Catalytic Fabric Recycling: Glycolysis of Blended PET

with Carbon Dioxide and Ammonia

Yang Yang1, Shriaya Sharma1, Carlo Di Bernardo1, Elisa Rossi5, Rodrigo Lima1, Fadhil S.
Kamounah1, Margarita Poderyte1, Kasper Enemark-Rasmussen4, Gianluca Ciancaleoni5,6*,
Ji-Woong Lee1,2,3*

1Departmentof Chemistry, University of Copenhagen; Universitetsparken 5, 2100,

Copenhagen Ø, Denmark.
2NanoscienceCenter, University of Copenhagen; Universitetsparken 5, 2100,
Copenhagen Ø, Denmark.
3NovoNordisk Foundation CO2 Research Center; Gustav Wieds Vej 10, Aarhus 8000,
Denmark.
4DTU Chemistry, Technical University of Denmark; Kemitorvet 207, DK-2800 Kgs
Lyngby, Denmark.
5Dipartimento di Chimica e Chimica Industriale, Università di Pisa; Via G. Moruzzi 13, I-
56124 Pisa, Italy.
6CIRCC; via Celso Ulpiani 27, I-70126 Bari, Italy.
*Corresponding authors. Email: [email protected]; [email protected]

Abstract
Abstract: The ubiquity of non-biodegradable polyethylene terephthalate (PET) materials has
led to significant waste management challenges. Although PET plastics can be recycled,
blended materials, such as PET/cotton fabrics, complicates the recycling process due to the
labile glycosidic bonds in cotton. In this study, we presented a practical and scalable approach
for recycling of PET and PET/cotton interwoven fabrics via catalytic glycolysis with
ammonium bicarbonate (NH4HCO3), which decomposed to ammonia, carbon dioxide, and
water. This catalytic approach outperformed conventional acid/base and metal catalysis in
selectively recovering and upcycling cotton-based materials. We demonstrated the large-scale
recovery of textile from blended fabrics (up to 213 grams), showcasing the advantages of
traceless catalysis using ammonia and CO2 from ammonium bicarbonate. Owing to our metal-
free reaction conditions, high-purity bis(hydroxyethyl)terephthalate (BHET) was obtained
which was thermally re-polymerized to PET. Through thermal analysis, kinetics, and control
experiments, we show that ammonia and CO2 are crucial for achieving optimal glycolysis via
transesterification. Our method offered a traceless, environmentally friendly, and practical
approach for polyester recycling and cotton recovery, representing a significant step toward
sustainable, closed-loop production of plastics and textiles.
Keywords: polyethylene terephthalates, plastic, fabric, carbon dioxide, glycolysis,

1
Introduction

Synthetic polymers represent one of the most significant polluting agents threatening the
sustainable growth of human society. The worldwide polymer production (ca. 388 million
metric tons in 2019) has grown exponentially over the years.1,2 Among them polyethylene
terephthalate (PET) stands out as one of the most commonly produced polymers, with ca. 70
million metric tons being produced every year and an expected annual growth rate exceeding
4%.3,4 PET-based polymers are primarily utilized in the production of beverage bottles, while
approximately one-third of the produced PET is blended with cotton-based fibers and viscose
to manufacture fabrics in the textile industry.5,6 In 2020 alone, over 109 million metric tons of
textile fiber were produced, with polyester (accounting for 52% of the volume share) and cotton
(representing 24% of the volume share) being the two most prevalent fiber types.7-9 However,
less than 20% of textile waste (equivalent to 65-92 million tons) is recycled annually,10 with
the remaining 80% being either landfilled or incinerated.11 Therefore, recycling these
composite plastic-based materials has become an urgent societal issue. Chemical recycling or
upcycling of plastic waste has emerged as an attractive option to mitigate fossil fuel depletion,
reduce greenhouse gas emissions, and minimize negative environmental impacts resulting from
energy recovery in waste incinerators.12–16
The catalytic and enzymatic glycolysis of PET yields valuable intermediate
bis(hydroxyethyl)terephthalate (BHET) (Fig. 1A and 1B),17–19 which can be recycled as a
precursor for PET via repolymerization,20–25 and other biodegradable polymers.26 Traditionally,
Lewis acidic metals have served as catalysts at high reaction temperatures (160–220 oC),22, 27,
28 to overcome the substantial reaction barrier and enhance the solubilization of PET substrates.

