Chemistry–Sustainability–Energy–Materials

Accepted Article

Title: Recent Progresses in the Chemical Upcycling of Plastic Wastes

Authors: Xi Chen, Yudi Wang, and Lei Zhang

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To be cited as: ChemSusChem 10.1002/cssc.202100868

Link to VoR: https://doi.org/10.1002/cssc.202100868

01/2020
ChemSusChem 10.1002/cssc.202100868

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Recent Progresses in the Chemical Upcycling of Plastic Wastes
Xi Chen,*[a] Yudi Wang,[a] Lei Zhang[a]

[a] Dr. X. Chen, Y. Wang, L. Zhang

China-UK Low Carbon College
Shanghai Jiao Tong University
3 Yinlian Rd, Pudong District, Shanghai, China 201306
E-mail: [email protected]

Accepted Manuscript
Abstract: The massive generation of plastic wastes without chemically resistant to decomposition under natural conditions
satisfactory treatment has induced severe environmental problems (e.g., the decay period of plastic bottles in land can be centuries),
and gained increasing attentions. In this mini-review, recent impose heavy burdens on the ecosystems and cause grim
progresses in the chemical upcycling of plastic wastes by using environmental problems. For instance, the lightweight plastic
various methods (mainly in the past three to five years) will be debris that floated with the water streams could entangle or be
summarized. The chemical upcycling of plastic wastes points out a ingested by numerous animal species (e.g., ~1 million seabirds
“plastic-based refinery” concept, which is to use the plastic wastes as killed by plastic wastes per year). Moreover, recent studies have
platform feedstocks to produce highly valuable monomeric or revealed that plastic wastes would tear down into small micro- and
oligomeric compounds, putting the plastic wastes back into a circular nano-plastic particles which have been probed in air, water and
economy. The different chemical methods to upcycle plastic wastes food supplies, threatening the health and lives of human beings.[2-
including the hydrogenolysis, photocatalysis, pyrolysis, solvolysis, etc. 5]
As a result, it is imperative to establish efficient protocols to
will be introduced in each session to valorize diverse plastic satisfactorily cope with the plastic wastes and solve the “white
feedstocks into value-added chemicals, materials or fuels. In addition, pollution” problem.
other emerging technologies as well as the new generation of plastic Currently, the commercialized ways to treat plastic wastes
thermosets will be covered at last. mainly include landfill, incineration and (mechanical) recycling.
Landfilling is a relatively temporary solution that did not eliminate
plastic wastes. Moreover, the landfilled plastics may leach
harmful substances and induce other environmental issues such
1. Introduction as groundwater contaminations.[6] Incineration is a “waste-to-
energy” approach to exploit the plastics as a resource into heat
Nowadays, plastics can be found almost everywhere in the and electricity. However, it still cannot terminate plastic waste
modern society. Derived from the Greek word “plastikos”, plastic problems because of the release of toxic airborne pollutants into
generally refers to a diversity of polymer materials that are fit for the atmosphere and the residues of microplastics in the bottom
molding and can be easily processed into different shapes. In ashes as potential pollution sources.[7] Additionally, incineration
history, the use of natural plastic materials such as amber for caused excessive carbon emissions which may exacerbate global
decoration purposes can be dated back to thousand years ago. warming. In contrast, the plastic recycling provides a “waste-to-
The first semi-synthetic and synthetic plastic materials (cellulose value” strategy to utilize used plastics as a resource to produce
nitrate and Bakelite) has been invented in the 1850s and 1900s useful commodities, which simultaneously contributes to plastic
respectively. Afterwards, considerable efforts have been paid in waste management and sustainable development. Nonetheless,
synthetic plastics and the massive production of plastics kicked the commonly-used mechanical recycling that adopts mechanical
off since the 1950s. Plastics have been prevalently applied forces to grind spent plastics into secondary raw materials often
around the world for packaging, construction, textiles, electricals, leads to declined structural properties, and thus only a limited
transportation, etc. with the unparalleled merits of lightweight, portion of the plastic wastes could be reclaimed for the original
inexpensive, chemically inert and adaptable. The global plastic purpose. Besides, the scope of substrates was confined to
production has reached 368 million metric tons in 2019 and is relatively uncomplicated, single-component plastic wastes
predicted to keep rising in the forthcoming years. So far, the hindering its applications.
accumulative manufacture of plastics has already exceeded an Beyond mechanical recycling, increasing endeavors have
astounding ~8 billion metric tons in the past decades.[1] been made to explore more efficient, powerful and beneficial ways
Plastic products usually have a relatively short service period to valorize the plastic wastes.[8, 9] Chemical upcycling, which aims
such as the single-use plastic bags in packaging, etc., and large to transform plastic feedstocks into high-value/high-quality
quantities of plastic wastes are generated annually. As estimated, monomeric or oligomeric compounds by various chemical
more than 80% of the total plastic production has ended up as protocols, has recently gained rising attentions as an alternative
wastes and entered the lands and oceans, without being properly recycling strategy (a comparison of the four treatment methods is
handled or processed.[1] The enormous plastic wastes, which are provided in Figure 1). The target products have considerably

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Accepted Manuscript
Figure 1. A comparison of the four plastic treatment methods.

reduced molecular weight (MW) and may be employed as building

blocks for further upgrading into a diversity of valuable chemicals,
materials and fuels. Moreover, through rational catalyst and
parameter designs, the chemical upcycling is possible to deal with
contaminated plastics or complex plastic mixtures which are
difficult to achieve by simple mechanical recycling. As a result, the
chemical upcycling put forward a “plastic-based refinery” strategy
to potentially solve the environmental pollution problem with
mitigated carbon emissions and bring out extra values for
chemical production towards a circular economy.
For the plastic upcycling into value-added products, different
chemical methods have been reported including hydrogenolysis,
photocatalysis, pyrolysis, solvolysis, etc. So far, there are many
excellent reviews on plastic recycling and plastic waste
Figure 2. The main framework of the mini-review.
management,[10-18] while mostly stressed on the plastic pyrolysis
and/or solvolysis. On the other hand, fast growing academic
progresses have been witnessed in the very recent years
Xi Chen received her Bachelor (2010) and
especially for the catalytic chemical transformations. Therefore, Master (2012) degrees from Wuhan
this mini-review intends to offer an up-to-date account of relevant University in China. She then obtained her
advances in the chemical upcycling of plastic wastes, with an Ph.D. in Chemical Engineering from the
emphasis on the new catalytic systems developed in the past National University of Singapore (NUS)
three to five years. The main framework of the mini-review is under the supervision of Prof. Ning Yan in
shown as Figure 2. Plastic hydrogenolysis (a H2-involved 2016, where she stayed as a postdoc. She
chemical method) will be introduced first, since prominent joined the China-UK Low Carbon College at
breakthroughs have been achieved recently. Considering the Shanghai Jiao Tong University in 2018 and
structural robustness of plastics, the development of efficient is now an Associate Professor. Her group
catalysts is crucial for the hydrogenolysis to selectively generate focuses on the chemical utilizations of
valuable chemicals, and novel heterogeneous metal catalysts will various waste resources including biomass, plastics and CO2.
be discussed. Then, the photocatalysis as a relatively new
method to upcycle plastic wastes will be presented, followed by Yudi Wang obtained her B.S. degree in
the more traditional methods of plastic pyrolysis and solvolysis to Environmental Engineering at College of
convert various plastic wastes into useful products. In addition, Chemistry and Environmental Science,
other emerging strategies (such as plasma, microwave irradiation, Hebei University in 2020. Currently, she is a
etc.) as well as the new generation of upcyclable plastic Master student at the China-UK Low Carbon
thermosets will be covered. College, Shanghai Jiao Tong University. Her
research interests include the catalytic
hydrogenation of CO2 and other waste
feedstocks.

