Photocatalytic Removal of Polyester Polyurethane, and Polyethylene
Microplastics via ZnO-Fe-Mg-C Nanocomposite to H2
DELİA TERESA SPONZA, RUKİYE ÖZTEKİN*
Department of Environmental Engineering
Dokuz Eylül University
Tınaztepe Campus, 35160 Buca/Izmir,
TURKEY
* Corresponding Author
Abstract: - In this work H2 generation was studied via polyester, polyurethane, and polyethylene microplastics
using a novel nanocomposite namely zinc oxide-iron-magnesium-carbon (ZnO/Fe/Mg/C). The probability of H2-
production from plastic wastes was researched. The characterization of this nanocomposite were performed by
XRD, FTIR, Raman, SEM, EDS and TEM analysis. XRD analysis showed that lattice planes of ZnO/Fe/Mg/C
nanocomposite were distributed as (100), (002), (101), (102), (110), (103), (200), (112) and (004) according to
FTIR analysis, it was found that the ligth abundances at 610, 682 and 779 cm-1 were associated with the Zn and
O moeities, while the maximum peak at 399 cm-1 can be defined with Zn, Fe and Mg oxides and they connected
to Zn and OH radicals. Raman spectra exhibited the G-band at 1499 cm−1 as special properties of sp2 carbonated
moeities. SEM results showed that a brittle and porous structure containing spherical nanosized particles was
detected in the ZnO/Fe/Mg/C nanocomposite, where various voids were formed, while the zinc particle size
containing carbon-Mg-Fe was increased by excess carbon and ZnO/Fe/Mg/C nanocomposite. Furtheremore the
effects of some operational conditions (time, nanocomposite concentration, temperature) on the yields of H2
productions from both micropollutants were examined. The maximum H2 production was detected at 250 mg/l
polyethylene microplastic as 9800 ml/h with ZnO/Fe/Mg/C nanocomposite a, containing 2% Fe while the H2
production was detected as 7800 ml/h from polyester polyurethane with the same nanocomposite. Optimum
operating conditions; maximum H2 production efficiencies of 99% polyethylene and 88% polyester polyurethane
were achieved at 3 mg/l ZnO/Fe/Mg/C nanocomposite a, concentration, at 3 minutes and at 5 minutes
experimental times and at 125oC temperature, respectively.
Key-Words: - Hydrogen (H2) production; H2, fuels; Microplastics; Polyester Polyethylene; Polyurethane;
Photocatalytic removal; ZnO/Fe/Mg/C nanocomposite.
1 Introduction
In recent years microplastic wastes affect negatively
the ecosystem. Microplastics are plastic wastes with
a diameter < 5 mm. they cannot be treated from the
ecosystems with some conventional processes since
they have very small bodies, [1], [2]. Nanoplastics
have a dimension of 0.1 µm. The remediation of
microplastics is very important phenomenon since
they have extensively used, [3], [4]. The novel
progress is the recovery of microplastics to the
economical valor having organics as ultimate end
products. The polymers containing no olefins
exhibited completely different structures from the
plastics containing olefin. These products were:
polyethylene (PE), polypropylene (PP), and
polystyrene (PS), [5], [6], [7], [8], [9]. The
physicochemical properties of microplastics based on
fabrication procedure is effective in microplastic
transformation. From remediation processes the
polymers can be emitted to the ecosystems, [10].
Polystyrene, polyurethane and polyethylene was
detected in municipal sludge and in environments
containing garbage.
Polyethylene contained low weight carbon
benzene and can be generated from the degradation
of ethylene, [11], [12], [13], [14], [15], [16], [17],
[18]. Polyethylene is a resin from polyolefin group. It
is extensively utilized microplastic and can be
generated from the food wrap and some plastic
bottles and fuel boxes. It can degraded to fibers or
and emitted from the rubbers. Types of polyethylene
were summarized as follows, [19], [20], [21], [22],
[23], [24]:
1. Low-Density Polyethylene (LDPE): LDPE is
used extensively since it was not expensive. It
can be suitable for plastic film applications like
5HFHLYHG1RYHPEHU5HYLVHG$SULO$FFHSWHG0D\3XEOLVKHG-XQH
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grocery bags and food packaging. Despite its
lower tensile strength and temperature
resistance, LDPE’s flexibility and toughness
make it a popular choice in the market.