They often necessitate laborious purification steps to ensure high purity of BHET, minimizing
the environmental risk of metal contaminations.28–30 For instance, Zn(II) (including ZnO) is a
commonly used catalyst, but it exhibits significant cytotoxicity in vitro with a greater risk
compared to cobalt, iron, copper, and manganese.31-33 One potential solution to prevent metal
contamination lies in the use of metal-free organocatalysts.34-37 Recently, the combination of a
strong acid and a strong base (1,5,7-triazabicyclo[4.4.0]dec-5-ene, TBD) has been reported for
PET glycolysis.38,39 Ionic liquids have also been explored as reaction media in PET
glycolysis.40–42 For these approaches, the price and recycling of the catalysts are still the major
obstacles to practical application. Thus, there is a need for cheaper, more accessible and
practical catalytic protocols to handle the mountainous PET wastes, especially the PET blended
fabrics.
The challenge in chemical recycling of blended fabrics lies in the selective recovery of
either fiber type, given their blended and intertwined nature.43, 44 Acidic media and Lewis acid
catalysts can cause the degradation of cotton due to the labile glycosidic bonds present (Fig.
1E), resulting in a more challenging purification of monomers,45 especially for terephthalic acid
(TPA).46 Basic media, such as over-stoichiometric amounts of inorganic bases, can be utilized
to depolymerize PET/viscose blended fabric (filament, PET 30%) into TPA and viscose
through PET hydrolysis (Fig. 1C), requiring an additional re-protonation step.47,48 In this
process, mercerization or even degradation of cotton and cellulose-based materials is
essentially unavoidable during the depolymerization reaction.49
Recently, Zn(OAc)2 has been investigated for the selective glycolysis of
polyester/cotton blends (at a 5 g scale).50 The scalability raises questions including the heavy
metal contamination, considering 1) the additional cost associated with the use of betaine-based
deep eutectic solvents, and 2) the known degradation of cotton under glycolysis conditions,
such as elevated temperatures and the presence of Zn(II) catalysts.51 Thus, it is crucial to
develop a mild catalytic chemical recycling method for PET/cotton blends under practical
conditions, avoiding the acid- and base-mediated hydrolysis of cotton materials.52, 53
 A. Challenges in PET recycling B. PET degradation via (catalytic)hydrolysis and glycolysis
metals O
enzymes
organocat. OH OH
PET HO
bottles HO
packaging TPA EG
O
O
challenges:
OH
• catalyst contamination 2+ O
• sorting mixed plastic waste Zn
O
• various functional groups HO
EG
PET O BHET
cotton (Zn 2+
cytotoxicity, purification needed)
polyesters
C. (catalytic) blended fabrics via hydrolysis
NaOH O O
(excess)
blended fabrics O O
O
O
O recycled
TPA-2Na+
cotton (Na+)
D. This work: CO2/NH3-catalyzed glycolysis of blended fabric
O
OH
OH
NH3 + CO2 O OH
(cat.) O
HO OH
traceless catalysis O BHET recycled
no catalyst contamination cotton
(free OH)

E. Reactive sites of PET and cotton in catalytic chemical recycling of polymers

PET cotton H deprotonation

O O (mercerization)
OH O
+ O O H+ or Zn2+
HO O
H O
OH m
O n susceptible for H+ degraded cotton
electrophilic for not compatible
nucleophiles (H2O, ethyleneglycol) for catalytic degradation
and reducing reagents with PET
Fig. 1. Comparison of approaches to PET and blended fabrics chemical recycling. A)
Challenges in chemical recycling of PET and blended fabric, B) catalytic hydrolysis to access
terephthalic acid (TPA) and ethylene glycol (EG), C) NaOH-promoted hydrolysis of
PET/cotton blended fabrics D) ammonia and CO2-catalyzed glycolysis of PET to BHET, and
recovery of cotton from PET/blended fabrics. E) Chemical structures of PET and cotton and
cellulose-based materials and their multiple reactive sites.

We have previously demonstrated the successful utilization of CO2 in catalysis and

(bio)polymer degradation. Specifically, CO2 can accelerate chemical recycling of Nylon-6,6
through a CO2-catalyzed transamidation reaction and amide bond activation.54 Upon
completion of the reaction, CO2 can be easily removed without leaving any residue, resulting
in a purification-free process. Building on these findings, our objective was to develop a
practical, efficient, and scalable method for recycling PET using catalytic glycolysis with a
traceless catalyst—CO2, thereby streamlining the green chemical recycling process.
Herein, we showcase catalytic chemical recycling of blended materials,55 addressing
the challenges associated with glycolysis of PET in the presence of cotton-based materials.
These materials present several unresolved challenges, particularly the need for selective
glycolysis of PET while preserving the cotton fabrics in the blends (Fig. 1A and 1E).
Sustainable recovery methods for cotton are crucial due to its significant carbon footprint, high
water usage, and labor issues during production. Consequently, there is a growing interest in
environmentally responsible alternatives for cotton or chemical recycling methods for
polyester-blended fabrics (Fig. 1D). In this study, we demonstrated a traceless and selective
catalytic transesterification of PET/cotton blended fabrics using NH4HCO3 as an inexpensive
and easy-to-handle pre-catalyst (up to 25 mol%). This pre-catalyst decomposed into CO2, basic
ammonia, and water at temperatures above 36°C.56,57 Our reaction operated under practical,
mild conditions (pH ca. 7–8) and effectively produced high-purity BHET while recovering
cotton fabrics without significant mercerization or hydrolysis. This approach paves the way for
large-scale chemical recycling and upcycling of blended composites and PET-containing
waste.