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Lei Zhang obtained his Bachelor (2017)
from Zhengzhou University and received
his master's degree (2020) from Shanghai
University in China. He was a joint-training
master of Shanghai Advanced Research 2. Hydrogenolysis
Institute, Chinese Academy of Sciences.
He is now a PhD student at China-UK Low The hydrogenolysis is a catalytic chemical method to break down
Carbon College, Shanghai Jiao Tong the C-C bond or C-heteroatom bonds such as C-O
University. His research mainly focuses on (hydrodeoxygenation, HDO) in the feedstocks by using H2. With
catalysis and waste resource valorization.
the rational design of an efficient catalyst, the hydrogenolysis
approach can selectively generate valuable oligomeric or
monomeric compounds from waste plastic components or even

Accepted Manuscript
Table 1. Overview of the discussed papers in the hydrogenolysis of plastics.

Substrate Catalyst Reaction conditions Products Yield% Solvent Ref.

PE, PP silica-supported Zr-H 150-190 °C, 1 bar H2, 5-15 h short-chain alkanes 40-84% none 27

Ni & NiMo sulfides/HZSM-5

HDPEs 375 °C, ~70 bar H2, 1 h gasoline-range fuels 42-65% none 28
+Si-Al support

Pt/HZSM-5; Pt/HY; paraffins, olefins &

PE 120-340 °C, H2 flow N.A. none 29
Pt/HMCM-41 alkyl aromatics

Poly(cyclohexylethyle
PS, LDPE, PEP PtRe/SiO2 170 °C, ~35 bar D2, 17 h ne); low MW >90% Isooctane 30
oligomers

branched, short-
Squalane Ru/CeO2 240 °C, 35 bar H2, 3-48 h ~70% none 31
chain alkanes

branched short-chain
Squalane Ru-V/SiO2 240 °C, 35 bar H2, 96 h >70% none 32
alkanes

PEs, PP Ru/CeO2 200-240 °C, 20-35 bar H2, 8-144 h liquid fuels & waxes 83-92% none 33

narrowly-ranged
PEs Pt/SrTiO3 300 °C, ~12 bar H2, 96 h lubricant-like 42~99% none 34
products

methanolysis: 140-200 °C, 3.5-14 h;

hydrogenation: Pt/C; hydrogenation: 80-160 °C, 50 bar H2, C7-C8 cycloalkanes &
PET Overall ~94% methanol 35
HDO: RuCu/SiO2 1-10 h; HDO: 350-400 °C, 40 bar H2, aromatics
8-22 h

methanolysis: 140-200 °C, 3 h; HDO:

PC HDO: Pt/C + H-β polycycloalkanes Overall ~72% methanol 36
100 °C, 30 bar H2, 1 h

1st step: 190 °C, Raney Ni, 1 h; 2nd C6-C15 isopropan

PC Raney Ni + USY step: 190 °C, USY added, 1-5 h (H2- ~75% 37
cyclic hydrocarbons ol
free for the two steps)

propane-2,2-
PC Rh/C + H-USY 200 °C, 35 bar H2, 12 h ~95% water 38
diyldicyclohexane

alkanes:
gaseous and liquid
PEs Ru/C 200-225 °C, 20-30 bar H2, 2-16 h ~82%; CH4: none 39
alkanes, CH4
~100%

SnPt/γ-Al2O3 + Re2O7/γ-
PE 200 °C, 20-40 bar He, 15 h Low MW oligomers N.A. n-pentane 40
Al2O3

PET,
H2O/octa
PS, PC, PPO & Ru/Nb2O5 280-320 °C, 3 bar H2, 8-16 h arenes 75-85% 41
ne
mixtures

PET Ru/Nb2O5 220 °C, 20 bar N2, 12 h BTX ~91% water 42

alkylaromatics &
LDPE/HDPE Pt/γ-Al2O3 280 °C, H2-free, 24 h 55-80% none 43
alkylnaphthenes

PET single-site MoO2/C 260 °C, 1 bar H2, 24-96 h TPA & ethylene 85-90% none 44

mixtures. So far, a number of homogeneous and heterogeneous hydrogenolysis.[19-26] This session will mainly focus on the
catalytic systems have been explored for plastic heterogeneous catalysis of waste plastics since heterogeneous

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catalysts are easier to recover and facile for product separation in and Nakagawa’s group has explored a Ru/CeO2 catalyst to cleave
practical applications. Table 1 shows a general summary of the a model compound Squalane (C30 branched hydrocarbon
discussed papers in the session. extracted from algae) by hydrogenolysis with minimal side
Dufaud et al. attempted the catalytic hydrogenolysis of reactions.[31] Branched, shorter-chain alkanes were obtained
commercial polyolefins including polyethylene (PE) and using Ru/CeO2 catalyst with a narrower distribution than other
polypropylene (PP) plastics as early as in 1998.[27] A well-defined, catalysts. Under 35 bar H2 at 240 °C, the internal C-C bonds
highly electrophilic silica-supported Zr-H catalyst was fabricated between branches of the substrate were selectively divided, and
to convert PE and PP into a range of short-chain alkanes. Low the C30 substrate was degraded first into branched C14-C16
MW PE was cleaved under about 1 bar H2 at 150 °C. The alkanes and then primarily C6-C10 finally into C1-C5 products with
conversion was 5%, 25% and 84% at 1 h, 2 h and 5 h, respectively. the reaction time from 3 h to 48 h. The remarkable selectivity of
Meanwhile, the fractions of lower alkane products gradually Ru/CeO2 was tentatively ascribed to the high dispersion of Ru
increased with prolonged time. Initially, only oligomers with even nanoparticles (NPs) (< 1.5 nm, with the Ru-Ru coordination
number carbon atoms were detected and those with odd number number of ~5). Following this, the same group has screened