2. High-Density Polyethylene (HDPE): HDPE is
praised for its high strength and stiffness. These
attributes, combined with its resistance to many
solvents, make it appropriate for extensive
utilizations, from milk bottles to fuel tanks and
piping systems.
3. Linear Low-Density Polyethylene (LLDPE):
Bridging the gap between LDPE and HDPE,
LLDPE offers superior tensile strength, large-
scale deformability, and excellent resistance to
environmental stress cracking. It is used in
applications like stretch wrap, toys, and flexible
tubing.
Nano sized ZnO, was extensively utilized in
drinking and polluted water remediations, since has
elevated redox potential, elevated electron activity
and good photocatalytic activity, [12], [14]. ZnO
nanocomposite exhibited elevated surface and high
durability compared to other metal oxides. This,
cause to an excellent photodegradation activity, [15].
In order to extend the photocatalytic yields of ZnO,
nonmetals, and carbonated chemicals can be doped
on ZnO surface to improve the activity of electrons
in holes, [20]. By combining of a metal, the
photodegradation yields can be elevated since redox
reactions improve the light activity. These improves
the surface resonance of the photocatalyst.
Electromagnetic band gap energies of the metal
nanocomposites resulting in transformation of
electrons from valence band (VB) to conduction band
(CB) ending with photocatalysis, [14], [19], [20],
[21], [22], [23]. The presence of Ni2+ and Fe3+ in the
nanocomposites cause to super magnetic structure of
Ni ferrites, [11], [12], [14], [19], [20], [21], [22], [23].
Combining of ZnO with some metals like Fe, and Ni
was performed to improve its ferro magnetic
properties, [15], [24], [25]. The recent studies
showed that photodegradation properties were
performed by ZnO connected with certain ratios of
NiFe2O4, [26], [27]. The Photoactivity of nano
composites are influenced by the generation rules,
nanocomposite diameter, and certain ratios of dopant
molecules. Fe-Ni nanocomposites were utilized are
used to photodegrade the microplastic residues with
excessive H2 productions.
The doping of Fe to Ni improved the
nanocomposite activity, [28], [29], [30], [31], [32].
Physicochemical analysis results indicated that
doping of Ni increase the metal nanocomposite
diameter and oxygen releasing. Fe-Ni nanocomposite
show high catalytic performance resulting in 98%
hydrogen production from microplastic residues. Ni
having nanocomposites exhibited excellent
performance due to C and H bond degradation ending
with excellent photocatalytic performances, [20],
[22]. Nano metal oxides having Zn, Mg and Ca
exhibits excellent microbial inhibitions, [33], [34],
[35], [36], [37], [38]. In recent works, it was found
that, ZnO nanocomposites exhibited inhibitions
versus microorganisms, [39], [40], [41], [42], [43],
[44], [45], [46], [47]. The recent literature showed
that antimicrobial effects of ZnO NPs. In some
studies, emissions of Zn2+ from nanocomposites
cause to death of microorganisms, [48], [49], [50]. It
is important to note that the solubility of ZnO is very
low.
Carbon nanotubes (CNT) were used for remediate
the pollutants. CNT structure and its electro
equations can be changed quickly by doping of some
metals to its surface, [21]. CNT was effectively used
since is elastic and has some mechanical, and
electrical structures ending with hydrogen
production, drug transportation and treatment of
polluted ecosystems. CNT can be utilized to energy
storage with high electrolyte properties, and
equilibrium. CNT exhibits excessive surface, fast
reaction kinetic and degradation of pollutants like
Pb2+, Cu2+, Cd2+, and, dyes, [19], [23]. CNT have also
been utilized for treatment of pollutants with perfect
structure, conductive, and chemical structures, [11],
[16], [24]. CNTs have a mesoporous structure and
provides effective adsorption, [9], [15], [25].
In this study, the photodegradation of ZnO was
improved by connecting Fe, Mg and C nanoparticles
on the its structure, and the photodegradation
capacity of ZnO/Fe/Mg/C nanocomposite was
examined to produce H2 from polyester polyurethane
and polyethylene microplastics. The effect of time,
temperature and nanocomposite concentrations on H2
yields were studied for polyester polyurethane, and
polyethylene microplastics.
