerization of Specific Components

OH
O OH
O 1 O HO
O Monomers + O O O
n HO OH OH n
O Selective
degradation cotton
polyester
or O
OH O
OH O
O HO
O O n
HO OH OH
O + Sugars or HMF
n O
2 (yield <15%)
cotton polyester

· High concentration acid or alkali

· Additional steps required to recover the other components

c. Synergistic Co-degradation Strategy (This Work)

O
O O
n O OH
O OH O O
polyester GVL/TsOH HO HO OH
+ +
O TPA EG HMF
OH 1h
O HO
OH Yield>95% Yield 100% Yield 25%
O O O
HO OH OH n
cotton
· New strategy of recycling mediated by internal circulating water
· The co-hydrolysis of substrates ensured by swelling/dissolution of GVL
· Low concentration acid
Fig. 1 | Chemical recycling strategies of polyester/cotton blends. a Degradation after separation strategy and b selective depolymerization of specific components in the
traditional method. c Synergistic co-degradation strategy in this work.

while preserving the integrity of the others. However, additional steps However, the generation of HMF involves a dehydration step, and an
will be required to recover the other components, which results in increase in water content may impede the favorable progression of
additional energy costs. the reaction. The yield of HMF recovered from cotton degradation is
In addition, in the process of recycling the mixture, the by- often less than 15%3,27,28. Considering that the acidic hydrolysis of
products produced by one polymer may have unexpected effects on both polyester and cotton is a water-consuming process, it is pro-
the transformation of another polymer. Recently, Ma26 reported a mising to achieve synergistic co-degradation of polyester/cotton
method of in-situ utilization of chlorine released by PVC, which blends by utilizing the byproduct water from the HMF dehydration
successfully converted PET into terephthalic acid and 1,2- dichlor- step to meet the water consumption requirement for the hydrolysis
oethane with high yield. Different from the previous experiences of polyester and cotton. However, due to the differences between the
where chlorine in PVC was usually considered to be harmful to the two polymers, there are two main issues that need to be addressed in
transformation of other polymers due to catalyst poisoning, the the acidic co-hydrolysis of polyester/cotton blends into TPA and
above work demonstrated that chlorine can also play an active role in HMF. One is to avoid the formation of undesirable byproducts from
the transformation of the mixture into valuable products. However, cotton in high concentrations of acid, such as 80 wt% para-
the simultaneous transformation of textile blends into high-valued toluenesulfonic acid (TsOH)29. The high acid concentration is
chemicals is more intriguing but very challenging due to different, necessary for polyester hydrolysis due to the heterogeneous nature
even conflicting, degradation needs among different components. of the reaction but may lead to excessive degradation of cotton,
We found that 5-hydroxymethylfurfural (HMF) is an important bio- forming undesirable byproducts. The other is to strike a balance
based platform chemical for the production of renewable monomers between HMF transformation and polyester/cotton hydrolysis
and bio-fuels, which can be produced by acidolysis of cotton. through internal water circulation.