Accepted Manuscript
carbon atoms appeared after 2 h, showing a statistical break- several Ru-based bimetallic components and Ru-V/SiO2 was
down of all the C-C bonds in low MW PE. Under similar conditions, identified as the most efficient one for the hydrogenolysis of
high MW LDPE (low-density polyethylene, ~125,000 Da) could be Squalane with an enhanced selectivity to branched C14-C16
completely converted into saturated oligomers after 5 h or lower alkanes by suppressing CH4 formation.[32] The incorporated V has
alkanes after 10 h at 150 °C, while PP (MW ~250,000 Da) was decorated on the Ru NPs and mitigated its particle size. However,
transformed at a higher temperature of 190 °C. The possible the introduction of V has reduced the overall catalytic activity and
mechanism for the reaction was proposed as follows: C-H bond aggravated carbon deposition.
activation of the polyolefins happened first with the liberation of After achieving the hydrogenolysis of Squalane, the group
hydrogen which was then grafted to the Zr center of the catalyst. utilized the Ru/CeO2 catalyst for the direct hydrogenolysis of
Next, the β-alkyl transfer occurred followed by the Zr-C bond different PE and PP plastics.[33] The efficient Ru/CeO2 catalyst
cleavage and the hydrogenation of the terminal double bond. converted the LDPE (MW ~4,000 Da) into liquid fuels (C5-C21) and
At the same time, Ding et al. developed the Ni and NiMo waxes (C22-C45) under 20 bar H2 at 200 °C with a total yield of
sulfides/HZSM-5 and Si-Al support (a hybrid support material) for 92%. The Ru NPs on the CeO2 support was in its metallic state
the hydrocracking of high-density polyethylene (HDPE) waste into with a small particle size (~1 nm), which acted as the main
gasoline-range products at a relatively high temperature of 375 °C catalytic centers. Compared to the Pt/H-USY, the Ru/CeO2
under ~70 bar H2 with a reaction time of 1 h.[28] The catalysts were catalyst showed a much higher selectivity to produce the major
not easily poisoned by impurities such as N, S, etc. in the plastic product n-hexane which was in agreement with previous findings.
wastes and could be reused after recalcination and resulfiding. Due to the acidity of the H-USY support, isomerization happened
Hesse et al. examined the hydrocracking of PE by using Pt to a large extent and branched C6 alkanes were dominantly
catalysts on different supports (HZSM-5, HY and HMCM-41).[29] obtained. Conversely, the basic nature and weak Lewis acid sites
The pore size and the acidity of the employed catalysts played of CeO2 would barely induce such side reactions. Besides, the
combinational effects on the reaction. Besides, the reaction CeO2 support also inhibited coke formation during the
temperature was also a key factor determining the product hydrogenolysis. Apart from LDPE (MW ~4,000 Da), the catalytic
distributions. system was able to efficiently transform LDPEs with higher MW
Supported noble metal nanomaterials are the most (~35,000 and ~50,000 Da) as well as HDPE (MW ~64,000 Da)
frequently-used catalysts for the hydrogenolysis of waste plastics. into the liquid fuels and waxes with a total yield of 88%, 87% and
Ertem et al. exploited the bimetallic PtRe/SiO2 catalyst for the 87% respectively, with the reaction time of 18 h, 24 h and 10 h.
hydrogenolysis of four different plastics including PS, two types of The PP plastic with a MW of ~12,000 was also degraded after a
linear LDPE, and poly(ethylene-alt-propylene) (PEP) under prolonged reaction time of 72 h with 83% product yield. Lastly, the
pressurized D2 gas at about 170 °C.[30] The polystyrene (PS) commercial plastic bag was employed producing the liquid fuels
feedstock has been completely hydrogenated into and waxes in high yields (see Figure 3). Based on previous
poly(cyclohexylethylene) with negligible hydrogenolysis occurred. density functional theory (DFT) calculations, the outstanding
On the contrary, the linear LDPE was considerably degraded by catalytic activity of Ru/CeO2 was probably because lower free-
hydrogenolysis during the H/D exchange reaction, with the MW energy barrier was determined on the Ru metal than other metal
dropped to less than 1/10 of the original value. The decomposition species for the cleavage of C-C linkage in alkane, which is the
presumably involved the C-C bond cleavage from a four-carbon rate-determining step (RDS) for PE hydrogenolysis.
side chain species absorbed on the catalyst surface. Tomishige

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Accepted Manuscript
Figure 3. Hydrogenolysis of a plastic bag and waste PEs with Ru/CeO2 catalyst. Reprinted with permission from Ref 33. Copyright 2021 Elsevier Ltd.

Celik et al. synthesized the highly-dispersed Pt NPs/SrTiO3 catalyst under 50 bar H2 at about 140 °C after 7 h. The DMCD
nanocuboids by atomic layer deposition (ALD) to selectively was then transformed to the C7-C8 cycloalkanes and aromatics by
degrade linear PE chains into a narrow MW distribution of liquid HDO with the bimetallic RuCu/SiO2 catalyst at 400 °C under 40
hydrocarbons (ca. 200-1000 Da),[34] which can be utilized as bar H2. The high-yield products could be potentially blended with
lubricant oils or further upgraded into other products, under the the gasoline or jet fuels to enhance the heat values and
optimal conditions of ~12 bar H2 at 300 °C after 96 h without a sustainability. In line with this work, the same group has employed
solvent. PE with different MWs as well as the commercial plastic a two-step method to transform polycarbonate (PC) waste into
bags could be cleaved by hydrogenolysis into narrowly-ranged polycycloalkanes.[36] (see Figure 4b) The first step is the
lubricant-like products in 42~99% yield. The combined methanolysis of PC into bisphenol with > 90% yield and the
experimental and computational results suggested that the PE second step is the HDO of bisphenol by using Pt/C and H-β as
chains preferentially interacted with the Pt NPs rather than the the catalysts at around 100 °C under 30 bar H2. The acidic zeolite
support, while Pt NPs with smaller size and larger surface fraction as a co-catalyst remarkably boosted the selectivity towards the
of low-coordinated sites facilitated the undesired over- desired product, and H-β performed the best among other tested
hydrogenolysis to produce lighter hydrocarbons. Therefore, the ones because of its large pore size and ample acidity. The
elaborate control of the Pt NPs size by adjusting the ALD polycycloalkanes were formed from PC with a high overall yield of
parameters was critical to guarantee a high selectivity toward the ~80% and lies in the jet fuel range which could be utilized as
desired lubricant-range products. Besides, the strong metal- waste-derived aviation fuels or fuel blends. Afterwards, the group
support interaction between Pt NPs and SrTiO3 has played a reported a one-pot method to transform PC into cyclic
notable role in alleviating the catalyst sintering. hydrocarbons with the highest ~75% yield by using the co-
Li’s group has developed a catalytic route to convert waste catalysts of inexpensive Raney Ni and USY in isopropanol by
polyethylene terephthalate (PET) into C7-C8 cycloalkanes and transfer HDO at about 190 °C.[37] The isopropanol served as both
aromatics by the methanolysis of PET and the subsequent the solvent and hydrogen donor. Meanwhile, a one-step route to
solvent-free hydrogenation and HDO.[35] (see Figure 4a) The first convert PC into a jet fuel range dicycloalkane with very high yields
methanolysis step was non-catalytic which exclusively was achieved by the same group using the catalysts of Rh/C and
depolymerized PET in methanol to the monomer dimethyl H-USY by the aqueous phase HDO at 200 °C under 35 bar H2
terephthalate with 97.3% yield at 200 °C after 3.5 h. Afterwards, after 12 h.[38]
the monomers were nearly quantitatively hydrogenated into
dimethyl cyclohexane-1,4-dicarboxylate (DMCD) by using Pt/C

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Accepted Manuscript
Figure 4. The catalytic routes for the transformations of PET and PC wastes (a, b, c & d) into liquid fuels or fuel additives by Li’s group. Adapted with permission
from Ref 35-38. Copyright 2019 & 2021 The Royal Society of Chemistry.