2 Materials and Methods
2.1 Production of ZnO/Fe/Mg/C
Nanocomposite
ZnO particles were produced from Zn(NO3)2.6H2O
and NaOH was added to adjust the pH. 5.990 g of
Zn(NO3)2.6H2O was mixed with 100 ml distilled
water. The temperature was elevated and at a
temperature of 70oC, 1 ml of 4 M NaOH was added
up to the mixture pH was become 10.0. After 2 h
mixing a precipitate was found. This section was
separated by a centrifuge. The filtered precipitate was
dried at 90oC for 10 h. The temperature was adjusted
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to 500oC for 2 h in an incubator. Then 10 g
ZnO(NO3)2.4H2O was mixed in 200 ml of water. 1 ml
of 6 M NaOH (6 M) was added to reach a pH of 9.0.
To produce the ZnO/Fe2+ (30%) nanocomposite,
0.600 g ZnO was added. 0.420 g Fe(NO3)3.9H2O was
dissolved mixed in 20 ml water. The produced
mixture was added to an autoclave at 190oC for 28 h.
The settled mass was dried.
MgO was produced by addition of
Mg(NO3)2.6H2O as Mg2+ addition, and settled by
using NaOH, [29]. For MgO production, 0.32 M
Mg(NO3)2 was added to 150 ml of distilled.
Afterwards, 1 ml 2M NaOH solution was added to
Mg(NO3)2 to reach a pH of 9.0. The settling of
Mg(OH)2 was performed. The produced precipitate
was centrifuged and dried in an incubator at 140oC
for 6 h. Then, the powder was calcined at 700oC for
7 h in an oven. The produced nanocomposite was
ZnO/Fe/Mg/C nanocomposite.
2.2 Detection of Polyethylene and Polyester
Polyurethane in GC-MS
600 mg of liquids were autoclaved at 141oC for 30
min. The samples were centrifuged at 8000 rpm for
10 min at 4oC. Then the liquids were maintained at
−25oC while the suspension was withdrawn. The pH
was adjusted to 2.0 after 2 h. Then extracted with the
passage of N2 gas to a volume of 70 µl. The liquids
were extracted with N,O-bis(trimethylsilyl)trifluoro
acetamide before measurements in an Agilent 6890
model gas chromatography (GC) coupled with an
Agilent model 5973 mass spectrometer (MS), in an
GC-MS. The samples were separated on HP-5ms
capillary column (40 m x 0.30 mm diameter x 0.35
µm film). The temperature was adjusted as follows:
the initial temperature of 90oC for 5 min and then at
a temperature of 10oC up to 230oC.
2.3 Measurement of the Photodegradation
Yield of the ZnO/Fe/Mg/C Nanocomposite
Photocatalytic degradation of catalysts was
performed in 250 mg/l liquids. About 5 mg of
ZnO/Fe/Mg/C nanocomposite was dissolved in
70 ml of deionized water. The microplastic
photodegradations were performed in an GC-MS as
aforementioned.
3 Results and Discussions
3.1 XRD Analysis Results of ZnO/Fe/Mg/C
Nanocomposite
The first two and third specimen diffraction line
profiles are determined from 2θ = 2o to 2θ = 100o.
The created lattice planes of ZnO/Fe/Mg/C
nanocomposite samples are indicated as (100), (002),
(101), (102), (110), (103), (200), (112) and (004)
(Fig. 1). These 2θ values were measured as 31.62o,
34.38o, 36.11o, 56.32o, 62.61o, 65.06o, 68.06o and
72.52o, respectively (Fig. 1). These planes are
consistent with the standard spectra of the hexagonal
phase of wurtzite-type ZnO with space group P63mc,
defined by interpretation of the resulting PDF
number 5-664. The diffraction peaks of the
ZnO/Fe/Mg/C nanocomposite sample are of medium
height and appear to be single peaks originating from
the sample. Moreover, it is stated in the studies in the
literature that no other peak from other crystalline
phases provides the crystallinity conformation of
ZnO, [26], [27], [51], [52], [53], [54].
* Fig. 1 can be found in the Appendix section.
XRD patterns of Fe-doped samples containing 2%
and 4% Fe, ZnO/Fe/Mg/C nanocomposite a and
ZnO/Fe/Mg/C nanocomposite b, showed
corresponding diffraction peaks for another phase
with ZnO crystallites without any peaks.
