pubs.acs.

org/journal/ascecg Research Article

Heterogeneous Metal Azolate Framework‑6 (MAF-6) Catalysts with

High Zinc Density for Enhanced Polyethylene Terephthalate (PET)
Conversion
Ren-Xuan Yang, Yen-Tsz Bieh, Celine H. Chen, Chang-Yen Hsu, Yuki Kato, Hideki Yamamoto,
Chia-Kuang Tsung,* and Kevin C.-W. Wu*
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sı Supporting Information

ABSTRACT: Polyethylene terephthalate (PET) has been exten-

sively used for the fabrication of various packaging materials,
creating million tons of waste per year. Degrading and recycling
PET waste has been identified as a prominent issue. Herein, we
demonstrate an effective process to chemically convert PET to
bis(2-hydroxyethyl) terephthalate (BHET) through the use of
metal azolate framework-6 (MAF-6) as a catalyst in the presence of
ethylene glycol. MAFs are a subclass of metal−organic frameworks
(MOFs), with MAF-6 comprised of the metal ion Zn2+ and the
organic ligand 2-ethylimidazole. We have optimized the reaction
temperature, reaction time, and catalyst amount to achieve up to a
92.4% conversion of PET and an 81.7% yield of BHET at 180 °C for 4 h. MAF-6 was easily recovered and reused for at least five
times. We have also hypothesized a mechanism for the high conversion and yield of the PET glycolysis reaction catalyzed by MAF-6.
The use of MAF-6 as a catalyst opens a new route for the postconsumer recycling of PET with remarkable practicality.
KEYWORDS: Polyethylene terephthalate (PET), Metal azolate frameworks (MAFs), Glycolysis reaction, Waste recycling treatment,
Polymer depolymerization

■ INTRODUCTION
The global production of synthetic plastics has rapidly grown
over the past 50 years due to their diverse range of
applications, reaching about 350 million metric tons in 2017.
However, approximately 79% of plastic wastes were accumu-
lated in landfills or the natural environment, 12% were
incinerated, and only 9% were recycled.1 Most of the plastic
wastes are extremely difficult to degrade in the natural
environment, causing a long-lasting damage to local
ecosystems.2−5 Among the wide range of plastic materials,
polyethylene terephthalate (PET), commonly referred to as
“polyester”, has generated an immense amount of waste due to
its extensive use in the fabrication of food packaging, soft drink
bottles, and fibers in the textile industry.6,7 The robustness and
durability of PET makes it extremely resistant to chemical
degradation. Moreover, the waste PET can be photodegraded
into small fragments over time, resulting in microplastics in
aquatic and marine ecosystems. Eventually, the microplastics
from waste PET can be ingested and accumulated in living
organisms.8 The annual production of PET exceeded 30
million tons in 2017;9 therefore, researchers have put in
considerable effort to develop efficient treatments for PET
waste recycling to further convert plastic wastes into useful
materials.10−13 In general, PET recycling can be categorized
into four approaches: namely primary recycling, energy
recovery, mechanical recycling, and chemical recycling.14,15
Among these methods, chemical recycling has attracted
considerable attention because the process is less energy
intensive and the obtained product can be utilized for the
remanufacturing of PET materials.16,17 The chemical recycling
route is a chemical depolymerization process that breaks down
PET ester linkages to form segments and converts the
segments into small-chain fragments. This chemical depolyme-
rization can be achieved through hydrolysis,18 methanolysis,19
aminolysis,20 ammonolysis,21 or glycolysis.22 Therefore, PET
conversion, especially for the chemical depolymerization of
PET, holds great promise for the upcycling of waste PET to
equivalent- or higher-value purposes, such as the synthesis of
new PET or other value-added chemicals.23
Currently, glycolysis is the most promising approach because
the main product, bis(2-hydroxyethyl) terephthalate (BHET),
Received: November 3, 2020
Revised: April 10, 2021
Published: May 5, 2021

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can be utilized for the commercial-scale reproduction of
PET.24 In addition, the reaction occurs under comparatively
mild reaction conditions with less volatile solvents. Recent
advances in chemical glycolysis reactions have focused on
developing transesterification catalysts to enhance the reaction
rate and BHET monomer yield.10 Several efficient catalysts
such as metal oxide,25 nanoparticles,22 ionic liquids (ILs),26
protic ionic salts,24 and deep-eutectic solvents27−29 have been
developed. Although they are able to convert PET wastes into
BHET monomer with high reaction efficiency under milder
conditions, some similar demerits of these catalysts still exist
such as the requirement of PET pregrinding, low monomer
yields, or elusive separation of products. Consequently, the
development of new types of catalysts for PET to BHET
conversion is still in high demand.