Rorrer et al. employed n-octadecane as a model compound material (a representative for HDPE, ~54,000 Da) was converted
and screened several metal-based catalysts for the under employed conditions and the MW of the PE plastic dropped
hydrogenolysis.[39] The Ru/C catalyst displayed the most by ~73% after the reaction with products such as n-hexane, n-
outstanding performances, which almost quantitatively converted heptane, etc. obtained.
the model compound into gaseous and liquid alkanes at 200 °C Wang and Yan’s group reported a powerful, multifunctional
and into predominantly CH4 at 250 °C. The product evolution with Ru/Nb2O5 catalyst to upcycle a variety of aromatic plastic wastes
time at 200 °C has shown that n-alkane products were observed and the mixtures into monomeric arenes with high yields.[41] The
(C8-C17) at 2 h and then gradual cleavage of both terminal and conversion of aromatic plastic polymers back into the monomers
non-terminal C-C bonds happened shifting the long-chain liquid that are precursors for aromatic plastic synthesis meets the
alkanes to gaseous ones. Next, the Ru/C catalyst has been demand of a circular economy (see Figure 5), which is important
applied to transform low MW PE (~4,000 Da) into liquid and for the sustainable development of the plastic industry. With the
gaseous alkanes and the reaction parameters have been Ru/Nb2O5 catalyst, 87.1% yield of arenes were obtained from PET
optimized. The H2 pressure, temperature and reaction time played hydrogenolysis at elevated temperature under 3 bar H2 after 12 in
significant roles on the product distributions. In addition, different water, with a distinctively high selectivity to p-xylene. The direct
PE substrates including commercial LDPE MI25, LDPE plastic transformation of Coca-Cola bottle was also attempted, and
bottle, etc. have been completely transformed under employed monomeric products were formed in 90.9% yield with a high
conditions into a mixture of liquid and gaseous alkanes. Notably, selectivity of 78.4% to arenes. Similarly, the PS, PC and
the LDPE plastic bottle was transformed into CH4 with almost polyphenylene oxide (PPO) plastic wastes were transformed into
100% selectivity at 225 °C with a reaction time of 16 h, offering a corresponding arenes with 75-85% yields either in water or in
highly selective way to generate natural gas product from waste octane solvent at 280-320 °C under low pressured H2 (3 bar).
plastics. Besides, the Ru/C catalyst exhibited satisfactory stability Moreover, the plastic mixtures were efficiently degraded by the
in the recycling tests. Meanwhile, the same group has adopted a break of C-C and C-O linkages and yielded the desired arene
dehydrogenation-olefin metathesis protocol to degrade PE products in as high as 78.9% yield. This demonstrates the
plastics by using a physical mixture of SnPt/γ-Al2O3 and Re2O7/γ- feasibility of the developed protocol on processing not only single-
Al2O3.[40] Initially, model reactions were used for catalyst selection component plastic but also complex plastic mixtures. The small
and temperature optimization. It was found that the bimetallic Ru clusters were highly dispersed on the surface of the Nb2O5
alloys of SnPt/γ-Al2O3 and Re2O7/γ-Al2O3 exhibited inferior support with low-coordination, inhibiting the undesired
performances to the physical mixture, probably because the close hydrogenation of the aromatic rings. Besides, the Nb2O5 support
contacts of SnPt with Re might impose negative effect on the boasted high oxygen affinity and Brønsted acid sites for C-O and
activity of the Re-catalyzed olefin metathesis. The linear PE C-C bond activation respectively. The Ru/Nb2O5 system enables

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Accepted Manuscript
Figure 5. Ru/Nb2O5-catalyzed hydrogenolysis of various aromatic plastic wastes into arenes in a circular economy. Reprinted with permission from Ref 41. Copyright
2020 Wiley-VCH GmbH.

a selective and effective way for the chemical upcycling of waste Kratish et al. reported a non-noble metal system for the
aromatic plastics into the valuable arenes contributing to the catalytic hydrogenolysis of PET plastics.[44] The carbon-supported
future establishment of the circular plastic economy. Afterwards, single-site MoO2 catalyst was inexpensive, stable and recyclable,
Wang’s group developed a H2-free route to convert PET into BTX which could efficiently convert PET without the addition of solvent
(benzene, toluene, xylene) products in water by using the at about 260 °C under merely 1 bar H2 gas into terephthalic acid
Ru/Nb2O5 catalyst,[42] in which the reaction of hydrolysis (the H2 (TPA) and ethylene products with high yields (maximal ~90%). By
needed originated from the EG intermediate), reforming and using a model compound 1,2-ethanediol dibenzoate, the reaction
hydrogenolysis/decarboxylation happened, adding new options in pathway was proposed that retro-hydroalkoxylation (β-C-O
the circular economy of PET. cleavage) happened first and then the hydrogenolysis of the vinyl
A novel solvent- and H2-free catalytic method has been benzoate intermediate occurred subsequently. In the future, more
deployed by Zhang et al. which transformed LDPE and HDPE academic efforts are anticipated to explore novel non-noble metal
plastics into valuable alkylaromatics and alkylnaphthenes (chain catalysts along with the noble metal-based ones for plastic
length on average ~C30) by using the ultra-small Pt/γ-Al2O3 hydrogenolysis.
catalyst (Pt NPs ~1 nm).[43] The tandem hydrogenolysis and
aromatization enabled the conversion thermodynamically feasible
at a relatively moderate temperature range. In the reaction, the H2 3. Photocatalysis
needed was self-generated and then consumed. The reaction
was temperature sensitive that low product yields were detected Photocatalysis has been long-standing applied in many aspects
at below 250 °C whereas gaseous products became predominant of the chemical reactions[45-48] while plastic upcycling by using
at beyond 330 °C. Starting from a low MW PE (~3,500 Da), the photocatalysis is in its early stage as an emerging field. The
liquid/wax products were obtained in ~80 wt% after a reaction exploitation of sunlight energy to deal with plastic wastes provides
time of 24 h at 280 °C, with ~57% selectivity to alkylaromatics. a facile and green way to valorize the feedstocks for value-added
Under similar conditions, ~69 wt% and ~55 wt% liquid yields were chemicals and fuels. The photocatalysis can not only assist in
obtained from LDPE bag and HDPE bottle cap respectively, with plastic degradation in environments but also can initiate redox
a selectivity of ~44% and ~50% towards alkylaromatics. The one- reactions to generate useful chemical products.[49] In a typical
pot, Pt-catalyzed conversion furnishes a prominent way to photochemical reaction, a semiconductor material is employed as
efficiently upcycle waste PE feedstocks into liquid alkylaromatics a photocatalyst which generates in-situ photoexcited electron-
without the addition of a solvent or H2 gas, which are industrially hole pairs as the active sites to stimulate the redox reactions.[50]
important chemicals that have been applied in a broad scope of
areas. 3.1. Photo-reforming of plastic wastes to generate H2