Results and Discussion

First we attempted to study CO2 mediated glycolysis with PET bottle substrate, without
any prior chemical or thermal pre-treatment. An application of CO2 in transesterification at high
pressures (147 bar of CO2, at 100–110 oC; 5 h) has been reported by Otsuji et al., which
employed ethyl formate, HCO2Et, and n-octanol, rendered up to a 27% yield of a
transesterification product.58 Building on this work, we hypothesized that the addition of a base
could enhance general base catalysis, while a catalytic quantity of electrophilic (Lewis acidic)
CO2 would provide cooperative general acid catalysis under thermal conditions.
An examination of various organic and inorganic bases revealed that the conversion of
PET to BHET is related to the pKa values of the base catalysts. The maximum conversion was
achieved when employing weak bases (pKa ≈ 6, Fig. 2A) in the presence of 25 mol% of CO2.
Stronger bases displayed no significant improvement with or without CO2. Interestingly, weak
bases like ammonia and pyridine demonstrated exceptional performance, exhibiting enhanced
PET degradation to BHET in the presence of CO2 (Fig. 2B). These results suggest that the
glycolysis reaction mechanism follows a general base catalysis, highlighting the crucial role of
catalytic CO2 in reactions involving weak bases, especially ammonia—generated from
NH4HCO3 through thermal decomposition.

base (25 mol%) O

O with and w/o
OH
CO2 (25 mol%) O
OH OH
O HO O
180 oC, 6 h HO
H O
EG O
O (25 equiv.) BHET

PET (beverage bottle)

192 mg, 1 mmol
A) 100 B) 0.6
under N2 +25 mol% CO2 NH4HCO3

80 0.4
pyridine N-butylamine

log(conv.CO2/conv.N2)
conversion (%)

piperazine
60 0.2 quinoline hydrazine
TMG
imidazole
DMAP pyrrolidine TBD
aniline
40 0.0
morpholine n-dibutylamine
EDA NaOH
MEA
20 −0.2
N-methylmorpholine
TEA
w/o CO2, under N2
0 −0.4
e e e 3 le e e e A P e e e e e e G D H 4 6 8 10 12 14 16
n ilin olinidin CO zo olin zin olin ME MA zin min min min idin min M TB aO pKa
a u i yr H i d a r p h d r a p h
n D era dia yla yla rrol tyla T N
q p H4 im o h y o r p t
N l m m pi ene -bu ieth py ibu
hy yl N tr d
et th n-
- m e
N
Fig. 2. A) Conversion of PET to BHET with various bases in catalytic glycolysis with
additional 25 mol% of CO2 (red squares, for NH3, NH4HCO3 was used, green square) and with
only bases under N2 atmosphere (gray bars). B) Illustration of positive CO2 effect in glycolysis.
Abbreviations: ethylene glycol (EG), dimethylaminopyridine (DMAP), ethylenediamine
(EDA), monoethanolamine (MEA), triethylamine (TEA), 1,5,7-triazabicyclo[4.4.0]dec-5-ene
(TBD), 1,1,3,3-tetramethylguanidine (TMG).

Through further optimization, we successfully established practical reaction conditions,

even in scales ranging from 0.2 to 50 grams, that consistently produced high-purity BHET
without the need for complex purification steps, (Table 1). Under an N2 atmosphere and in the
absence of catalysts, no background glycolysis was observed (Entry 2; see pictures of time-
dependent PET flakes degradation with and without a catalyst). The utilization of CO2 alone,
whether in catalytic amounts (15-30 mol%) or as a reaction atmosphere (1 atm), had no
discernible effect on the reaction, even with extended reaction times (up to 24 hours at 150-
200 °C; Entry 1).
With this observation, we swiftly conducted comparative studies to evaluate our
glycolysis method against existing PET depolymerization techniques. Zn-based Lewis acidic
catalysts, such as Zn(OAc)2 and ZnCl2, have been widely used in industrial glycolysis of PET
and have demonstrated satisfactory conversion of PET to BHET—44% and 75%, respectively
(entries 3 and 4).27, 59 However, an elemental analysis of the isolated BHET from these
experiments with Zn2+ revealed varying degrees of metal impurities after hot filtration and
crystallization of BHET (see Table S9), likely due to residual zinc ions. These impurities might
hinder their application in the repolymerization of BHET to PET.28
Under our optimized glycolysis conditions, the use of NH4HCO3 as a catalyst allowed
us to conduct a larger scale reaction (260 mmol, 50 grams of waste PET bottle substrate). This
catalytic system achieved quantitative conversion of PET, yielding BHET with an isolated
yield of 64% in a single crystallization step without any by-products (Table 1; Entry 5).60 This
result represents, to the best of our knowledge, the first demonstration of the synergistic effect
of catalytic CO2 and an amine in glycolysis. Solely using ammonia as a catalyst without CO2
(aqueous ammonia and an NH3 solution in methanol, Table S1, Entry 22) was not effective,
yielding inferior results compared to the NH4HCO3 catalyst, highlighting the importance of
CO2. The use of ammonium carbonate (NH3)2CO3, a reagent commonly employed in the
Bucherer-Berg reaction, yielded comparable results to the ammonium bicarbonate catalyst
(87% yield of BHET, Table S1, Entry 18). In contrast, inorganic bases led to the contamination
of BHET with the hydrolysis product, terephthalic acid (TPA), as summarized in Table S1.62