The study of molecular catalysts has shed light on the design
of the next-generation catalysts for PET conversion. Early
studies have revealed that molecular catalysts show high
activity and monomer yield. For instance, Ghaemy and
Mossaddegh have determined the order of activity of their
catalysts as Zn2+ > Mn2+ > Co2+ > Pb2+.30 It is valuable to
convert these aspects to heterogeneous catalysts, which are
more industrially favorable, because they display easy
separation from reactants and products through filtration and
can bring about less waste production through recycling.26
Metal−organic frameworks (MOFs) provide a solution for
this. MOFs are a new class of crystalline nanoporous materials
self-assembled by metal ions/clusters (joint) and organic
ligands (linkers).31,32 The diverse combinations of metal ions
and organic ligands make MOFs impressive candidates for a
range of applications, including gas storage,33 chemical
separation,34 drug delivery,35 electronic devices,36,37 energy
storage,38 separation,39 and catalysis.40−42 Most importantly,
the high density and highly tunable metal joints of MOFs
could serve as active centers and make them promising
catalysts for PET to BHET conversion. Therefore, they have
the potential to display high activity and selectivity as
molecular catalysts and are able to be recycled by simple
separation from the reaction mixture. The diverse nanoscale
structures and superior chemical stability of zeolitic imidazo-
late frameworks (ZIFs) have received great scientific interest in
various applications.43 Indeed, Suo et al. have demonstrated a
result of using zeolitic imidazolate framework-8 (ZIF-8),
[Zn(mim)2] (mim = 2-methylimidazole), for PET glycolysis.44
ZIF-8 exhibited a relatively low BHET yield (68.1%) in
comparison with the inexpensive zinc chloride (70.0%)45 and
other heterogeneous catalysts.28 Notwithstanding the advances
in PET conversion, the small pore size of ZIF-8 may inhibit the
activity of PET conversion, and the reaction mechanism is not
been fully understood as well. The present work aims at
establishing a protocol of PET to BHET conversion catalyzed
by a large-pore MOF material and clarifying the overall
mechanism. On the basis of the knowledge from molecular
catalyst studies, we hypothesized that using MOFs with similar
metal centers while the coordination environment is fine-tuned
could promote BHET yield.
As far as we know, to date, no large-pore MOF catalyst has
been applied to PET conversion. To demonstrate that large-
pore MOF materials, tuned by adjusting the length of the
ligand, may render higher reaction efficiency, we selected metal
azolate framework-6 (MAF-6), RHO-[Zn(eim)2], which is
comprised of Zn2+ ions coordinated by 2-ethylimidazole
(Heim) linkers to use in the PET conversion.46,47 Although
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the coordinated composition of MAF-6 and ZIF-8 only differs
by one methylene group in the imidazolate ligand, a larger pore
size of MAF-6 (16.7 Å) in comparison to ZIF-8 (11.6 Å)48 can
be obtained. In this work, the reaction activity catalyzed by
large-pore MAF-6 and the reaction mechanism are investigated
thoroughly.
Further developments have examined the activities of an
isomeric series of [Zn(eim)2], including ANA-[Zn(eim)2]
(MAF-5) and the nonporous isomer qtz-[Zn(eim)2] (MAF-
32) with active center similar to that of MAF-6 but with
different coordination environments.49,50 Here, we report the
first PET to BHET conversion catalyzed by the large-pore
MAF-6 material, as illustrated in Scheme 1, with the highest
PET conversion being 92.4% and BHET yield being 81.7%.