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The general principle of photo-reforming of plastics as well photocatalytic activity, a CNx/Ni2P panel instead of NPs as the
as the reported photocatalysts are shown in Figure 6. An initial photocatalyst was constructed by immobilizing the CNx/Ni2P
study on the photocatalytic conversion of plastic wastes can be material on textured glass, and the purposes of the new
dated back to 1981,[51] in which a Pt/TiO2 photocatalyst was configuration are to ease the recycling of the catalyst and obviate
employed to reform PVC into H2 gas in water at room temperature. the competing light absorption by the matrix.[54] Upscaled panels
Nonetheless, the activity was rather low, and recent studies have of 25 cm2 area of the photocatalyst were employed to transform
improved the product yield with new heterogeneous catalysts various waste solutions such as cellulose, PET and municipal
developed. In 2018, Reisner’s group developed a CdS/CdOx solid waste in flow at ambient temperature and pressure under
quantum dots to transform various plastic feedstocks including simulated solar light in 0.5 M KOH solution to generate
PET, poly(lactic acid) (PLA) and polyurethane (PUR) in 10 M satisfactory yields of H2 gas. Moreover, ~50% of the
NaOH aqueous solution at room temperature under atmospheric photocatalytic activity was maintained under even milder
N2 and simulated solar light (AM 1.5G, 0.1 W/cm2).[52] H2 gas as conditions (seawater, 0.2 sunlight irradiation).
well as useful organic chemicals have been selectively produced.

Accepted Manuscript
To further improve the reaction activity, a pretreatment method 3.2. Photocatalytic conversion of plastics into C2 chemical
was adopted to first impregnate the plastic powders in the 10 M
NaOH solution for 24 h at 40 °C in dark and the supernatant was Apart from H2, the photocatalytic transformation of plastic
used for subsequent transformation. The pretreatment has wastes can also lead to the formation of C2 chemical as a crucial
promoted the hydrolysis of the polymer chains and enhanced the product. Sun and Xie’s group have reported an innovative
activity for PET and PUR conversion to 4-times compared to photocatalytic way to transform waste plastics into acetic acid
untreated samples. Finally, a PET plastic bottle was transformed product (CH3COOH) via CO2 intermediate by a successive C-C
under employed conditions and constant H2 production was bond scission and coupling pathway without the use of sacrificial
observed for a lasting period of 6 days with an activity of ~4.1 agents.[55] (see Figure 7) The plastics including PE, PP and
mmol/gcat/h. The work puts forward a proof-of-concept system to polyvinyl chloride (PVC) were first completely decomposed into
remediate plastic wastes under mild conditions by utilizing visible CO2 as the predominant product by using the single-unit-cell thick
light and a low-cost catalyst in photocatalysis. Nb2O5 layers (sheet-like morphology with an average thickness of
~3 nm) under simulated natural environment conditions after a
reaction time of 40 h, 60 h, 90 h respectively. Then, the formed
CO2 was further upgraded to produce CH3COOH with prolonged
reaction time. Moreover, complex plastic wastes including single-
use bags, food containers and wrap films were also able to be
transformed in this way under employed conditions. Combining
the experimental and computational results, the photooxidation of
the C-C bonds of the plastic chains led to the selective production
of CO2 and the oxygen atoms came from both H2O and O2 in the
air. The O2 molecules and H2O-derived radicals were the active
components to initiate the oxidation process. On the other hand,
the CH3COOH product was generated from the photoreduction of
CO2 by the C-C coupling with the COOH intermediates. In the
reaction pathway, the formation of the HOOC-CO intermediate
was the RDS with a high energy barrier. The deficient adsorption
Figure 6. The general principle of plastic photo-reforming and the reported capacity of this intermediate as well as the unsatisfactory
photocatalysts. desorption ability of CH3COOH molecule on the Nb2O5 surface
have been assigned as the major reasons for the low efficiency of
the plastic-to-C2 chemical reaction. Although the product yields in
The same group then fabricated a nontoxic and inexpensive the photocatalytic valorization of waste plastics were generally not
CNx/Ni2P catalyst for the photo-reforming of different plastics in high, the existing studies pointed out the huge potentials to
alkaline aqueous solution.[53] The Ni2P NPs with a diameter of ~10 upcycle the plastic wastes under very mild conditions with the
nm was decorated on the cyanamide-functionalized CNx material assistance of renewable solar energy into a feasible pool of
which enhanced the charge separation, catalytic activity and chemicals and fuels. In the future, the efficiency of the
photostability. The plastic feedstocks were first pretreated as photochemical reactions may be improved by the development of
previous description and reacted in KOH solution under novel catalysts, the optimizations of system, etc.
atmospheric N2 and room temperature with exposure to simulated
solar light. A diversity of plastic substrates including PE, PP, PLA,
PET, PS, PUR and rubber were attempted, and the PET and PLA
afforded the highest H2 yield. The H2 gas generation was about
83 and 178 μmol/gsub from PET and PLA after a 50-h irradiation
under employed conditions, and the H2 was completely derived
from the water molecules instead of the plastics as confirmed by
the isotope labelling tests. In addition, the experiment has been
scaled up from 2 mL to 120 mL with negligible decrease in the
photocatalytic activity and performance. To boost the

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ChemSusChem 10.1002/cssc.202100868

MINIREVIEW
properties of the gas products obtained from the thermal pyrolysis
of different feedstocks including PE, PET, PP, PS, PVC and their
mixtures at different temperatures in a vertical dual-chamber
reactor.[58, 59] Elevating the temperature favored the formation of
gaseous products, and the highest gas yield of ~67 wt% was
achieved by using PP at 900 °C. From the energy aspect, the
thermal pyrolysis of PE and PP at 500 °C afforded the gas
fractions with the largest gross calorific values.
The thermal pyrolysis of PP has been inspected at distinct
temperatures and heating rates under either atmospheric or
vacuum pressure.[60] High yield of condensable products (> 81
wt%) was obtained at moderate temperatures, and the heating
rate has more remarkable effect on the product distribution under