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Table 1 | Degradation of polyester and cotton [a] sole cotton was degraded, but a continuous decrease for the polyester/
cotton blends (Fig. 2b). This phenomenon suggests that an equilibrium
Entry Substrate Solvent Yield (%)
is reached between the water consumption from cotton hydrolysis and
TPA [c] HMF [d] water production from fructose dehydration in the case of cotton.
1 polyester GVL 96.3 ± 1.6 / However, the water content after reaching equilibrium is not con-
2 polyester H2O <1 / ductive to HMF formation. With the addition of polyester, water con-
3 cotton GVL / 19.7 ± 1.1 sumption increased. The reaction equilibrium above was broken,
4 cotton H2O / 4.34 ± 1.1 which promoted HMF formation. As a result, the introduction of
external water is not conducive to the forward progress of the gen-
5 polyester/ GVL 95.8 ± 1.9 24.1 ± 1.0
cotton eration of HMF (Fig. 2c). When GVL was replaced by water, the yield of
6 polyester/ H2O <1 4.73 ± 0.9
HMF was only about 4%, which is 5 times lower than the one in GVL no
cotton matter whether polyester/cotton blends or pure cotton (Table 1, entry
7 polyester/ GVL/ H2O [b] 28.3 ± 1.4 7.38 ± 1.3 6 and entry 4). Besides, the increase of water content decreased the
cotton degradation rate of polyester accordingly due to weakened swelling/
Polyester and cotton were cut from textiles; [a] Reaction under 170 °C for 60 min with 7.5 wt% solubility of PET in GVL (Fig. 2d). This also explained why polyester
TsOH, the solvent is 20 mL. Unless otherwise specified, the polyester/cotton blends utilized in fiber hardly depolymerized at the same temperature and time in
this work is 1 g (with a polyester to cotton mass ratio of 8:2). In experiments involving the aqueous solution (Table 1, entry 2, Supplementary Fig. 6).
individual use of cotton or polyester, the masses of polyester and cotton are 0.8 g and 0.2 g,
respectively. [b] The volume ratio of GVL to H2O is 5:5; [c] Yield determined by weight; [d] Yield
To further elucidate the mechanism of water circulation, the
determined by NMR and HPLC. degradation rate of polyester/cotton blends and HMF yield at different
reaction times was investigated (Supplementary Fig. 7-8, Supplemen-
tary Table 1). Within the initial 10 min of the reaction, almost no
In this work, we show a water coupling strategy to co-hydrolyze polyester depolymerization and HMF formation were observed,
polyester/cotton textile blends into polymer monomers and platform except that only a minor amount of cotton hydrolysis occurred. It
chemicals. We consider gamma-valerolactone (GVL) as the reaction suggested that the glucose accumulated in the stage. Subsequently,
solvent, utilizing its excellent swelling and solubility properties on the glucose underwent isomerization and dehydration procedures to
polyester to enhance interfacial mass transfer (Fig. 1c). This, in turn, generate HMF (Supplementary Fig. 9-10). Meanwhile, the degradation
enabled the degradation of polyester at low acid concentration. Fur- rate of both polyester and cotton in the blends gradually rose. Com-
thermore, we found that internal water circulation meets the needs of pared to sole cotton, the degradation rate of cotton in the blends
the synergistic conversion of blends. The water generated from the showed minimal variation over time, demonstrating that the presence
production of HMF is utilized to participate in the degradation of of polyester did not significantly impact cotton degradation. However,
polyester, while the water consumed by the depolymerization of HMF yield was notably higher than that in sole cotton accordingly.
polyester promotes the conversion of HMF. This strategy opens up an Especially, there was a sharp acceleration in the polyester degradation
attractive path for managing commercial waste textiles and lays the in a period of 40 and 60 minutes, which corresponded to a rapid
groundwork for energy-efficient chemcycling for diverse waste blends. decrease of water content in the degradation solution. Accordingly,
the HMF yield also increased to 25%, indicating that the water con-
Results sumption in polyester depolymerization facilitated the dehydration of
Degradation of polyester/cotton blends fructose to produce HMF.
Here, we employed an eco-friendly solvent GVL to simultaneously
degrade polyester and cotton in polyester/cotton blends into high- Solvent effect on the degradation process
value products under a concentration of TsOH as low as 7.5% at 170 °C To further investigate the significant differences in the degradation of
for 1 h (Fig. 1c). The concentration of TsOH is only 10% of the one in the polyester and cotton in GVL and water, XRD spectra were performed
traditional hydrolysis of polyester29. Polyester was completely depo- on the residues of cotton reacted in GVL and water at different times,
lymerized to obtain TPA with high yield (>95%) and high purity (>99%) respectively. The crystalline peak of cotton at 22.6° significantly
(Supplementary Fig. 1-3), which is comparable to that by two-step decreased in GVL while showing slight changes in water with increasing
alkaline depolymerization of polyester30. Meanwhile, the cotton was reaction time up to 40 min (Supplementary Fig. 11). The crystallinity of
degraded into versatile platform compound HMF with yield of 25% cotton in GVL showed a trend of initially increasing and then
(Supplementary Fig. 4-5), which is almost twice as much as that in decreasing with time (Fig. 3a). This was because that the degradation in
traditional degradation method of cotton31. Furthermore, no addi- the initial stage of reaction were inclined to take place in the amor-
tional water was added in the whole process, indicating a good phous region of cotton, leading to an increase in its crystallinity of
matching between water production and consumption. residual cotton. However, with further extending of reaction time, the
crystalline region was destructed, resulting in a decrease in crystal-
Internal water circulation of polyester/cotton blends linity. At 30-40 min, the crystallinity of cotton decreased from 76% to
degradation 37%, indicating a significant conversion at this stage. In contrast, the
As observed in the experiment above, the yield of HMF from polyester/ crystallinity of cotton in water showed a steady upward trend, which
cotton blends is higher than that from pure cotton (Table 1, entry 5 was because the degradation rate of cotton in water was relatively
and entry 3). We speculate that polyester plays a positive role in the slow, and the crystalline region was destroyed in a limited degree. A
conversion process of cotton. It was further confirmed by the fact that similar phenomenon was observed in the reaction of polyester, where
the yield of HMF exhibited a decreasing trend as the polyester content the peak intensity of polyester in GVL changed more significantly than
in the blends gradually decreased (Fig. 2a). Transformation of HMF in water (Supplementary Fig. 12). The crystallinity of the residual solid
from cotton is a dehydration process, and prompt removal of water material after different reaction time in water remained stable at
will facilitate the further reaction. Through real-time monitoring of the around 43% (Fig. 3b), which was consistent with the previous obser-
water content in the degradation solution, it was observed that the vation that polyester was hardly degraded in water (Table 1, entry 2).
water content initially decreased and then remained stable when the However, in GVL, the crystallinity of polyester showed a trend of