Scheme 1. Schematic Illustration of MAF-6-Catalyzed
Glycolysis Reaction of PET to BHET
■
EXPERIMENTAL SECTION
Chemicals. PET pellets (2.0 mm × 2.0 mm × 2.5 mm) were
supplied by LIBOLON, Taiwan. Zinc oxide (Sigma-Aldrich, 99%), 2-
ethylimidazole (Sigma-Aldrich, 98%), ammonium hydroxide solution
(Honeywell, ∼25%), ethylene glycol (Alfa Aesar, 99%), methanol
(Macron, ≥99.8%), and cyclohexane (J.T. Baker, 99.5%) were used as
received without further purification. Deionized water was purified
with a Milli-Q system (Millipore, Bedford, MA, USA).
Synthesis of Metal Azolate Frameworks (MAFs). MAF-6,
MAF-5, and MAF-32 were synthesized at room temperature by rapid
mixing of an aqueous ammonia solution of zinc oxide (ZnO) and a
methanol solution of 2-ethylimidazole (Heim).50 For MAF-6, the
concentrated aqueous ammonia solution (25% NH4OH, 40 mL) of
ZnO (2 mmol) was added dropwise into a methanol (30 mL) and
cyclohexane (6.66% v/v) solution of Heim (4 mmol) with rapid
stirring at room temperature for 0.5 h. For MAF-5, a methanol (6
mL) solution of Heim (4 mmol) was rapidly poured into a second
solution of ZnO (2 mmol) dissolved in 25% NH4OH (40 mL) and
cyclohexane (3.25%, v/v). The solution was stirred at room
temperature for 0.5 h. MAF-32 was synthesized through a procedure
similar to that for MAF-5, except that no cyclohexane was added, and
the mixed solutions were stirred for 2 h. After the synthesis, the MAF
powders were collected by centrifugation and washing with methanol,
repeated three times. The washed powders were stored in a
lyophilizer overnight for drying.
General Catalytic Glycolysis Process of PET. In a typical
catalytic test, 5.0 g of PET pellets and 30 g of ethylene glycol (EG)
were placed in a 50 mL round-bottomed two-necked flask equipped
with a reflux condenser, a thermometer, and a magnetic stirrer.
Catalysts were placed in the flask, and the flask was immersed in an oil
bath at the target temperature for a predetermined time. The
glycolysis reactions were carried out at reaction temperatures ranging
from 160 to 190 °C for 2−6 h under atmospheric pressure. When
each reaction was complete, the reaction mixture was cooled to room
temperature and an excess amount of distilled water (300−400 mL)
was added to the solution with vigorous stirring. The catalysts and
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Figure 1. MAF-6 powder characterization. (a) PXRD patterns of the as-prepared and simulated MAF-6; (b) SEM image of MAF-6; (c) N2
adsorption (filled dots) and desorption (empty dots) isotherms of MAF-6; (d) TGA curve of MAF-6.
undepolymerized PET were filtered and separated from the products.
The undepolymerized PET was dried at 70 °C for 12 h and weighed
for the calculation of PET conversion, which is defined by eq 1
Wi − Wf
PET conversion (%) = × 100%
Wi (1)
where Wi represents the initial weight of PET and Wf represents the
weight of undepolymerized PET. In order to separate the oligomers
and dimers from the residual PET, 500 mL of distilled water was
added to the residual PET and the solution was boiled and stirred for
45 min. The residue on the filter was an oligomer, and the filtrate was
immersed in an ice bath. The white floccules that formed were
considered to be dimers. Moreover, the collected aqueous transparent
filtrate was concentrated to about 150−200 mL and stored in a
refrigerator at 4 °C overnight. White needle-like crystals were formed
in the solution and then filtered, dried, and weighed. The DSC scan,
GC-MS, and NMR characterization revealed that these crystals are
indeed BHET monomers. The BHET molar yield is defined by eq 2
WBHET/MWBHET
BHET yield (%) = × 100%
WPET/MWPET (2)
where WBHET and WPET correspond to the initial weight of PET and
the weight of obtained BHET, respectively. MWBHET and MWPET
refer to the molar mass of BHET (254 g mol−1) and the PET
repeating unit (192 g mol−1), respectively.