Accepted Manuscript
vacuum condition. The influence of pyrolysis temperature
(gradually heated to 400 °C) has been studied using a slow
pyrolysis process to treat the packaging plastics (mixtures of PP,
LDPE and HDPE).[61] With the increase in temperature, the
Figure 7. The photocatalytic conversion of various plastic wastes into C2 paraffin content inclined while the olefin content declined in the
chemical by C-C cleavage and coupling. Adapted with permission from Ref 55. pyrolytic oils. Quesada et al. reported the pyrolysis of diverse
Copyright 2020 Wiley-VCH GmbH. plastic species and the mixtures in a fixed-bed reactor at about
500 °C under N2, in which the liquid oils were the dominant
products (ca. 60~75 wt%).[62] PE film pyrolysis led to liquid oils
4. Pyrolysis with the most similar characteristics with the commercial diesel
fuel, but with a higher viscosity and waxy appearance.
Pyrolysis generally refers to the thermal processes to Zeolites are the commonly used catalyst for the catalytic
degrade polymers at relatively high temperatures under an inert pyrolysis of plastic waste. A pilot-scale reactor has been
atmosphere into gases, liquid products and solid chars. In established to treat different plastics and their mixtures in the
contrast to thermal pyrolysis without any additives, catalytic presence of natural or synthetic zeolite catalyst at 450 °C.[63] The
pyrolysis engaging an acid or base catalyst is also widely used to highest gas yield of 75.4 wt% was realized from PP pyrolysis with
lower down the pyrolytic temperature, increase the selectivity natural zeolite, while the highest liquid yield of ~60 wt% was
towards the desired products, etc.[56] Pyrolysis may be the most obtained from the pyrolysis of PS/PE/PP mixture with synthetic
prevalently-studied one for the chemical upcycling of plastic zeolite. In line with this work, the USY zeolite catalyst was
waste, probably due to its wide feedstock tolerance and versatility. employed to pyrolyze PP, PE and the mixtures in a continuous
Either by thermal or catalytic pyrolysis, the plastics are often pilot plant at 500 °C.[64] The liquid oils were predominant (nearly
converted into diversified product streams and the selectivity or 80 wt%, C5~C7 hydrocarbons), along with the formation of gas
yield towards a specific compound was rather low which may products (~20 wt%, C3~C4 hydrocarbons). Gasoline and diesel-
pose great challenges on product separation and upgrading. In like fuels could be collected by adjusting the separation
this regard, it is more cost-effective to valorize each product temperature after pyrolysis. The mass and energy of the pyrolysis
fraction without complex purifications. Namely, the flammable gas are shown in Figure 8. Apart from zeolites, the binder-free
fraction or the pyrolytic oils (liquid phase) can be collected as fuels. bentonite clay pellets were adopted as an efficient catalyst to
The relatively easy-to-recover solid carbons can be applied in boost the calorific values and decline the viscosity of the liquid oils
different areas including energy supplies, environmental from various plastics with diminished pyrolysis time (liquid yield
absorbents, electricity storages, etc. 85~90 wt%).[65] Aromatic hydrocarbons were formed from PS, and
aliphatic ones from LDPE, HDPE and PP, which could be
4.1. Production of gas and/or liquid fuels by the pyrolysis of potentially used as substitutes for diesel and gasoline fuel. Lei’s
waste plastics group has examined seven types of activated carbon as the
catalyst for the pyrolysis of PE.[66] Jet-fuel range hydrocarbons
The various pyrolysis conditions may have considerable (including alkanes and aromatics) as well as H2-rich gas products
effects on the product distribution and yield, such as reactor were generated in high yield. The acidic sites of the activated
design, feedstock type, pressure, heating rate, etc. A conical carbon played a critical role on product selectivity that weak
spouted-bed reactor has been employed to effectively pyrolyze acidity stimulated alkane formation while strong acidity promoted
the PET waste at 500-600 °C.[57] The excellent heat transfer and the production of aromatics. Following this, the same group
bed turbulence enabled the formation of high yield of gases combined the biomass-derived activated carbon and MgO as the
(~50%) which could be used as fuel (after CO2 removal). Honus catalysts for the pyrolysis, and the synergistic effect further
et al. have conducted a systematic investigation on the physical favored H2 generation (enhanced to ~95 vol% in gas phase).[67]

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ChemSusChem 10.1002/cssc.202100868

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Accepted Manuscript
Figure 8. Mass and energy balance of plastic wastes pyrolysis with the USY zeolite catalyst. Reprinted with permission from Ref 64. Copyright 2018 Elsevier Ltd.

Biomass resources include various renewable and abundant

materials such as cellulose, chitin, etc. that can be utilized for
chemical or fuel production.[68-79] The co-pyrolysis of plastic and
biomass furnishes a beneficial strategy to possibly improve the
quality of gas or liquid fuels, attenuate the carbon emissions and
aid the waste management (see Figure 9). The co-pyrolysis of
pinewood and waste plastics such as PET, PP, etc. has facilitated
syngas production in the gas phase and suppressed char
formation, in which the synergy between biomass and plastic
enhanced the conversion efficiency and flammable gas yield.[80]
Chen et al. explored the synergistic effects by co-pyrolyzing
biomass model components (cellulose, starch, etc.) and PP
plastic.[81] The presence of biomass feedstocks has reduced the
energy requirement, and the addition of hemicellulose and lignin
Figure 9. The co-pyrolysis of biomass and plastic wastes.
mitigated coke formation. However, delayed PP degradation was
observed for all the blends. The microwave-assisted co-pyrolysis
of plastic waste (bottles and lids mainly containing HDPE) and
4.2. Production of functional carbon materials by the
used frying oils (a grease-type biomass) was demonstrated to
pyrolysis of waste plastics
efficiently transform the two types of waste into diesel-like oils
(max. 81 wt%) with low-oxygen content and satisfactory energy
The solid fraction after pyrolysis is usually comprised of
values.[82] The synergistic effect has enabled fast heating rate and
carbonaceous materials. With varied pyrolysis conditions, the
rapid process time. A tertiary Ni-CaO-C catalyst has been recently
yield, pore structure, surface functionality, heating value, etc. of
developed for the co-pyrolysis of pine sawdust and LDPE, which
the carbonaceous materials can be adjusted. Figure 10 shows the
notably enhanced the selectivity to H2 and inhibited CO2 formation
distinct types of carbon materials that can be obtained from plastic
in gas phase.[83] There are several reviews with specific focuses
pyrolysis under different reaction conditions. The various
on the co-pyrolysis of plastic waste which can be referred to if
pyrolysis parameters may lead to carbon materials with different
interested.[84-87]
morphologies. For example, the thermal pyrolysis of plastics such
as PE, PS and the mixtures under inert atmosphere at around
700 °C could lead to the formation of carbon microspheres with
distinct sizes, which have potential applications in lubricants,
paints, etc.[88]. Kim et al. examined the effects of the HZSM-11
catalyst and the flow atmospheres (CO2 or N2) on the pyrolysis of
used teabags that contained both biomass and plastic
components.[89] The catalytic pyrolysis under CO2 flow has
resulted in a higher yield of solid chars with satisfactory heating
values of ~26 MJ/kg which can be employed as a fuel.

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Accepted Manuscript
Figure 10. The different types of carbon materials that can be obtained from plastic pyrolysis and their potential applications.