Table 1. PET bottle chemical recycling. a

O
O OH
catalyst O
OH OH
O HO O
180 oC, 6 h HO
H O
ethylene glycol O
O (25 equiv.) BHET

PET (beverage bottle)

no degradation
(little changes of the flakes)

catalytic glycolysis
(the flakes became smaller)

entry PET (g) catalyst (mol%) conversion (%) yield of BHET (%)
1b 0.2 g CO2 (15-30 mol% or 1 atm) not detected 0%
2 0.2 g N2 n.a. 0%
3 2g Zn(OAc)2 (25 mol%) 44% 40%
4 2g ZnCl2 (25 mol%) 75% 52%
5 50 g NH4HCO3 (25 mol%) 88% 64% (32 g)
aReaction conditions: PET bottle substrate (0.2–50 g); a catalyst and ethylene glycol were
added with a magnetic stirring bar, and the vial was heated for 6 h; Conversion (%) =
(Woligomers+BHET/WPET bottles)X100, yield of BHET (%) = (WBHET/WPET bottles)X100, W = weight.
The reaction mixture was diluted with water to precipitate oligomers and BHET, which was
crystalized to determine the yield of isolated BHET. bReaction time extended to 24 h.

With our optimized conditions for PET glycolysis, we aimed to depolymerize PET in
the presence of cellulose, as in blended fabrics, to separate BHET and recycled cellulose (Fig.
3). Under acidic conditions, cotton and cellulose-based materials are prone to decompose via
hydrolysis, as demonstrated in Fig. 3A. The catalytic reaction with Zn(II) catalyst resulted in
complete decomposition of the cotton fabric within 2 hours, with all visible cotton threads
disintegrating after 3 hours of reaction time. FT-IR (Fourier-transform infrared spectroscopy)
showed full conversion of ester functional groups on PET fabric (Fig. 3B, see full spectra in
Fig. S18) while the cotton fabric remained intact even after prolonged reaction times under
catalytic conditions with NH4HCO3, (18 hrs). Solid-state 13C NMR spectra were evident to
confirm the effective catalytic glycolysis of PET in the presence of cotton materials (Fig. 3C).
The spectra clearly showed the full conversion of PET and preservation of the recycled cotton
(green), with no presence of aromatic and sp2-carbons from PET starting material (black).63
The quality of the recovered viscose was further assessed using powder X-Ray
diffraction (PXRD, Fig. 3D). The peaks centered at angles 2θ = 12.5, 20 and 22 correspond to
the crystalline structure of cellulose II. Notably, the PXRD pattern of the recovered cotton
(green) using NH4HCO3 exhibited mild crystalization as reported in the literature under basic
conditions with NaOH (gray),49 while the use of ZnCl2 catalyst (black) significantly increased
the crystallinity of viscose after 6 hours.
Based on optical microscopy of the recovered materials (20-80 fold magnification, Fig.
3E. also see Figs S20-21), it was evident that glycolysis reactions of blended fabrics with Zn-
based catalysts resulted in complete degradation, with all fabric threads being degraded within
3 hours of reaction time. In contrast, NH4HCO3 effectively converted PET to BHET while
preserving the integrity of the textile thread. Additionally, the analysis using dynamic light
scattering (DLS) (Fig. S24) and thermogravimetric analysis (Fig. S25) confirmed the same
conclusion, further validating the quality of the recovered viscose materials under our
depolymerization reaction conditions compared to those obtained using ZnCl2 and NaOH.

Fig. 3. Catalytic depolymerization of blended textiles, and characterization of recovered

textile. A) catalytic glycolysis of blended fabric and gravimetric analysis of textile residue, B)
FT-IR analysis of the recovered cotton from the reaction with NH4HCO3 (green), without
catalysts (gray), commercial cotton (orange), and starting material (black), C) Solid-state 13C
NMR spectra and D) PXRD (powder X-Ray diffraction) patterns (smoothed) of the substrate
(orange, viscose) and recovered viscose from glycolysis conditions with ZnCl2-(black, 6 h),
NaOH-(gray, 19 h), and NH4HCO3-catalyst (green, 19 h), and E) Optical images of the
recovered cotton over time, starting from the blended fabrics (47% PET+53% cotton), with
ZnCl2 and NH4HCO3 as catalysts.

