Journal of Polymers and the Environment

https://doi.org/10.1007/s10924-023-02995-8

ORIGINAL PAPER

Recovery and Characterization of Nano‑Ag‑graphene‑TiO2: Active

Compound from Polylactic Acid (PLA)‑Based Film
Anca Peter1 · Leonard Mihaly Cozmuta1 · Camelia Nicula1 · Anca Mihaly Cozmuta1 · Goran Drazic2 · Antonio Peñas3 ·
Stefania Silvi4

Accepted: 5 July 2023

© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2023

Abstract
The recover of the used Ag-graphene-TiO2 composite extracted from the polylactic acid (PLA) film and its characterization
in comparison with the newly prepared composite was the aim of this study. The proposed recovery procedure will reduce
the amount of inorganic nanostructured material released into the environment as used food packaging. Morpho-structural,
environmental and photocatalytical characteristics of Ag-graphene-TiO2 composite recovered from an used PLA-based film
in comparison with those of the new prepared composite are reported. The recovered Ag-graphene-TiO2 composite displayed
color, consistence, appearance, homogeneity and dispersion of nano-Ag similar with the new prepared compound. The FTIR
spectroscopy showed the presence of Ti–O–C bonds suggesting the cross-linking between ­TiO2 and graphene both in new
and recovered composite. The gap energy (Eg) of the recovered composite is 1.4 times and 2.3 times lower than that of new
composite and T ­ iO2, respectively. The anatase`s content decreased by 70% during the recovering, while that of rutile rised
with the same magnitude. The photocatalytic activity of the recovered composite decreased only by 30% in comparison with
the new composite. Additionally, the Life-Cycle Analysis (LCA) showed that the recovering procedure had a considerably
lower environmental impact than the preparation of the new composite in terms of human health, ecosystem quality, climate
change and resources. In conclusion, the recovering of the nanostructed composites from the active PLA-based films should
be promising way to imporve the waste management.

Keywords Recovery · Ag-graphene-TiO2 · Morpho-structure · Photoactivity · Environmental impact

Introduction dioxide, alumina, etc.), metals and carbon-based materials

The economy and industry development has generated pol-
lutants of various types and in considerable quantities [1].
Due to the wide applicability of inorganic nanoparticles,
such as metal oxides (iron oxide, copper oxide, titanium
[10–12, 24, 25] in the various domains such as electrochemi-
cal senosors [11] or photocatalysis [10, 12], the probability
of unintended exposure of researchers, workers and popu-
lation, in general, to these substances increases. The main

* Anca Peter Stefania Silvi

peterancaluca@yahoo.com stefania.silvi@unicam.it
Leonard Mihaly Cozmuta 1
Faculty of Sciences, Technical University of Cluj Napoca,
mihalyleonard@yahoo.com
Victoriei 76, 430072 Baia Mare, Romania
Camelia Nicula 2
National Institute of Chemistry, Hajdrihova 19, POBox 660,
vargacamelia@yahoo.com
1001 Ljubljana, Slovenia
Anca Mihaly Cozmuta 3
Andaltec Pol. Ind. Cañada de la Fuente, Calle Vílches s/n,
mihaelamihalycozmuta@gmail.com
23600 Martos‑Jaén, Spain
Goran Drazic 4
Scuola di Bioscienze e Medicina Veterinaria, University
goran.drazic@gmail.com
of Camerino, Via Gentile III da Varano, 62032 Camerino,
Antonio Peñas MC, Italy
apenas@ujaen.es