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a b

c d

Water in Cotton Water in Polyester

OH
O OH
e O O O
HO
O HO
OH
O O
n
n OH
O Cotton
Feedback + +
Hydrolysis
Polyester H + H2O H 3O

OH
OH HO O
H 2O HO
Hydrolysis O O OH
OH
Glucose
HMF

Dehydration CH2OH OH Isomerization

O
O OH
OH
HO OH
+ HO OH CH2OH
O
TPA EG Fructose

Fig. 2 | Mechanism of internal circulation of water. a The effects of polyester/ solution is 0.31%); (c) Effect of different contents of water in GVL on HMF yield from
cotton blends ratios on HMF yield distribution. The data points are from N = 3 cotton and (d) on the degradation rate of polyester. e Internal water circulation in
independent experiments. b Water content in degradation solution of polyester/ the degradation process of polyester/cotton blends. Reaction under 170 °C with
cotton blends or cotton at different reaction time (the water content in the initial 7.5 wt% TsOH, the GVL is 20 mL.

initially decreasing and then increasing with the extending of hydro- during the process, signifying that there were no bonds broken apart
lysis time. It is contrary to the cotton. At the lower temperatures, from physical fragmentation (Supplementary Fig. 13). We further
polyester either experienced swelling or partial dissolution in GVL. examined the structural alterations in polyester during the dissolution
However, at 170 °C, a transparent solution was observed, indicating process at 170 °C in GVL (Fig. 3d). After a 0.5 h treatment, a white solid
the complete dissolution of polyester (Fig. 3c). Upon cooling, a white was obtained with original flake-like structure upon cooling the solu-
solid precipitated from the solution, signifying the ability of polyester tion. After 1 h, almost all of the polyester transformed into a paste-like
to dissolve in GVL, thus promoting its degradation at this reaction solid, and after 3 h, no polyester residue remained in the solution. It
temperature. However, in water, polyester remains basically unchan- explains a sudden increase of the degradation rate is due to the dis-
ged. The FT-IR spectra of polyester treated with GVL for different solution of polyester in GVL. However, the morphology of polyester
durations indicated that the ester groups of polyester remained intact fiber remained almost unchanged in water after 3 h treatment. Due to

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a b e

c 25°C 130°C 150°C 170°C Cooling In water f

Polyester 0.5 h 1h 3h 3h
d

Fig. 3 | Monitoring the degradation process of polyester/cotton blends. a XRD TsOH, 170 °C, 20 mL solvent. Polyester treated by GVL and water at different
spectra of cotton in GVL and water at different reaction time, b XRD spectra of temperatures for 3 h (c) and different time at 170 °C (d); XRD spectra of polyester
polyester in GVL and water at different reaction time. Reaction conditions: 7.5% (e) and cotton (f) treated with GVL at different time.