Characterization. The surface area, porosity, pore size, and pore
volume of the as-synthesized MAF catalysts were determined by using
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a nitrogen sorption analysis (BELSORP-max II analyzer). The
Brunauer−Emmett−Teller (BET) method was used to model the
specific surface area. The crystallinity and morphology of the catalysts
were analyzed by powder X-ray diffraction (PXRD, Rigaku) and
scanning electron microscopy (SEM, NovaTM NanoSEM 230). The
strength and type of acidic sites on the MAFs were evaluated by the
temperature-programmed desorption of adsorbed ammonia (NH3-
TPD) and IR spectra of adsorbed pyridine (see Figure S3 in the
Supporting Information). The reaction products were analyzed by an
elemental analyzer (EA, Elementar vario EL, cube type), a
thermogravimetric analyzer (TGA/DSC, TA Instruments SDT
650), nuclear magnetic resonance (1H NMR, Bruker drx500), and a
gas chromatograph−mass spectrometer (GC-MS, Agilent 6890/
5975).
■ RESULTS AND DISCUSSION
Characterization of As-Synthesized MAF Catalysts.
The morphology of MAF-6 was analyzed by SEM (Figure 1b).
In the SEM image, MAF-6 displays a homogeneous cubic
structure with particle sizes of 250−300 nm, and MAF-32 is
constructed by block-shaped particles with sizes of 200−300
nm. MAF-5 has a nonhomogeneous polyhedral structure with
larger sizes of 3−15 μm (see Figure S1 in the Supporting
Information). The PXRD patterns of MAF-6 fit well with
simulated patterns, which confirms the formation of MAF-6,
and show no other crystalline impurity phases (Figure 1a). In
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Figure 2. (a) Effect of amount of catalyst on PET glycolysis (temperature 180 °C, time 4 h). (b) Effect of temperature on PET glycolysis (catalyst
amount 0.05 g, time 4 h). (c) Effect of time on PET glycolysis (catalyst amount 0.05 g, temperature 180 °C). (d) Reusability of MAF-6 in PET
glycolysis (catalyst amount 0.05 g, temperature 180 °C, time 4 h).

Table 1. PET Glycolysis Catalyzed by Different Catalystsa Table 2. Hansen Solubility Parameters of Specific Solvents
Used for Solubility Tests
catalyst PET conversion (%) BHET yield (%)
no catalyst 0 0 entry solvent δd (MPa1/2) δp (MPa1/2) δh (MPa1/2)
zinc acetateb 71.0 51.8 1 hexane 14.9 0 0
zinc chlorideb 58.0 34.8 2 toluene 18 1.4 2
zinc oxideb 28.2 9.0 3 nitrosobenzene 20 12.7 4
MAF-5b 72.3 39.0 4 methyl ethyl ketone 16 9 5.1
MAF-6b 92.4 81.7 5 quinoline 20.5 5.6 5.7
MAF-32b 52.6 38.2 6 acetone 15.5 10.4 7
a 7 ethyl acetate 15.8 5.3 7.2
Reaction conditions: PET (5.0 g), EG (30 g), atmospheric pressure
at 180 °C, 4 h. bZinc acetate, zinc chloride, zinc oxide, MAF-5, MAF- 8 1,4-dioxane 17.5 1.8 9
6, and MAF-32 were added to the PET glycolysis system with the 9 dimethyl sulfoxide 18.4 16.4 10.2
same percentage content of Zn based on MAF-6 (7.7 mmol). The 10 dimethylformamide 17.4 13.7 11.3
actual amount of Zn was measured by ICP (see Table S2 in the 11 benzyl alcohol 18.4 6.3 13.7
Supporting Information). 12 N-methylformamide 17.4 18.8 15.9
13 1-propanol 16 6.8 17.4
addition, the strong intensities of the diffraction peaks suggest 14 diethylene glycol 16.6 12 19
that MAF-6 possesses high crystallinity. The structures of 15 formamide 17.2 26.2 19
MAF-5 and MAF-32 were confirmed by PXRD as well (see 16 ethanol 15.8 8.8 19.4
Figure S2a in the Supporting Information). N2 adsorption− 17 ethanolamine 17 15.5 21
desorption isotherms show a high Brunauer−Emmett−Teller 18 methanol 14.7 12.3 22.3
(BET) specific surface area of the MAF-6 sample (Figure 1c) 19 ethylene glycol 17 11 26
of approximately 1544 m2/g and a pore size of around 16.7 Å
(see Table S1 in the Supporting Information). MAF-6 exhibits MAF-6 was analyzed by thermogravimetric analysis (TGA)
a reversible type I physisorption isotherm on the basis of the under the N2 atmosphere (Figure 1d). The TGA result of
characterization of the International Union of Pure and MAF-6 showed no significant weight loss below 400 °C,
Applied Chemistry (IUPAC) classification, with a sharp indicating the good thermal stability of MAF-6. The thermal
increase at a low relative pressure, suggesting that MAF-6 stabilities of MAF-5 and MAF-32 were also analyzed by TGA
possesses a microporous feature. The N2 physisorption (see Figure S2c in the Supporting Information).