Additionally, biomimetic production of ZnO using
egg white and doping of various concentrations of
iron oxide (Fe2O3) appeared to cause changes in all
diffraction peaks and the height of both. 2% Fe2O3
doping brought about a decrease in the peak height in
crystallites. The opposite behaviour was noticed in
the case of the sample treated with 4 mol% Fe2O3. 2
mol% Fe2O3 Surface-doped ZnO/C system led to a
gradual decrease in the crystallite size of ZnO,
followed by an increase in strain and dislocation
density. In the case of doping using 5 mol% Fe2O3,
the opposite effect was observed. In general, doping
the studied system with 2 or 5 mol% Fe2O3 caused a
shift of one atom to its neighbour and an increase in
the lattice constants.
3.2 FTIR Analysis Results of ZnO/Fe/Mg/C
Nanocomposite
Fig. 2 shows the FTIR spectra of the components
present in the nanocomposite. The metal-oxygen
release mode corresponds to the absorption bands
within 850 and 390 cm−1 as shown in the FTIR
spectrum.
* Fig. 2 can be found in the Appendix section.
The weak bands at 610, 682 and 779 cm−1 related
to the Zn–OH group, whereas the characteristic broad
band at 399 cm−1 is attributed to metal–oxide
stretching vibrations of the Zn-O bond, [26], [27].
Vibrational modes of carbon groupings, together
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with Mg and Fe, may be responsible for the bands at
1090 and 1480 cm−1. Due to the capping agent in egg
white, these bands are attributed to C–H, C–O and C–
OH vibrations with the aforementioned metals, [26],
[27], [28]. The strong bands at 1640 and 5000 cm−1
are due to the stretching vibrations of O–H bonds
with C, indicating the presence of the aforementioned
metal during the preparation of the nanocomposite
pellet, [29], [51]. As can be observed from the FTIR
spectra, the addition of iron ions during doping
caused a modest repositioning of every absorption
band and a subsequent alteration in their intensities.
3.3 Raman Analysis Results of ZnO/Fe/Mg/C
Nanocomposite
With Raman spectra, the vibrational properties of
three separate samples materials are investigated.
Fig. 3 displays the Raman spectra of the examined
materials between 0 and 5000 cm−1 at room
temperature. The Raman spectra of the
ZnO/Fe/Mg/C nanocomposite a, and ZnO/Fe/Mg/C
nanocomposite b samples did not reveal the
distinctive vibrational modes connected to ZnO
crystals. However, these spectra show two large
peaks in the G and D bands at 1499 cm−1 and 2199
cm−1, respectively.
* Fig. 3 can be found in the Appendix section.
Typical carbon compounds exhibiting these bands
showed distinctive features, [55]. Indeed, the
appearance of the G-band at 1499 cm−1 is a
significant characteristic of sp2 hybridized carbon
materials. This band can provide specific points in
the in-plane vibration of sp2 bonded carbon regions,
[56]. On the other hand, the D-band occurs at 2199
cm−1 indicates the existence of sp3 defects or
abnormalities inside the hexagonal graphitic
structure, [33]. Additionally, the edges of this band
may violate the symmetry and selection criteria, and
may consist of amorphous carbon and hexagonal
graphite structure, or a combination of these, [35],
[53]. The crystallite shape of Fe with nanocomposites
exhibiting Mg and Fe and is proportional to the
relationship (ID/IG) corresponding to the intensities of
these bands, confirming the formation of crystallized
carbon.
It has been stated that increasing the dopant
content in ZnO/Fe/Mg/C nanocomposite b causes an
increase in the formation of amorphous carbon due to
the severe weakness in the intensities of the G and D
bands, [23], [26], [27], [57]. This finding indicates
that the standard error of the carbon material
decreases.
3.4 SEM Analysis Results of ZnO/Fe/Mg/C
Nanocomposite
The SEM analysis is conducted to study the
morphology of the biosynthesized pure and Fe-Mg
doped ZnO/C nanoparticles (Fig. 4).
* Fig. 4 can be found in the Appendix section.
SEM images showed that the shape and size of the
display fragile and porous flakes containing spherical
nanosized particles with the formation of various
voids in ZnO/Fe/Mg/C nanocomposite a, (Fig. 4a). In
other words, the as-synthesized materials are easily
broken or destroyed and also are easily crumbled.
The carbon-Mg-Fe containing zinc particle size
reduced via excess carbon and Fe in the
ZnO/Fe/Mg/C nanocomposite b since it was a
capping agent in the nanoparticles (Fig. 4b).