The porosity and surface sites of the carbon materials may which the MWCNTs were obtained after simple purification.[95]
be crucial factors on their performances as pollutant absorbents, The binary catalyst showed superior activity to the monometallic
battery electrodes, etc. Alkaline activation was often integrated counterparts which led to increased yield, surface area and
with plastic pyrolysis to improve the pore structures. Yuan et al. stability of MWCNTs. Similarly, Yao et al. exploited an efficient
conducted the sequential thermal pyrolysis-base activation NiFe/γ-Al2O3 catalyst to pyrolyze the mixed plastic substrates
process under inert atmosphere to convert waste PET bottles into (drinking cups, boxes and wraps) in a two-stage fixed bed
porous carbons, of which the specific surface area and the reactor.[96] The metal types and bimetallic ratios exhibited
micropores could be regulated by the pyrolysis temperature and considerable influences on the MWCNT formation. Jia et al.
base/carbon ratio.[90] The porous carbons were utilized as developed a pyrolytic method to convert LDPE and PP into
selective and effective materials for CF4 greenhouse gas MWCNTs, in which the waste plastics were first heated under N2
absorption at ambient conditions. Likewise, Zhang et al. first gas at 700 °C and the non-condensable products were passed
pyrolyzed the PET bottles at 700 °C, and then the pyrolytic carbon through a catalytic reactor at 800 °C.[97] Ni NPs on three different
was mixed with KOH and heated under N2 at 700 °C for 1 h.[91] supports were investigated and the metal-support interaction was
Hierarchical porous carbons were obtained through the tandem critical. The Ni/La catalyst was superior to Ni/Mg and Ni/Sr
pyrolysis and base activation, with ample surface functional because the moderate metal-support interaction enabled
groups and a large specific surface area of 2683 m2/g. The porous optimized surface coverage and size of Ni NPs. In addition,
carbons displayed excellent performances as supercapacitor Chaudhary et al. has transformed waste plastic polybags, bottles
electrodes. Amorphous carbon chips have been prepared via a and cups into luminescent C-dots (5-30 nm diameter) by pyrolysis
two-step solvothermal-pyrolysis approach, in which the LDPE and at 400 °C under N2.[98] The C-dots exhibited good emission
HDPE plastic bags were initially treated by concentrated H2SO4 properties and relatively high quantum yield, which has been
at 110 °C and then the sulfonated PEs were pyrolyzed under Ar applied as selective Cu2+ sensor in water by the fluorescence
flow at 900 °C.[92] The resulted carbon chips were engaged as an quenching. The high selectivity toward Cu2+ sensing was ascribed
efficient and stable anode material in Li-ion battery. to the intensive interaction between Cu2+ ion and the surface
Graphene-like materials can also be synthesized from the functional groups of C-dots.
pyrolysis of waste plastics. For instance, the catalytic pyrolysis of
waste PP using the organically modified montmorillonite (OMMT)
produced graphene flakes (GFs) consisting of several graphene 5. Solvolysis
layers with various surface groups (such as -OH, -COOH, etc.).[93]
The OMMT functioned as both the catalyst and template to In the solvolysis of plastic wastes, the plastic chains are
facilitate PP decomposition and the carbonization of light depolymerized by the solvent molecules (also serve as the
hydrocarbon and aromatic intermediates. Another protocol reactant) that present in excessive quantities through nucleophilic
integrating thermal pyrolysis (at 900 °C) with boron-promoted substitutions. Diverse solvent systems including water, methanol,
graphitization (at 2400 °C) has transformed PET into highly polyols, amines and ammonia have been adopted for the plastic
ordered graphite which then served as the feedstock to solvolysis, usually at elevated temperature and/or with the
synthesize thin graphene sheets via the microwave-assisted addition of a catalyst to facilitate the depolymerization.
liquid-phase exfoliation.[94] Apart from porous and graphene-like In 2018, Liu et al. have designed several ionic liquids (ILs)
carbons, other morphologies such as multi-walled carbon with distinct acidity-basicity properties as the catalyst to promote
nanotubes (MWCNTs) and carbon dots (C-dots) were fabricated the alcoholysis of PC waste at about 120 °C.[99] The solvolysis
by plastic pyrolysis. Shen et al. mixed the PP plastics with OMMT could be undertaken in various solvents such as methanol,
and Ni-Al2O3 binary catalyst and heated them at 800 °C, after ethanol, propanol, etc., but the efficiency declined with larger

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ChemSusChem 10.1002/cssc.202100868

MINIREVIEW
alcohol molecules and methanol was the most suitable one. were well fitted with the diffusion model. Apart from PET pellets,
Among the examined ILs, the [HDBU][LAc] displayed the best the post-consumer PET wastes including PET bottles, trays and
performance which enabled complete conversion of PC to films (transparent or colored) with monolayer or multilayer
produce the bisphenol A (BPA) monomers with ~99% yield after structures were employed as the substrates. The particle size and
a short reaction time of 1 h. Besides, the [HDBU][LAc] could be the thickness of the feedstock materials considerably affected the
reused for multiple times with negligible decrease of the catalytic hydrolysis efficiency. Smaller and thinner plastic materials were
activity. A plausible reaction mechanism was proposed for the IL- easier and more effectively hydrolyzed, for instance, the
promoted methanolysis of PC. The PC polymers were initially hydrolysis yield on multilayer PET trays was nearly half the value
dissolved/swollen while the [LAc] anion of the ILs interacted with of that on the monolayer counterparts. The potential diagram
the methanol molecules to generate the active oxyanion process to treat multilayer, colored PET trays has been proposed
intermediates (as evidenced by FTIR and 1H NMR). Afterwards, (see Figure 11) based on which a life cycle assessment (LCA) has
the active intermediates interacted with the ester bonds in PC via also been undertaken to evaluate the carbon footprints. The
nucleophilic attack and degraded it into shorter and soluble process contains the steps of conditioning, milling, alkaline

Accepted Manuscript
oligomers, which were further depolymerized by the activated hydrolysis, filtration/nano-filtration, distillation acidification, drying,
methanol into monomeric BPA and dimethylcarbonate (DMC). etc., which could separate the impurities such as carbon black
A two-step alkaline hydrolysis of various PET wastes has and other unhydrolyzed polyolefins and result in purified
been demonstrated under mild conditions of 80 °C and ambient monomeric products of TPA and EG. The LCA analysis has
atmosphere.[100] After systematic parameter optimizations, the shown that the carbon footprints of the alkaline hydrolysis method
PET pellets were converted into the monomers TPA (obtained were smaller than the conventional incineration method if the
after acidification) and ethylene glycol (EG) with a high yield of 95 feedstock to solvent ratio could be maintained at a relatively high
wt% in 5 wt% NaOH aqueous-ethanol solution (water: ethanol = level.
4: 6 v/v) within a reaction time of 20 min. The reaction kinetics

Figure 11. Possible flowsheet for separation of colours and polyolefins while obtaining pure PET monomers. Reprinted with permission from Ref 100. Copyright
2020 The Royal Society of Chemistry.