isotherms of MAF-5 and MAF-32 are displayed in Figure Catalytic Glycolysis Reaction Optimization of PET.
S2b in the Supporting Information. The thermal stability of Due to the high performance of MAF-6, we studied the
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Table 3. Solubility Scores of MOF Materials in Certain Organic Solventsa

entry solvent MAF-5 MAF-6 MAF-32 ZIF-8 ZIF-67
1 hexane 1 0 0 0 0
2 toluene 2 0 0 0 0
3 nitrobenzene 0 0 0 0 0
4 methyl ethyl ketone 0 0 0 0 0
5 quinoline 0 0 0 0 1
6 acetone 0 0 0 1 0
7 ethyl acetate 0 0 0 1 0
8 1,4-dioxane 0 0 0 0 0
9 dimethyl sulfoxide 0 0 0 0 0
10 dimethylformamide 0 0 0 0 0
11 benzyl alcohol 0 0 0 0 0
12 N-methylformamide 0 1 0 0 1
13 1-propanol 0 1 0 0 0
14 diethylene glycol 0 0 1 0 1
15 formamide 0 1 0 0 0
16 ethanol 0 0 0 0 0
17 ethanolamine 0 0 0 0 0
18 methanol 0 0 0 1 0
19 ethylene glycol 0 0 1 0 1
a
The value of the score was determined by 1 and 2 as being a good solvent and 0 as being a poor solvent.

Figure 3. Three-dimensional HSP plots and Hansen solubility spheres for each target compound. Blue spheres represent “good” solvents, and red
cubes represent “poor” solvents.

catalysis of MAF-6 in detail. The PET glycolysis over the
MAF-6 catalyst was carried with different amounts of catalyst,
reaction temperatures, and reaction times (Figure 2). First, the
PET glycolysis was performed at 180 °C for 4 h with variation
of the amounts of MAF-6 catalyst (Figure 2a). When the
amount of catalyst was 0.005 g, the conversion of PET and
yield of BHET were 58.6% and 48.8%, respectively. By an
increase in the amount of catalyst added to the glycolysis
system, the conversion of PET and yield of BHET showed a
significant increase. When the amount of catalyst was raised to
0.05 g, the conversion of PET and yield of BHET reached
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92.4% and 81.7%, respectively. The reason may be that the
smaller amount of catalyst possessed less surface area and
fewer active sites in comparison to that of 0.05 g of catalyst,
decelerating the process of reaching a chemical equilibrium.
However, when the amount of catalyst was increased further to
0.5 g, the conversion of PET and yield of BHET decreased to
89.6% and 60.3%, respectively. The possible reason is that
monomers will undergo a polymerization reaction by
themselves and occupy some active sites, which may cause a
slowing of the reaction rate and obtaining a lower yield of
BHET. Thus, the catalyst amount of 0.05 g was chosen to be
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Figure 4. Three-dimensional HSP of target materials and the affinity
(Ra) between PET and samples in ethylene glycol.