3.5 EDS Analysis Results of ZnO/Fe/Mg/C
Nanocomposite
Table 1 describes the less fragmentation structure of
the nanocomposite. As the surface area of the
nanocomposite decreased, while the percentage of
ZnO decreased to 3%. Under these conditions a slight
decrease in the pores and voids sizes was detected
due to the agglomeration of smaller nanoparticles,
especially, in the ZnO/Fe/Mg/C nanocomposite b.
This nanocomposite contains high amounts of Fe
additives. This is demonstrated by the presence of the
lowest surface area in the above-mentioned
nanocomposite, [23], [26], [27], [57].
* Table 1 can be found in the Appendix section.
The EDS pattern of ZnO/Fe/Mg/C nanocomposite
a, elementally, respectively; It shows the presence of
Zn (28.39 wt%), O (13.60 wt%), C (26.74 wt%), Fe
(12.67 wt%) and Mg (11.67 wt%) (Table 2).
* Table 2 can be found in the Appendix section.
The EDS patterns of ZnO/Fe/Mg/C
nanocomposite b showed the elemental content of
these samples, respectively: Zn (25.00wt%), Fe
(20.01 wt% and 5.36 wt%), Mg (8.99 wt%), O (4.32
wt%) and C (10.06 wt%). All of these
nanocomposites; It consists of the elements Zn, Fe,
O, C and Mg.
3.6 TEM Analysis Results of ZnO/Fe/Mg/C
Nanocomposite
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The results of the TEM analysis confirm that both
nanocomposite samples were encapsulated in
graphitic carbon layers (Fig. 5).
* Fig. 5 can be found in the Appendix section.
In the ZnO/Fe/Mg/C nanocomposite an exhibited
better dispersion, depending on a decrease in the
agglomeration formation rate of the nanocomposite
(Fig. 5a). While the average diameter of
ZnO/Fe/Mg/C nanocomposite a was measured as 8.3
nm (Fig. 5a), ZnO/Fe/Mg/C nanocomposite b
exhibited an increase in the agglomeration process,
with a size diameter of 5.9 nm (Fig. 5b).
3.7 The Selected Area Electron Diffraction
(SAED) Patterns of ZnO/Fe/Mg/C
Nanocomposite
In Fig. 6a, Fig. 6b, and Fig. 6c, various bright spots
were observed within the concentric rings, indicating
the polycrystalline structure of pure and Fe-doped
ZnO/C/Mg nanoparticles.
* Fig. 6 can be found in the Appendix section.
The Fe-doped ZnO/C/Mg nanoparticles b,
demonstrated maximum intensity of these bright
spots diminishes. In addition, increasing the Fe
dopant content exhibited an increase in the number of
concentric rings. These originated from the Fe-doped
ZnO/C/Mg nanoparticles b size reduction, with the
self-aggregation of some bulk layers, [58], [59], [60],
[61].
3.8 H2 Productions from 250 mg/l Polyester
Polyurethane, and 250 mg/l Polyethylene via
3 mg/l ZnO/Fe/Mg/C Nanocomposite after 10
min Irradiation under 60 W/m2 UV
The hydrolysis reaction of polyester polyurethane
and polyethylene to H2 was carried out within a 36-
hour reaction time using Fe-doped samples
containing 2% ZnO/Fe/Mg/C nanocomposite a and
4% ZnO/Fe/Mg/C nanocomposite b. The H2
productions were 7800 ml/h and 5600 ml/h,
respectively for polyester polyurethane while the H2
productions were measured as 9800 ml/h and 8700
ml/h for polyethylene reduction at 125oC (Table 3).
* Table 3 can be found in the Appendix section.
The H2 productions were extremely high since
polyethylene carbon bonds were lower than that of
polyester polyurethane, [59], [60], [61].
ZnO/Fe/Mg/C nanocomposite a, with a Fe content of
2%, exhibited higher H2 production than the other.
Microplastic yields at low temperatures were 100%
at 130oC and 54% yield at 110oC (Table 3).
The hydrolysis ratio of the polyethylene was
found to be higher since was readily degraded to H2.