Considering the diverse range of blended fabric waste to be recycled, including various
PET:cotton blending ratios, unidentifiable dyes,64 additives, and impurities, we subjected
different commercial textile materials to our catalytic glycolysis without any pre-treatment.
Reactions performed without the catalyst were visibly slower, with textile starting materials
still remained in the reaction vessels even after 24 hours of reaction time. In contrast, catalytic
glycolysis with NH4HCO3 enabled clean conversion of the starting materials to the desired
BHET, even in large-scale reactions without pressure build-up (Fig. 4A and 4B). For instance,
end-of-life sofa covers consisting of PET/cotton blended fabrics (213 g) yielded 62% and 94%
for BHET and cotton, respectively, without requiring substrate pre-treatment.
Furthermore, we evaluated the tolerability of our NH4HCO3-catalyzed glycolysis
method on different blended fabrics (47–100% PET with cotton, viscose, and lyocell). To our
delight, reasonable yields of BHET and quantitative yields for recovered cotton and other
fabrics were achieved through a straightforward separation process (Fig. 4B). The purity of
BHET obtained from our catalysis was confirmed by PXRD and high-performance liquid
chromatography (HPLC), with no indication of metal impurities or oligomers (Figs. S26-27).
The quality of the isolated BHET was further supported by catalyst-free thermal re-
polymerization to PET (rPET), as analyzed by FT-IR, thermal gravimetric analysis (TGA),
differential scanning calorimetry (DSC) (Figs. S28-29), and elemental analysis (Table S10).
Thermal gravimetric analysis (Fig. S19) and elemental analysis (Table S5) were also conducted
on the residual cellulose and solid materials from the glycolysis process to corroborate these
results. Although the low whiteness of the obtained BEHT can deteriorate the quality of rPET,
a new sublimation method can effectively improve the whiteness.64
To demonstrate the feasibility and robustness of our methodology, we mixed several
types of polymers (PVC, PP, PE, polyamide, PU, PS, ABS, POM, NBR, and SEBS) and even
included human hair, simulating realistic plastic waste from a waste collection point (Fig 4C).
Under our standard reaction conditions, selective glycolysis of PET was achieved, with a 23%
isolated yield of BHET after a single recrystallization step, and 75% yield of recovered cotton.
The other plastic materials were recovered with some deformation but without any signs of
chemical depolymerization. The formation of the pre-catalyst NH4HCO3 during the reaction
was confirmed, and the catalyst was easily recovered through simple sublimation.
Fig. 4. Impact of catalysis on the selective chemical recycling of textiles. A) Catalytic
glycolysis of PET containing textile (PET 75%) with and without the catalyst and the recovery
of cotton. B) Large scale PET/cellulose-blended textiles for catalytic glycolysis in large scales.
C) Combined mimicked plastic waste, catalytic glycolysis of PET, and isolation of BHET,
cotton and other plastic waste: polyethylene (PE), polypropylene (PP), polyurethane (PU),
polystyrene (PS), polyoxomethylene (POM), polyvinylchloride (PVC), polyacrylamide
(PAA), acrylonitirle butadiene styrene (ABS), acrylonitrile butadiene rubber (NBR), stryene-
ethylene-butylene-styrene (SEBS), human hair (peptides).
Fig. 5. A) Crystallinity of remaining PET bottle flakes from reaction mixtures under glycolysis
conditions (180 oC), B) Kinetic analysis (170–190 oC) and activation barriers of the polyester
fabric (PET 100%) degradation (e.u.: cal/K·mol)