the disintegration of the physical structure, polyester experienced within the temperature range of 150-170 °C, the polyester degradation
alterations in its crystallinity during the dissolution process. The rate was still less than 50% below 165 °C (Fig. 4b). The kinetic analysis
crystallinity of initial polyester was 42.2% and then decreased to 30.6% reveals that, in the temperature range of 110-150 °C, the reaction rate
after treatment with GVL for 3 h (Fig. 3e). constant for polyester experiences a slight increase, suggesting a low
It indicated that GVL not only efficiently dissolves polyester to reactivity within this temperature interval. The rate constant increased
increase the reaction surface area but also reduces its crystallinity by a factor of 20 at 170 °C compared to the one at 150 °C (Fig. 4c). This
during the degradation process. However, GVL did not significantly substantial increase can be attributed to the effective mass transfer
affect the structure of cotton. Even after treating cotton with GVL for due to the complete dissolution of polyester in GVL at 170 °C. This rate
5 h, its network structure remained intact (Fig. 3f and Supplementary constant in GVL is 100 times as much as the one in aqueous solution
Fig. 14). The above swelling/degradation process of polyester/cotton (Fig. 4d). As a result, only one-tenth of the acid dosage was required
blends in GVL may have undergone the following stages: Initially, compared to the one in the traditional polyester hydrolysis method29.
glucose accumulates during the decomposition of cotton. At this It greatly suppressed the possible side reaction in acidolysis of cotton
stage, PET is experiencing a swelling-dissolution process and is not yet (Supplementary Fig. 15-16). These findings confirmed that GVL can
involved in the water recycling process. Over time, glucose is iso- effectively accelerate the degradation rate in low acid concentrations.
merized into fructose and then fructose undergoes dehydration to To verify the stability of GVL in the reaction, we employed the struc-
form HMF. The water generates in this process, which is fed back into tural unit of polyester, bis(hydroxyethyl)terephthalate (BHET), as a
the hydrolysis process of polyester/cotton blends, facilitating internal model compound to simulate the reactivity difference. It was calcu-
water circulation and continuously driving the reaction forward. The lated that the Gibbs free energy of BHET and GVL was 15 kJ/mol and
entire reaction pathway is depicted in Fig. 2e. 31.5 kJ/mol, respectively (Fig. 4e), aligning with the experimental
The abrupt increase of degradation rate of polyester from 150 °C observation that only polyester can be degraded while GVL remains
to 170 °C further confirmed that the dissolution of PET in GVL accel- intact. This finding further supports the use of GVL as a suitable
erated the degradation (Fig. 4a). Below 20% degradation rate for reaction solvent for polyester.
polyester was observed while more than 90% for cotton at 150 °C. TPA as an acidic substance might affect the cotton conversion. No
Further, by increasing the temperature to 170 °C, 100% of the degra- degradation of cotton was observed in the absence of an acid catalyst.
dation rate of both polyester and cotton was achieved. Even if we However, when TPA was added, the degradation solution was light
conducted an extensive analysis of the polyester degradation rate yellow. Roughly 18% of the cotton underwent degradation but no HMF

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a b

c d

e O
O OH
OH OH O OH
O HO O
O O
HO O
O GVL 4-HV
BHET TPA

4-HV

TPA
ΔG=31.5 KJ/mol
ΔG=15.6 KJ/mol
BHET GVL

Fig. 4 | Degradation kinetics studies of polyester/cotton blends. a The effects of rate constants of polyester at different temperatures in GVL. d The reaction rate
reaction temperature on the degradation of polyester and cotton, and the dis- constants of polyester in GVL and aqueous solutions at 170 °C. e Calculation of
tribution of products. b Variation of polyester degradation rate from 150–170 °C. Gibbs free energy of reaction solvent GVL and model compound BHET.
The data points (a) and (b) are from N = 3 independent experiments. c The reaction

was detected at the presence of TPA (Supplementary Fig. 17), sug- cotton blends, the internal water circulation promotes cotton con-
gesting TPA was only active in catalyzing the degradation of cotton not version, increasing HMF yield from 19.7% to 25%. HPLC analysis showed
the conversion to HMF (Fig. 5a). The degradation rate of cotton that in addition to HMF, the remaining major product was glucose,
increased then plateaued as TPA amount increased (Supplementary with a yield of approximately 46%, resulting in an overall carbon yield
Fig. 18). This could be attributed to the partial dissolution of TPA in of 71% (Supplementary Fig. 9). The carbohydrates and HMF can be
GVL at the reaction temperature, promoting the cotton conversion. It recovered by extraction from GVL into an aqueous phase by addition
should be noted that EG, the other monomer generated from polyester of NaCl or liquid CO232. Compared with current work on the recovery
depolymerization, has negligible impact on the cotton conversion of HMF from cotton, our study demonstrated a significant advantage
(Supplementary Fig. 19). in achieving a higher HMF yield of 25% in GVL (Fig. 5b)3,27,28,31,33,34. Even
Furthermore, the self-separation of TPA from the solvent sig- in different blends of polyester and cotton, the HMF yield is sig-
nificantly reduced the acid needed for separation and purification nificantly higher compared to the one in sole cotton (Fig. 5c). Com-
during subsequent processing. It is worth noting that in polyester/ pared with the traditional hydrolysis method of polyester, a much

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a b c

d 1/Acid (10-3) This work

e
240 Ref. 29
200 Ref. 37
160
0
120
-3 80
0
1/E (10 ) TPA yield (%)
40
0
0

catuh )
STY (10 g/(kg-1 -1
1/T (10-4)