Table 4. Hansen Solubility Parameters of Specific
Substances in the 3D Diagram (Figure 4)
applied in the other reactions because of the highest
conversion of PET and yield of BHET. The characterizations
of the product are shown in Table S3 and Figures S4−S6 in the
Supporting Information. Figure 2b presents the influence of
reaction temperature on PET conversion and BHET yield. The
conversion of PET increased significantly with an increase in
temperature from 160 to 180 °C, with the maximum value
reaching 92.4% at 180 °C with an 81.7% BHET yield. The
results revealed that high temperature could afford sufficient
energy to expedite the catalytic reaction rate, and the PET
polymer chain could be broken down into monomers.
However, the PET conversion (94.0%) and BHET yield
(78.3%) decreased slightly when the temperature was further
increased to 190 °C, indicating that a reaction temperature
over 180 °C would affect the reaction equilibrium between the
BHET monomer and the dimer.27
A time-dependent analysis of the PET glycolysis catalyzed
by MAF-6 is presented in Figure 2c. In the period of 1−4 h,
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both the conversion and yield increased with an increase in
time. When the reaction time was extended to 4 h, 92.4%
conversion of PET could be achieved at 180 °C. Nevertheless,
if the reaction time was prolonged to 6 h, the yield of BHET
decreased, which was caused by the chemical reaction
equilibrium between the BHET monomer and the dimer. In
short, with a reaction time extending to 6 h, the dimerization of
BHET was carried out as a side reaction. Thus, it can be
concluded that the operating time is a critical factor for the
glycolysis of PET.
The feasibility of recycling this heterogeneous catalyst was
also evaluated in this study, as shown in Figure 2d. At the end
of each run, the catalyst was separated from the reaction
mixture by filtration and directly reused for a subsequent
reaction under the optimized reaction conditions, which were
180 °C for 4 h under atmospheric pressure. After five runs, the
catalytic performance retained a 71.2% product yield. From the
XRD pattern, shown in Figure S3c in the Supporting
Information, the phase composition of used MAF-6 is same
as that of fresh MAF-6. In addition, an ICP-MS measurement
revealed that only 3.7% of metal ions leached out after five
times of recycling. These results demonstrate that the high
stability of MAF-6 provides a sustainable and practical future
application for the PET glycolysis reaction.
In the catalytic evaluation tests, the reactions were catalyzed
by as-synthesized MAFs and other zinc salt catalysts, and the
results are summarized in Table 1. In the catalysis by MAF-6,
PET is depolymerized with a particularly higher yield of 81.7%
BHET in comparison with conventional metal salts reported in
previous literature. The reason can be ascribed to the high
specific surface area of MAF-6. Thus, aside from this, the
solubility discrepancies of the reactant and catalyst in ethylene
glycol may affect the yield of BHET, as an important factor in
this system.
Affinity Evaluation. The solvent usually plays a crucial
role in the uniformity of a reaction mixture. The solubilities of
the reactant and catalyst in organic solvents are important
properties for giving high catalytic performance in both
conversion and yield. The Hansen solubility parameters
(HSPs) have recently attracted attention and are widely used
to evaluate the solubility of materials. The HSPs are comprised
of δd, δp, and δh (MPa1/2), which are dispersion, polar, and
hydrogen-bonding forces in the cohesive energy density of the
target compound, respectively.51 In addition, the solubility
parameter (δt) can be expressed as three partial terms, as
shown in eq 3:
δt = (δd 2 + δp2 + δ h 2)1/2 (3)
The HSPs of MOF catalysts were determined via the Hansen
solubility sphere method for an affinity evaluation. The series
of 19 solvents with a wide range of solubility parameters shown
in Table 2 were selected for solubility tests. The corresponding
dispersion stability scores for the target material in each
organic solvent are shown in Table 3. An example of the score
measured experimentally by the solubility test, known as a
dispersion stability evaluation in certain types of solvents, is
shown in Figure S7 in the Supporting Information. Figure 3
displays the three-dimensional (3D) HSP plots of good and
poor solvents for each target substance on the basis of the
solubility test results. Blue spheres and red cubes represent
solvents with good and poor affinity, respectively. When the
scores obtained from solubility tests are input into the
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Scheme 2. Proposed Reaction Mechanism for PET Glycolysis Catalyzed by MAF-6
Scheme 3. Size of MAF-6 and of the Dimer and Monomer (BHET)
calculation program, Hansen solubility parameters in practice
(HSPiP) made by Steven Abbott TCNF Ltd. UK (5th
edition),52 show that a good solvent in a certain region can
form a sphere in the 3D diagram representing the Hansen
solubility sphere. Good solvents are plotted inside the
solubility sphere, while poor solvents are plotted outside.