However, polyester polyurethane showed ineffective
depolymerisations and small amounts of
polyurethane oligomers were observed. High
hydrolysis rate of water-soluble polyethylene ending
with high H2 productions. When polyester
polyurethane conversion is not completed; A
metabolite residue was recovered, indicating that
polyester polyurethane polymers consist of a
metabolite with a lower molecular weight. After use,
the ZnO/Fe/Mg/C nanocomposite catalyst can be
easily recovered by centrifugation, and reused in
other catalytic experiments under the same
conditions; this shows a slight decrease in H2
production of 3% (data not shown), [47], [60], [61],
[62], [63].
3.9 Effect of Nanocomposite Concentration on
H2 Productions in 250 mg/l Polyester
Polyurethane and Polyethylene Microplastics
after 10 min Irradiation under 60 W/m2 UV
The effects of increasing ZnO/Fe/Mg/C
nanocomposite a, catalyst concentration from 1, 3, 5,
7 and to 10 mg/l was detected on H2 productions in
both microplastics (Table 4).
* Table 4 can be found in the Appendix section.
The maximum degradation capacity of 250 mg/l
polyester polyurethane was 89% while the
degradation yield was 99% at 250 mg/l polyethylene
concentration at 3 mg/l ZnO/Fe/Mg/C
nanocomposite a with a Fe ratio of 2% (Table 4).
Then, the degradation yields of both microplastics
dropped slightly from 99% to 94% and from 89% to
80% at 7.0 mg/l nanocomposite concentrations, for
polyethylene and polyester polyurethane
microplastics. This may be because, at low
nanocomposite dosages, nanocomposite sites are
more exposed to microplastics and degradation has
occurred more rapidly. On the other hand, there is
additional numbers of unoccupied nanocomposite
sites at higher nanocomposite concentrations, which
reduces the photodegradation capacity.
3.10 Effect of Time on H2 Productions in 250
mg/l Polyester Polyurethane and Polyethylene
Microplastics via 3 mg/l ZnO/Fe/Mg/C
Nanocomposite a
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The effects of contacting time (3–30 min) on the
photocatalytic degradation of both microplastics to
H2 were studied. The results showed that the
degradation efficiencies of polyester polyurethane
and polyethylene microplastics increase readily with
increasing irradiation time interval from 3 min up to
6 mins. At the beginning the microplastic
concentration is more for degradation which later
decreased with time (Table 5).
* Table 5 can be found in the Appendix section.
This also may be because initially large number of
metal radicals present in the solution and they were
attacked on microplastic molecules with the time.
When the metal radicals lowered, the speed of
degradation process may also decrease. The
percentage of degradation efficiency for polyester
polyurethane and polyethylene microplastics were
88% and 99% after 4 min and 6 min, respectively.
The degradation efficiency increased sharply at the
beginning while the degradation rate of increases
very rapidly up to 10 min in polyester polyurethane,
and then the degradation rate decreases slightly after
the optimum time. The maximum degradation time
of polyethylene was detected after 4 min
photodegradation then the yields decreased after 5
min.
3.11 Effect of Temperature on H2 Production
from Polyester Polyurethane and
Polyethylene Microplastics via 3 mg/l
ZnO/Fe/Mg/C Nanocomposite a
The effect of temperature on the thermal degradation
rates of polymers has been extensively explored
because of the need to predict the service lifetime of
consumer plastics. In some studies, it was found that
the results are consistent with an Arrhenius
relationship, [14], [20], but other studies have found
non-Arrhenius behavior, [21], [22], [23]. There is
some indication that the non-Arrhenius behavior is
due to the complex degradation pathways referred to
above, and therefore the relatively straightforward
degradation process in polymers with metal–metal
bonds might provide some fundamental insights that
are not obtainable with standard carbon-chain
polymers.
The temperature dependence of the quantum yields
for the degradation of polymer could depend on: (1)
the inherent temperature dependence of the
photolysis and radical trapping reaction of the
ZnO/Fe/Mg/C nanocomposite a, (2) the temperature
dependent behaviour of the polymer morphology, or
(3) a temperature-dependent dynamical property of
the photogenerated radicals in the polymer. There is
a significant increase in the quantum yields for
polyester polyurethane with increasing temperature.
In contrast, for polyethylene dispersed with Mg–Fe-
ZnO chromophores are unattached to the polymer
chains there are only slight increases the quantum
yields over this temperature range, [23], [26], [27],
[47], [57], [58], [59], [60], [61], [62], [63]. Big
increase in the quantum yield with temperature for
polyester polyurethane is not attributable to an
inherent temperature dependence of the photolysis
and subsequent radical trapping reaction of the
nanocomposite (Table 6).