To gain insight into the reaction mechanism of NH4HCO3-mediated PET degradation,

we conducted kinetic experiments on the glycolysis of PET bottle substrates. The aim was to
confirm the catalytic performance of NH4HCO3 compared to non-catalytic conditions by using
thermal gravimetric analysis (Kessinger Model). Our analysis revealed comparable
degradation kinetics with NH4HCO3 catalyst to that of the industrially widely used ZnCl2
catalytic system for the depolymerization of PET under identical reaction conditions. This
finding was surprising, considering that ammonia and CO2 exhibit catalytic activities
comparable to strong Lewis acidic zinc(II). Additionally, differential scanning calorimetry
(DSC) analysis of the residual PET flakes collected at different reaction times indicated that
the PET depolymerization with NH4HCO3 resulted in lower crystallinity of the PET substrates
(Fig. 5A, green), while Zn-catalysis significantly increased the crystallinity of the remaining
PET substrate under thermal conditions over time (Fig. 5A, gray). These observations suggest
that the NH4HCO3-catalyzed glycolysis may have distinct mechanistic features compared to
the Zn-catalyzed process, leading to differences in the crystallinity of the residual PET flakes.
Therefore, further kinetic studies were performed in terms of degradation of textile
substrates (100% PET) and its conversion into BHET (Fig. 5B) at different temperatures. For
the catalytic ZnCl2, an activation barrier of 20.2 kcal/mol was obtained, which is consistent
with previously reported cases.65 In contrast, our catalyst NH4HCO3 exhibited a higher
activation barrier (34.9 kcal/mol), as supported by our DFT (density-functional theory)
calculations using methyl benzoate as a substrate (see Fig. S30). It is noteworthy that a positive
activation entropy (+3.9 e.u., cal/K·mol) was calculated based on the Eyring equation for
NH4HCO3, contrasting with the results obtained with the Zn(II) catalytic system (–27 e.u.).
This positive entropy value is reasonable for addition/elimination reactions, where the addition
step can be rate-determining and unfavorable negative activation entropy is commonly
observed. In terms of the reaction mechanism, we postulate that NH4HCO3, as a thermally
labile pre-catalyst, undergoes decomposition, resulting in an enthalpy loss of 8.2 kcal/mol but
a significant entropic gain of 283 cal/K·mol (ΔGrxn = ‒11.9 kcal/mol) due to the liberation of
ammonia, water, and CO2. This entropic gain likely impacts the energy profile of the
transesterification reaction, lowering the ΔG‡.
It is important to note that the decomposition of NH4HCO3 and the catalysis are separate
events, and further mechanistic studies are required to fully understand the relationship
between the entropy gain and the reduction of free energy of activation. Nevertheless, our
experimental observations suggest continuous regeneration of NH4HCO3 via decomposition
and precipitation on a reflux condenser as ammonium (bi)carbonate, which falls back into the
reaction mixture. Qualitative analysis on CO2/ammonia (Fig S21) and control experiments (Fig
S21g) were conducted to confirm the fate of CO2 and ammonia after completion of the
glycolysis. We detected higher concentrations of ammonia in the presence of CO2, confirming
our hypothesis on the role of CO2 suppresing ammonia evaporation, in turn effectively
increasing the catalyst concentration.
To further support our mechanistic hypothesis regarding CO2 and ammonia-mediated
transesterification, we conducted control experiments with PET bottle substrate and model
compound 1 (Scheme 1). Trace amounts of amide by-products (3) were isolated as expected
under standard depolymerization conditions at a low temperature of 80 oC (Scheme 1A). We
found that transesterification with CO2/ammonia was effective even at low temperatures: 57%
of BHET was isolated at 80 oC, along with a mono-functionalized product (2, 36%).
Interestingly, amide 3 (< 1%) was isolated as an aminolysis byproduct presumably originating
from ammonia. It is plausible that ammonia can act as a nucleophile in the reaction mixture,
with the amide intermediate subsequently being converted to BHET. To investigate this, we
subjected monoamide (3) and diamide (5) to the standard conditions (Schemes 1B and 1C).
Mono-transesterification predominantly produced product 4 (75% 1H NMR yield), while the
primary amide functional group remained stable and BHET was obtained as a minor product
(25%). Under standard glycolysis conditions for PET, terephthalamide 5 and TPA were
converted to BHET in 11% and 37% yields, respectively. Consequently, we have ruled out
reaction pathways involving amides and carboxylic acid intermediates resulting from ammonia
acting as a nucleophile (see also DFT calculations, Fig. S31). After eliminating a nucleophilic
catalysis mechanism, we propose that ammonia and CO2 function as general base and acid
catalysts,66-68 as indicated in the experimental data (Fig. 2 and see Table S11 for DFT
calculations of various reaction pathways).
These control experiments implied that CO2 can suppress the aminolysis of PET. To
further verified this, we employed over-stoichiometric amounts of nucleophilic pyrrolidine
under similar glycolysis conditions (Scheme 1D). The diamide 6 was a major product (33%)
under a catalyst-free N2 atmosphere due to the high nucleophilicity of pyrrolidine. In contrast,
BHET was detected as the primary product in the presence of pyrrolidine when the reaction
was carried out under ambient CO2 conditions (1 atm). This result unambiguously confirms
our hypothesis: CO2-assisted ammonia-catalyzed transesterification takes place, with CO2
effectively preventing aminolysis and maintaining an optimal concentration of catalytic
ammonia in the solution.

Conclusion

We have discovered the remarkable advantages of NH4HCO3-catalyzed selective

depolymerization of PET, which allows for the production of high-purity BHET monomer on
a large scale (213 g), while preserving the integrity of cotton and cellulose-based materials.
Comprehensive structural analysis of the recycled cellulose fabrics was performed using solid-
state 13C NMR, FT-IR, TGA, DSC, elemental analysis, and microscopy, confirming the quality
of the recovered materials.
Significant contributions from CO2 as a molecular catalyst, combined with ammonia in
the general base-catalyzed PET glycolysis, were observed: 1) NH4HCO3, being a more user-
friendly catalyst precursor due to CO2, eliminates the use of toxic and volatile ammonia gas;
2) the presence of CO2 effectively suppresses aminolysis reactions; 3) the avoidance of catalyst
contamination in BHET simplifies repolymerization processes.69
 A. Glycolysis of diester 1 under mild conditions and the detection of aminolysis product