Therefore, the central coordinate of the solubility sphere can
be defined as the HSP value of the target substance.
The index described as Ra in eq 4 represents the distance
between the HSPs of two substances in the 3D diagram of the
Hansen sphere and can be used to evaluate the affinity between
substances quantitatively
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Ra =
[4 × (δd,1 − δd,2)2 + (δp,1 − δp,2)2 + (δ h,1 − δ h,2)2 ]1/2
(4)
where δd,1, δp,1, and δh,1 represent the HSP values of
component 1 and δd,2, δp,2, and δh,2 represent the HSP values
of component 2. The HSPs of each material can be illustrated
in a 3D diagram, as shown in Figure 4. A smaller Ra value
means a higher affinity of each substance because the
interaction forces between the molecules are similar. Table 4
shows the HSPs of specific substances and the distance
between the HSPs of MOF materials from ethylene glycol
(EG) and PET. The affinities of the PET reactant and MOF
catalyst in ethylene glycol are critical values in achieving good
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Figure 5. Reactions with different PET feedstocks.
catalytic performance in the PET glycolysis system. Therefore,
both values should be taken into consideration. A better
catalytic performance can be attributed to the case of the
similar interaction distances (Ra) of the MOF catalyst from EG
and PET. Among all the MOF catalysts included in the HSPs
test, MAF-6 has the most similar affinity in Ra index, indicating
great compatibility and good dispersibility between the PET
reactant and MAF-6 catalyst in the organic solvent, rendering
higher possibilities of effective collisions and interactions
between two particles during the PET glycolysis reaction and
further enhancing the yield of BHET.
Reaction Mechanism of PET Catalytic Glycolysis. The
reaction mechanism of PET glycolysis catalyzed by MAF-6 is
proposed in Scheme 2. Zinc ions of MAF-6 act as a Lewis acid
to catalyze consecutive transesterification reactions.25,27,29,53,54
These are SN2 nucleophilic substitution reactions, in which the
lone pair electrons of the carboxyl oxygen in the ester linkages
of the PET unit are attacked. In the first step, Zn ions on the
surface of MAF-6 attack the carboxyl oxygen and facilitate
polarizing carboxyl oxygen. This process further enhances the
electrophilicity of the adjacent carbon. Therefore, the oxygen
in the hydroxyl of ethylene glycol is capable of nucleophilic
attack at the carboxyl carbon, resulting in a tetrahedral
transition state, further pushing off the metal ion, and breaking
the ester linkage of PET. Afterward, the oligomers and dimers
are generated sequentially by means of continuously repeating
these reaction processes. Eventually, the desired monomeric
product, BHET, can be formed. On the basis of this reaction
mechanism, we can assume that the Zn node on the external
surface of MAF-6 can do the first few steps. After more bonds
are broken into small fragments, such as dimers, the reaction
can be catalyzed by the Zn node in the pore of the MAF-6
scaffold.