* Table 6 can be found in the Appendix section.
Since the quantum yields for polyethylene
dispersed show only a slight temperature
dependence, the temperature dependence observed
for polyester polyurethane. The maximum H2
production rates were detected at a temperature of
125oC with H2 yields of 99% and 88% for
polyethylene and polyester polyurethane
microplastics, respectively. Like higher temperatures
like 150oC and 175oC did not improve the H2 yields.
4 Conclusions
H2 production was examined by producing
ZnO/Fe/Mg/C, a new nanocomposite from polyester
polyurethane and polyethylene microplastics. The
potential for converting plastic wastes to H2 was
studied in this study as fuel. Physicochemical
analyses were performed to determine ZnO/Fe/Mg/C
nanocomposite a, and ZnO/Fe/Mg/C nanocomposite
b containing 2% and 4% Fe ratios.
Raman analyses showed that the G band at 1499
cm−1 is an important feature of sp2 hybridized carbon
materials. The D-band occurs at 2199 cm−1, and
indicates the presence of sp3 defects or abnormalities
within the hexagonal graphite structure. The
crystallite shape of Fe with nanocomposites
exhibiting Mg, ZnO and C, and is proportional to the
relationship (ID/IG) corresponding to the intensities of
these bands, confirming the formation of crystallized
carbon.
The selected area electron diffraction (SAED)
results of the ZnO/Fe/Mg/C nanocomposite exhibited
bright spots inside concentric rings, indicating the
polycrystalline nature of the Fe-doped ZnO/C/Mg
nanocomposites a. The 4% Fe-doped ZnO/C/Mg
nanocomposites b, demonstrated maximum intensity
of these bright spots. Elevated high Fe dopant content
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E-ISSN: 2945-0454
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exhibited an increase in the number of concentric
rings resulting in size reduction.
Selected area electron diffraction (SAED) results
of ZnO/Fe/Mg/C nanocomposite a exhibited bright
spots within concentric rings; This case is based on
Fe-doped ZnO/C/Mg nanocomposite a; It shows
polycrystalline nature. ZnO/C/Mg nanocomposite b,
containing 4% Fe exhibited an increase in the number
of concentric rings, leading to size reduction.
The XRD analysis showed that lattice planes of
ZnO/Mg/C/Fe nanocomposite were distributed as
(100), (002), (101), (102), (110), (103), (200), (112)
and (004).
According to FTIR analysis, the weak bands at
610, 682 and 779 cm-1 are related to the Zn-OH
group, while the characteristic broad band at 399 cm-
1 is; It was observed that metal-Zn-O with Mg and C
bonds had oxide stretching vibrations.
Additionally, the effects of some operating
conditions (time, nanocomposite concentration,
temperature) on H2 production from both
micropollutants were investigated. The maximum H2
production was detected at 250 mg/l polyethylene
microplastic as 9800 ml/h with ZnO/Fe/Mg/C
nanocomposite a, containing 2% Fe while the H2
production was detected as 7800 ml/h from polyester
polyurethane with the same nanocomposite.
Optimum operating conditions; maximum H2
production efficiencies of 99% polyethylene and
88% polyester polyurethane were achieved at 3 mg/l
ZnO/Fe/Mg/C nanocomposite a, concentration, at 3
min and at 5 min experimental times and at 125oC
temperature, respectively.
Acknowledgement:
Experimental analyzes in this study were performed
at the Laboratories of the Canada Research Center,
Ottawa, Canada. The authors would like to thank this
body for providing financial support.
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Contribution of Individual Authors to the
Creation of a Scientific Article (Ghostwriting
Policy)
Prof. Dr. Delia Teresa Sponza and Post-Dr. Rukiye
Öztekin took an active role in every stage of the
preparation of this article.
The authors equally contributed in the present
research, at all stages from the formulation of the
problem to the final findings and solution.
Sources of Funding for Research Presented in a
Scientific Article or Scientific Article Itself
This research study was undertaken in the
Environmental Microbiology Laboratories at Dokuz
Eylül University Engineering Faculty Environmental
Engineering Department, İzmir, Turkey. The authors
would like to thank this body for providing financial
support.