Beckham’s group utilized EG as the biomass-derived solvent diminished energy consumption and carbon emission. The work
to deconstruct PET polymers by the titanium butoxide catalyst at provides a potential way to upcycle the virgin plastic wastes into
220 °C for 4 h via transesterification.[101] Then, the glycolyzed PET high-value materials by incorporating with biobased reactants to
was reacted with biobased dimethyl muconates by using the improve the environmental benefits. Beydoun et al. integrated the
same catalyst to produce new types of unsaturated polyesters upcycling of polyoxymethylene (POM) plastic wastes with
(UPEs) which were further upgraded into fiberglass reinforced biomass-derived diols to produce useful cyclic acetals, in which
plastics (FRPs) (see Figure 12). Based on the study, the upcycled the carbon content in POMs functioned as a C1 source.[102] 99%
FRPs materials exhibited superior properties and higher values yield of 1,3-dioxane could be obtained from POM powder using
than the original PET plastic, which simultaneously resulted in the Bi(OTf)3 catalyst at 80 °C for 2 h with the 1,3-propanediol as

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ChemSusChem 10.1002/cssc.202100868

MINIREVIEW
the reactant. The commercial POM mixtures were transformed diols were further upgraded into new materials of valuable
under similar conditions and the 1,3-dioxane was generated with aliphatic polycarbonates (APC), which displayed excellent
91% yield after distillation. Sardon’s group has employed linear properties to be applied as renewable polymer electrolytes for
diols to depolymerize the PC plastic wastes into the monomer solid-state batteries. Following this, the same group adopted this
BPA and carbonate-containing diols at 160 °C under N2 with organocatalytic procedure to produce functionalized cyclic
1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and methane sulfonic carbonates from PC wastes under similar conditions.[104]
acid (MSA) as the catalyst.[103] The obtained carbonate-containing

Accepted Manuscript
Figure 12. Overview of the two routes to convert PET waste into higher value products. Reprinted with permission from Ref 101. Copyright 2019 Elsevier Inc.

6. Other emerging strategies Jin and Yoshioka’s group has proposed the simultaneous PVC
dechlorination and the CO2 reduction[109, 110] into valuable formate
6.1. Energy-associated techniques for plastic treatment under hydrothermal conditions.[111] In the work, bicarbonate and
carbonate salts were employed as the starting materials to
Aside from the abovementioned approaches, other emerging represent absorbed CO2 solutions. The PVC was added into the
distinctive strategies have also been exploited for plastic waste aqueous solutions and the mixtures were heated to about 300 °C.
upcycling. Tour’s group has adopted the flash Joule heating (FJH) After a reaction time of 4 h, the dichlorination rate reached 98-
technique to convert plastic wastes into flash graphene (FG) 99.5% and the formate was exclusively produced from the
materials, along with the production of chemicals such as light bicarbonate/carbonate salts with 4-5% yield. In the reaction, the
hydrocarbons, carbon oligomers, etc.[105] The technique utilized Cl group of PVC was substituted by -OH group in high
electricity to generate FJH in the feedstocks, elevating the temperature water and functioned as a reductant to convert
temperature to a high level within a rapid period. Alternating bicarbonates/carbonates into formate. The study exemplifies the
current FJH was superior to direct current mode in treating plastic possibility for the co-valorization of CO2 and plastic wastes.
wastes, and the energy input was estimated to be 23 kJ/g. The Microwave irradiation has been widely applied to assist
FJH method is versatile to deal with different plastic feedstocks plastic waste treatments, which could improve the conversion
and their mixtures. Besides FJH method, Yao et al. reported the efficiency, shorten the reaction time, etc. Recently, a one-step,
non-thermal plasma-assisted hydrogenolysis of HDPE to light microwave-assisted protocol was put forward using the low-cost
alkanes (C1-C3, > 95% selectivity) at ambient conditions.[106] The Fe-based catalysts as the microwave susceptors to intrigue fast
cold H2 plasma has dramatically favored the thermodynamics, degradation of plastic powders (commercial plastic commodities
boosted the reaction kinetics and efficiently break down the after mechanical pulverization) within minutes.[112] H2 fuel was
polymer chains. obtained in high yield of 55.6 mmol/gplastic (equal to 97% of the
Ball mill, which offers a means to combine the chemical and maximal theoretical value), meanwhile, the MWCNTs were
mechanical forces, has been explored to remove the halogens in produced as a valuable carbon material. Ghosh et al. utilized the
waste plastics to reduce the environmental burdens and to ease ultrafast microwave irradiation process to convert the PET
its further transformation. Cagnetta et al. processed bromine- plastics into disodium terephthalate in a common household
contaminated PP wastes in a high-energy ball mill by adding iron microwave oven (1 kW) within 2 min.[113] These works
powders and quartz sands to enable the total debromination and demonstrated the advantageous potentials of microwave
mineralization of the plastic feedstock, in which the rate of technique in waste plastic valorization.
debromination was positively correlated to the polymer-to-
haloorganics mass ratio.[107] Lu et al. demonstrated the 6.2. The new generation of recyclable thermosets
dechlorination of PVC in a ball mill reactor using 1 M NaOH in EG
solvent at 190 °C and the removal rate could achieve > 99%.[108]

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ChemSusChem 10.1002/cssc.202100868

MINIREVIEW
In general, plastic materials could be categorized as catalysts, in which the reactor design as well as process
thermoplastic (dominant in the market) and thermoset. Compared optimization can be coupled to maximize the efficiency during
to the thermoplastics that can be remolded, the recycling and operation. To sum up, the chemical upcycling is a promising and
upcycling of thermosets are often more challenging due to the powerful strategy to synthesize various useful chemicals from
cross-linked network structures and the irreversible curing plastic wastes, leading to a “plastic-based refinery” to help
property. New generation of thermosets has been devised to alleviate the plastic pollution problem and contribute to the
solve the problems, by creating reversible networks among/within sustainable development of the chemical industry.
the polymer chains while concurrently maintaining the high
chemical/thermal resistances and structural robustness.[114, 115]
Zhu et al. fabricated a polymer material using γ- Acknowledgements
butyrolactone with a trans-ring fusion at the α and β positions, and
the high MW polymer was formed at room temperature without a The work was supported by the Young Scientists Fund of the
solvent.[116] Bearing excellent thermostability, the polymer could

Accepted Manuscript
National Natural Science Foundation of China (No. 21908145)
be quantitatively converted to the monomers via simple
and the Shanghai Sailing Program (19YF1422100).
chemolysis to achieve the close-loop utilization of the thermoset
material. García et al. reported a one-pot facile method to
Keywords: plastic waste • chemical upcycling • catalysis •
condensate paraformaldehyde and 4,4ʹ-oxydianiline (forming
polymers • sustainable chemistry
hemiaminal dynamic covalent networks) at low temperature,
which were then cyclized into poly(hexahydrotriazine)s at high
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Entry for the Table of Contents

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The chemical upcycling of plastic wastes offers a powerful and efficient strategy to utilize the waste as a resource for a diversity of
valuable fuels, chemicals and materials. The recent advances in this field will be introduced in the mini-review.

17
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