For the sake of verifying the dimers’ abilities to diffuse into
the pores of MAF-6, the size effect was examined and is
displayed in Scheme 3. The molecular size of dimers with
minimized energy turns out to be capable of passing through
the large pores and generating BHET. In contrast, the smaller
pore size of MAF-5 and nonporous MAF-32 (see Table S1 in
the Supporting Information) made it difficult for dimers to
diffuse into the pore structure. This result demonstrates that
dimers can diffuse into the pore structure of MAF-6, so that
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pubs.acs.org/journal/ascecg Research Article
the reaction rate can be accelerated due to the abundant active
sites in the pore structure. The larger pore size of MAF-6
exhibits a selective diffusion of dimers into pores for further
conversion into BHET monomers. Chen et al. found a similar
result in the selective hydrogenation of cinnamaldehyde that
the flexible framework of ZIF-8 can allow cinnamaldehyde to
pass more easily through the pores and contact the active sites
in the pore structure in comparison to the rigid framework of
ZIF-71.55
The reaction protocol is also applicable in the catalysis of
postconsumer PET bottles. As shown in Figure 5, on
conversion of wasted PET beverage bottles into BHET by
means of a glycolysis reaction, a 92% conversion of PET and
61.7% yield of BHET can be achieved. Thus, the reaction
strategy in this work is considered to be a promising route for
depolymerization reactions, rendering greater possibilities in
further practical applications.
■ CONCLUSION
In summary, we have developed a catalytic process of PET
glycolysis over MAF-6 catalyst in the presence of ethylene
glycol. This process achieved an efficient and sustainable PET
recycling. The outstanding catalytic performance can be
attributed to MAF-6’s high specific surface area, large pores,
and good dispersibility between PET and ethylene glycol. A
remarkable yield of BHET (81.7%) was achieved in the
presence of MAF-6 (0.05 g), ethylene glycol (30 g), and PET
(5.0 g) for 4 h of glycolysis at 180 °C. The MAF-6 catalyst can
be recycled for at least five sequential runs without sacrificing
the performance. The results show that the large pore size of
MAF-6 can provide guidance for the design of more efficient
and selective catalysts, which may be taken into consideration
for continuous conversion of PET wastes by the process
design. Consequently, this work is capable of providing a
highly efficient recycling route of PET wastes and shows
promising prospects for further industrial applications.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.0c08012.
https://doi.org/10.1021/acssuschemeng.0c08012
ACS Sustainable Chem. Eng. 2021, 9, 6541−6550
ACS Sustainable Chemistry & Engineering
Characterization of as-synthesized MAFs catalysts,
characterization of PET glycolysis products, and Hansen
solubility parameters of the catalysts (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Chia-Kuang Tsung − Department of Chemistry, Merkert
Chemistry Center, Boston College, Chestnut Hill,
Massachusetts 02467, United States; orcid.org/0000-
0002-9410-565X; Email: frank.tsung@bc.edu
Kevin C.-W. Wu − Department of Chemical Engineering,
National Taiwan University (NTU), Taipei 10617, Taiwan;
Center of Atomic Initiative for New Materials (AI-MAT),
National Taiwan University, Taipei 10617, Taiwan;
orcid.org/0000-0003-0590-1396; Email: kevinwu@
ntu.edu.tw
Authors
Ren-Xuan Yang − Department of Chemical Engineering,
National Taiwan University (NTU), Taipei 10617, Taiwan;
Center of Atomic Initiative for New Materials (AI-MAT),
National Taiwan University, Taipei 10617, Taiwan;
orcid.org/0000-0001-9589-629X
Yen-Tsz Bieh − Department of Chemical Engineering,
National Taiwan University (NTU), Taipei 10617, Taiwan
Celine H. Chen − School of Engineering, Brown University,
Providence, Rhode Island 02912, United States
Chang-Yen Hsu − Department of Chemical Engineering,
National Taiwan University (NTU), Taipei 10617, Taiwan
Yuki Kato − Department of Chemical and Environmental
Engineering, Faculty of Environmental and Urban
Engineering, Kansai University, Suita, Osaka 564-8680,
Japan; orcid.org/0000-0002-8520-3389
Hideki Yamamoto − Department of Chemical and
Environmental Engineering, Faculty of Environmental and
Urban Engineering, Kansai University, Suita, Osaka 564-
8680, Japan; orcid.org/0000-0001-7113-0070
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.0c08012
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the Ministry of Science and
Technology (MOST), Taiwan under the Shackleton Program
award number 108-2638-E-002-003-MY2, and the other
MOST grant (109-2917-I-564-015).
■
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