Conflict of Interest
The authors have no conflicts of interest to declare
that are relevant to the content of this article.
Creative Commons Attribution License 4.0
(Attribution 4.0 International, CC BY 4.0)
This article is published under the terms of the
Creative Commons Attribution License 4.0
https://creativecommons.org/licenses/by/4.0/deed.en
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APPENDIX
Fig. 1. XRD spectra of ZnO/Fe/Mg/C nanocomposite
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Fig. 2. FTIR spectra of ZnO/Fe/Mg/C nanocomposite
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Fig. 3. Vibrational Raman spectra of ZnO/Fe/Mg/C nanocomposite
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Fig. 4. SEM analysis results in ZnO/Fe/Mg/C nanocomposite a (a) and ZnO/Fe/Mg/C nanocomposite b (b) (SEM
images size: 50 nm).
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Table 1. Energy dispersive spectroscopy of the ZnO/Fe/Mg/C nanocomposite
Raman Shifts (cm-1)
Intensity (counts)
ZnO/Fe/Mg/C Nanocomposite a
ZnO/Fe/Mg/C Nanocomposite b
500
900
625
1000
1450
1250
1500
1875
1725
2000
1625
1375
2500
1975
1600
3000
2000
1740
3500
2000
1740
4000
2000
1740
4500
2000
1740
5000
2000
1740
Table 2. Elements of ZnO/Fe/Mg/C nanocomposite a, and ZnO/Fe/Mg/C nanocomposite b
Elements (wt%)
Names of Nanocomposite
ZnO/Fe/Mg/C Nanocomposite a
ZnO/Fe/Mg/C Nanocomposite b
Zn
28.39
25.00
C
26.74
10.06
Fe
12.67
20.01
Mg
11.67
8.99
O
13.60
4.32
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(a)
(b)
Fig. 5. TEM images of the ZnO/Fe/Mg/C nanocomposite a (a) and ZnO/Fe/Mg/C nanocomposite b (b)
(TEM images size: 100 nm).
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(a)
(b)
(c)
Fig. 6. SAED patterns of the ZnO/Mg/C nanocomposite a (a), Fe-doped ZnO/C/Mg b (b) and ZnO/Fe/Mg/C (c)
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Table 3. H2 productions from polyester polyurethane, polyethylene via ZnO-Mg-Ni-Fe-C nanocomposite a and
ZnO-Mg-Ni-Fe-C nanocomposite b
Microplastic Names
Name of Nanocomposite and H2 Production (ml/h)
ZnO/Fe/Mg/C Nanocomposite
a
ZnO/Fe/Mg/C nanocomposite
b
Polyester polyurethane
7800
5600
Polyethylene
9800
8700
Table 4. Effect of ZnO/Fe/Mg/C nanocomposite a, concentration on H2 productions in 250 mg/l polyester
polyurethane and polyethylene microplastic concentrations
Nanocomposite
Microplastic Names and Yields
ZnO/Fe/Mg/C nanocomposite
a, Concentration (mg/l)
Photodegradation Yield of
Polyethylene (%)
Photodegradation Yield of
Polyester Polyurethane (%)
1
67
59
3
99
89
5
98
88
7
94
80
10
89
70
Table 5. Effect of time on H2 productions in the presence of polyester polyurethane and polyethylene
microplastics via 3 mg/l ZnO/Fe/Mg/C nanocomposite a
Time
Microplastic Type and H2 Yield Percentage (%)
Polyethylene
Polyester Polyurethane
3
92
67
4
99
77
5
98
82
6
98
88
8
97
88
10
97
87
15
97
86
30
97
85
International Journal of Applied Sciences & Development
DOI: 10.37394/232029.2024.3.9
Deli
a Teresa Sponza, Ruki
ye Özteki
n
E-ISSN: 2945-0454
114
Volume 3, 2024
Table 6. Effect of temperature increase on H2 production yields of polyethylene and polyester polyurethane
Temperature (oC)
H2 Production Yield (%) from
Polyethylene
H2 Production Yield (%) from
Polyester Polyurethane
35
97
60
70
98
70
90
99
80
125
99
88
150
99
88
175
99
99
International Journal of Applied Sciences & Development
DOI: 10.37394/232029.2024.3.9
Deli
a Teresa Sponza, Ruki
ye Özteki
n
E-ISSN: 2945-0454
115
Volume 3, 2024