Fig. 5 | Results of this work compared to traditional work. a Effects of TPA of polyester. e Degradation of PET mixed plastics. It should be noted that in the case
produced by polyester on cotton conversion in GVL with 7.5 wt% TsOH at 170 °C for of PBT/PET mixed plastics, TPA yield refers to the total yield of TPA obtained from
60 min. b Comparation of HMF recycled from cotton between this work and dif- the hydrolysis of both PBT and PET. 1/Acid: reciprocal of acid concentration; 1/E:
ferent degradation methods in references. c Degradation of different cotton mix- reciprocal of environmental factor; 1/T: reciprocal of reaction temperature; STY:
tures. d Radar contrast diagram of this method and traditional hydrolysis method space-time yield.

lower acid concentration was successfully adopted in our work, which in an aqueous solution. Besides, the excellent swelling and dissolu-
is only 10% of that of the traditional method, while obtaining a con- tion properties of GVL on polyester enable the reaction to occur
siderable TPA yield (Fig. 5d)29,35. Besides, the whole process of this work under much lower acid concentrations compared to traditional
exhibits lower environmental factors (E), which may provide valuable methods, requiring only one-tenth of the acid concentration used in
references for the recycling process36. A lower hydrolysis temperature traditional methods. GVL showed exceptional stability in the reac-
and a higher space-time conversion rate indicate that the process is tion. This solidifies the foundation for the cooperative degradation of
energy-efficient. As a further step towards real-world applications, we polyester/cotton blends while effectively preventing excessive
submitted the system to different PET wastes. The post-consumer PET degradation of the cotton component. Moreover, HMF yield shows
waste is of high crystallinity and complex mixtures. More than 95% the same upward trend across different polyester-cotton mixture
pure white monomer TPA can be obtained by degradation in GVL materials. This approach is highly tolerant of impurities and additives
(Fig. 5e) in various physical mixtures of PET plastics, including poly- in post-consumer PET products and achieves complete PET degra-
butylene terephthalate (PBT), polyamide (PA), polyvinylchloride dation and high TPA yield in various PET mixed plastics. Considering
(PVC), polypropylene (PP) and polyethylene (PE). This shows that the the diversity of mixed plastics and textiles, we expect that this work
method is highly inclusive of impurities and additives in post- will stimulate more development and design of recycling approaches
consumer PET products and can deal well with commercial PET waste. for mixed wastes.

Discussion Methods
In summary, we demonstrate synergistic co-hydrolysis of polyester/ Materials
cotton blends in GVL utilizing internal water circulation. Polyester Polyester/cotton blends (80% Polyester, 20% Cotton), pure polyester
hydrolysis can break the water balance between cotton hydrolysis textile, and pure cotton were purchased from Jingdong Mall.
and subsequently transform into HMF by consuming the water gen- p-toluenesulfonic acid (TsOH), potassium hydroxide (KOH) and
erated during the HMF production step. It drives the reaction in the gamma-valerolactone (GVL) were purchased from Chengdu Cologne
forward direction of HMF formation, increasing the HMF yield by Chemical Co., Ltd. 5-hydroxymethylfurfural (HMF), glucose and fruc-
25%. The introduction of external water is not conductive to the tose were purchased from Aladdin. Ultra-pure water was used in all
swelling/dissolution of polyester in GVL and thus decreases degra- experiments. All the above reagents are analytically pure and are not
dation rate. This rate constant in GVL is 100 times as much as the one further purified before use.

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Degradation of polyester/cotton blends Calculation of Gibbs Free Energy. All calculations were carried out
Polyester/cotton blends were cut into 3 mm × 3 mm squares after with the Gaussian 16 software. The M06-2X functional37 and TZVP
thoroughly dried in vacuum oven at 80 °C. Polyester/cotton blends basis38 set were adopted for geometry optimization and frequency
were added to 50 mL of PTFE-lined hydrothermal reactor with 20 mL calculations. The SMD implicit solvation model was used to account
GVL solution followed by TsOH. The mass fraction of blends and TsOH for the solvation effect (eps=42.82). Then, the Gibbs free energy
were 5% and 7.5%, respectively. Depolymerization was carried out at change was calculated by the following formula (1):
170 °C for 60 min with a stirring rate of 400 rpm. Afterward, the pre-
cipitate was separated from the solution by filtration to obtain crude deltaG = Gproduct
Greactant ð1Þ
terephthalic acid (TPA). An equivalent amount of 1 M KOH aqueous
solution was used to dissolve the crude TPA, and then the pH of the Data availability
solution was adjusted to around 3 using HCl to precipitate TPA and All data supporting the findings of this study are available within the
purified TP was finally obtained after filtration. article, as well as the Supplementary Information file. All data are
available from the corresponding author upon request.
Characterization
Nuclear Magnetic Resonance (NMR) spectra (1H and 13C). 1H NMR, References
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