O O
O
NH4HCO3 (24 mol%) OH NH2
O
OEt or no catalyst (N2 ,1 atm)
EtO EtO
EtO BHET
ethylene glycol (20 equiv.)
O 2 O 3
O 80 oC, 24 h
57% 36% <1%
1 (1 mmol) no cat.: 3% no cat.: not detected
no cat.: not detected

B. Esterification of monoamide 3 with ethylene glycol

O O

NH2 NH4HCO3 (24 mol%) NH2

EtO O BHET
ethylene glycol (20 equiv.) HO
O 150 oC, 24 h O
4, 75% 25%
3 (0.1 mmol) full conversion by 1H NMR

C. Esterification of terephthalamide 5 or terephthalic acid (TPA) with ethylene glycol with catalytic ammonium bicarbonate

O O
NH4HCO3 (24 mol%) NH4HCO3 (24 mol%)
NH2 OH
BHET
H 2N ethylene glycol (20 equiv.) ethylene glycol (20 equiv.) HO
180 oC, 6 h 180 oC, 6 h
O O
11% conversion 37% conversion
5 (1 mmol) TPA (1 mmol)
D. Selective aminolysis versus glycolysis with pyrrolidine controlled by CO2

O N2 or CO2 (1 atm) O
OH pyrrolidine (0.5 mL)
O ethylene glycol (1.5 mL) N
H O BHET N
70 oC, 65 h
O n
O 6
PET
under N2: <1% 33%
(beverage bottle)
under CO2: 13% 4%
540 mg
Scheme 1. Control experiments.

As a result, our approach enables more environmentally friendly chemical processes,

utilizing NH4HCO3 or other combinations of organic and inorganic bases with CO2. The
synergistic effect of CO2 as a catalyst will be further explored in renewable
transesterification,70 catalytic polymerization, and depolymerization of other plastics, building
on the insights gained from our detailed mechanistic studies of PET depolymerization and
cotton recovery. By offering a practical and sustainable solution, our method contributes to
achieving closed-loop production of PET and PET blended fabrics. The utilization of recycled
cellulose-based materials and cotton also addresses the challenges posed by the fast fashion
industry and plastic-based textile waste.8, 11, 71-72

Experimental Section

General information. All chemicals, unless stated otherwise were purchased from
commercial suppliers and used without further purification. CO2 was directly used from a CO2
cylinder of 99.7% purity without any treatment for reactions. Solvents used were High-
performance liquid chromatography (HPLC) grade. Analytical thin layer chromatography was
done on Merck DC-Alufolien SiO2 60 F254 0.2 mm thick pre-coated TLC plates. Column
chromatography was performed using SiO2 from ROCC (SI 1721, 60 Å, 40−63 µm). Liquid
1H and 13C NMR (Nuclear Magnetic Resonance) spectra were recorded with 500 MHz

Ultrashield Plus 500 spectrometer and 125 MHz on a Bruker. 1H, and 13C NMR spectra were
also recorded at 500 MHz, and 126 MHz, respectively, on a Bruker Avance III spectrometer
with a BBFO probe. All chemical shifts ( ) are quoted in ppm and all coupling constants (J)
are expressed in Hertz (Hz). The following abbreviations are used for multiplicity for NMR
resonances: s = singlet, bs = broad singlet, d = doublet, t = triplet, q = quartet and m = multiplet.
LC-MS (Liquid Chromatography-Mass Spectroscopy). LC-MS analyses were carried out by
connecting the above mentioned HPLC (High Performance Liquid Chromatography) apparatus
to a Bruker MicrOTOF-QII system equipped with an ESI source with nebulizer gas at 1.2 bars,
dry gas at 10 L/min, dry temperature at 200 °C, capillary at 4500 V and end plate offset at –
500 V. The ion transfer was conducted with funnel 1 and funnel RF’s at 200.0 Vpp and
hexapole RF at 100.0 Vpp while the quadrupole ion energy was set at 5.0 eV with a low mass
cut-off at 100.00 m/z. In the collision cell, collision energy was set at 8.0 eV, collision RF at
100.0 Vpp, and a transfer time of 80.0 µs and pre-pulse storage of 1.0 µs were used. FT-Infrared
spectra were recorded on a Bruker ALPHA-P FT-IR spectrometer with a single reflection ATR
module. Unless otherwise noted, all solvents and reagents were purchased from commercial
suppliers and used without further purification. The ethylene glycol was ordered from Sigma-
Aldrich. The model compound diethyl terephthalate was ordered from TCI. Textile wastes used
without any further treatment for the depolymerization reactions. Drinking bottles were
collected from end users. The thermogravimetric analysis (TGA) was performed using a
Discovery TGA from TA instruments (New Castle, DE, USA) under constant flow of 25
mL/min nitrogen. The samples were heated in a platinum TGA pan from room temperature to
600 °C at a heating rate of 10 °C/min. From the TGA results, the thermal decompositions and
the first derivative of TGA (dTGA) temperatures of the samples were determined using Trios
v5.1.1.46572 software (TA Instruments, New Castle, USA). Differential scanning calorimetry
(DSC) analysis was performed using a Discovery DSC (TA Instruments, New Castle, USA).
The samples of 4-5 mg were weighed in Tzero aluminum pans with a perforated lid. Analyses
of the samples were conducted under nitrogen flow of 50 mL/min using a linear heating rate
of 10 °C/min. The samples were heated from 30 to 300°C. The melting point temperatures
(Tm) and melting enthalpy ( Hm) were determined using Trios v5.1.1.46572 software (TA
Instruments, New Castle, USA). The purity of the isolated BHET
(bis(hydroxyethyl)terephthalate) was measured with HPLC (column: Kromasil 5-AmyCoat
(4.6 x 250 mm), iso-propanol/n-heptane (60/40, v/v), 0.5 mL/min, 8.9 MPa, detector A: 220
nm, detector B: 254 nm.). The X-ray powder diffraction (PXRD) patterns were recorded for 2
h using a Bruker AXS D8 powder diffractometer (Bruker, Germany) with λCuKα = 1.5406 Å
(40 kV, 40mA) covering a 2θ range from 5 to 50°. The 13C solid-state NMR measurements
were performed with a 600 MHz Avance III HD spectrometer (v13C = 150.9 MHz) equipped
with a 4 mm CP/MAS broadband probe. The reported spectra were acquired with the 13C-{1H}
CP-TOSS pulse sequence employing a ramped contact pulse of 1.5 ms (vRF = 55 kHz), an
interscan delay of 5 seconds, a MAS frequency of 5 kHz and high-power SPINAL64 1H
decoupling (vRF = 100 kHz) during acquisition. 2000 scans were acquired for each spectrum.
Chemical shifts are referenced relative to TMS using the down-field signal of neat adamantane
as a secondary reference ( = 38.48 ppm). All measurements were performed at 25 oC.

Glycolysis of PET bottle flakes. A reactor equipped with a magnet was charged with bottle
flakes (by mola, calculated with molar mass of the repeating unit of PET), ethylene glycol (25
equiv.) and ammonium bicarbonate (25 mol%). The reaction mixture was stirred and heated
up to 150-200 oC. The conversions (In Table S1 and S2) were detected by analyzing aliquot
samples by 1H NMR spectroscopy.

Large scale glycolysis of PET/cellulose blended fabrics. To a three necked round bottom
flask equipped with reflux condenser was added fabrics (47% – 50% PET, 80 – 213g), ethylene
glycol (25 equiv., referred to PET), and NH4HCO3 (25 mol%). Then the reaction was heated
up to 187 – 195 oC for 18 – 24 h. Then hot filtration of the reaction mixture was performed.
The filtrate was cooled down to room temperature and further down to 5 oC for overnight. The
cotton residual was washed with water, EtOH and Et2O respectively, and then dried overnight
in open air. The BHET crystals were separated from the mother liquor by filtration as the first
crop of product. Then the second crop of product was gained via crystallization with the mother
liquor by adding a few crystal seeds and water (water/ethylene glycol = 1/1).
Supporting Information. The Supporting Information is available free of charge at
https://XXX. Materials and Methods, supplementary text, Reaction optimization,
characterization, kinetics, NMR spectra, TGA traces, HPLC traces, PXRD patterns, DSC
analysis, FT-IR spectra, DFT calculation

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Acknowledgments: The generous support from the Department of Chemistry, University of

Copenhagen, the Carlsberg Foundation (CF21-0308), NNF CO2 Research Center (CORC), and
the Novo Nordisk Foundation (NNF20OC0064347) is gratefully acknowledged. We thank
Prof. Troels Skrydstrup for the fruitful discussion on depolymerization and Dr. Theis Brock-
Nannestad, Christian Tortzen, and Prof. Pernille Harris for the analysis and acquisition of
optical microscope images. The NMR Center • DTU and the Villum Foundation are
acknowledged for allowing us access to the 600 MHz spectrometer. We acknowledge Prof.
Heloisa Nunes Bordallo and CPHarma, Department of Pharmacy, Faculty of Health and
Medical Sciences, University of Copenhagen, for the access to TGA and DSC measurements.
We also thank our analytical departments for their kind support.
Competing interests: JL, YY, SS, CDB, FSK filed a patent application (EP 23150108.1).
There are no other interests.
The Supporting Information is available free of charge at https://pubs.acs.org/journal/
Materials and Methods, supplementary text, reaction procedures, substrate preparation,
optimization, kinetics, cotton recover procedures, characterization of BEHT and cotton,
spectroscopy (NMR and FT-IR), power X-ray diffraction analysis of BHET and viscose,
mechanistic studies and DFT calculation.