13
Vol.:(0123456789)

routes of exposure are inhalation, skin contact and ingestion
[2].
The materials exert a double impact on health during
preparation and handling and on the environment after their
use. Therefore, their recovery after use would be a solution
to reduce the environmental impact and toxicity. Reuse and
recovery methods are significantly more environmentally
friendly in comparison with the synthesis routes and the
working procedures involving these composites [2].
TiO2-based nanomaterials are some of the most widely
used photocatalysts, due to the ease of generating, under
UV action, of charge carriers, electrons and holes, which
combines with oxygen and water, producing highly reactive
superoxide and hydroxyl radicals. These powerful oxidants
are used to degrade organic molecules fixed on the ­TiO2
nanostructures`surface. In addition, the deposition of noble
metal nanoparticles [3], as well as graphene [3] on ­TiO2,
it is an effective way to enhance its photocatalytic activity.
The precursors used to prepare these types of composites
based on silver, titanium dioxide and graphene are relatively
toxic and have an impact on the researcher`s or worker`s
health. Also, the release of these composites into the envi-
ronment after use has an impact on soil, water and air. Thus,
the possibility of recovery and reuse of the photocatalyst
after use would have the following beneficial effects, by
reducing: (a) the health risks caused by handling reagents,
(b) the costs of composite synthesis, (c) the environmental
impact due to the amount of waste after use, (d) the global
warming effect associated to cabon dioxide and methane
emmisions, (e) the use of non-renewable energy, (f) the
use of mineral extraction sources, and g) the land occupa-
tion (mineral extraction sites, dump site, road network, roal
embakment, etc.). Moreover, the materials, even when they
are made of inert elements like gold, become very active at
the nanometer range [4, 5]. Of course, the possibility and
ease of recovery depends on the material in which the com-
posite is incorporated or the process in which it is involved.
For example, the composite can be recovered relatively eas-
ily by calcination if it has been incorporated into the organic
matrix such as a biodegradable organic film (polylactic acid,
polycaprolactone, polyvinyl alcohol) [6].
Gayathri Menon et al. [7] have tested the capacity to reuse
the ­TiO2–ZnO composite used as photocatalyst, during the
estrogens removal from water. The results showed that the
nanocomposites kept their photoactivity without loss in effi-
cacy even after 3 cycles of reuse under visible irradiation.
Huang et al. [1] have tested the photoactivity and reuse
possibility of T ­ iO2/carbon-clay and established that this
composite presented good durability explained by the pres-
ervation of the dye removal percent even after 5 cycles reuse.
Liu et al. [5] have prepared ­AlCl3 and ­TiO2 flocs with
high photoactivity in the methyl orange (MO) removal
under UV light, as a result of the oxygen vacancies from the
13
Journal of Polymers and the Environment
catalyst`s surface. Moreover, the obtained flocs displayed
good recyclability and no sacrificial reagent was used.
Gupta et al. [10] have successfully obtained reduced
graphene oxide designed for the electrochemical sensing of
dopamine by cyclic voltammetry. The obtained electrodes
showed good electrocatalytic activity for the oxidation of
dopamine. They succeeded to determine the concentration
of dopamine in the range of 0.5 μM to 20 μM with a detec-
tion limit of 1.11 μM.
Wang et al. [11] have showed that the ternary nanocom-
posite CdSH/ZnO-graphene, designed for the photoelec-
trochemical selective sensing of C ­ u2+, exhibited enhanced
photoelectrical activity with a photocurrent density of
6.8 mA·cm−2 under illumination at 0.5 V vs. SCE. In this
way, they could expand the research for the successfully
detection of C ­ u2+ in real industrial waste water and sea
water.
Harrum et al. [12] have synthetized a highly dense nano-
sized ­TiO2–ZnO-graphene thin film via solution immer-
sion method, used as efficient photocatalyst in treating the
wastewater.
Life cycle assessment (LCA) investigates the materials
impact over the environment and human health. The nano-
sized materials`toxicity has been intensively studied, tak-
ing in consideration the mechanisms of dust overloading in
lungs and phagocytosis.
The chemicals and derivatives products for which no
other specific regulation exists are subject to the Regula-
tion EC No 1907/2006 concerning the Registration, Evalu-
ation, Authorization and Restriction of Chemicals (REACH)
(EC 2006). ­SiO2 or ­TiO2 used as coatings or composites are
included in this category. The European Chemicals Agency
(ECHA) published the guide including physical–chemi-
cal properties, toxicology, toxicological-kinetic and safety
assessments. The use of a nanomaterial as active compound
from a biocidal substance must be approved according to a
nano-specific risk assessment (EC 2012).
Inhalation, oral toxicity, aggregation, dispersion and
delivery of nanomaterials are major factors affecting the
environment. Nanomaterials may induce strong effects at
low dose, as a result of their agglomeration capacity. Some
nanomaterials exhibit intrinsic photocatalytic activity and
significant toxicity when appropriate light wavelengths are
used [8].
With this background, it is clear that when a new additive
is intended to be included in food packaging for consump-
tion, it is necessary to carry out several studies. In this case,
a preliminary study is carried out, from the ecotoxicity point
of view.
This study aims to establish whether there are signifi-
cantly differences between the newly prepared Ag-TiO2-gra-
phene composite and the same composite recovered from a
polylactic acid-based film designed for food packaging, in
Journal of Polymers and the Environment
terms of morpho-structure, photoactivity and environmental
impact. The study is important because, its results may be
helpful for the reducing of: (i) wastes, (ii) costs and toxicity
of raw materials necessary for the composite`s preparation,
(iii) toxicity from exposure of the worker during the prepara-
tion of the compound, (iv) allows the composite`s recovery
and recycling.
The originality of the study consists in the fact that
reports aspect that are not founded in the other literature
data, namely: recovery of a nanostructured material from a
biomaterial and including it in a new biomaterial; charac-
terization of the recovered nanostructured material in com-
parison with the new one; comparison the preservative role
as package for curd cheese between the recovered and the
new film.
Materials and Methods
Materials
Titanium tetraisopropoxide (Ti(OC3H7)) (99.9999% purity),
nitric acid ­(HNO3) (99.9999% purity) and potassium bro-
mide (KBr) (spectral quality) were purchased from Merck
(Darmstadt, Germany). Anhydrous ethanol ­(C 2H 5OH)
(> 99.5% purity), silver nitrate ­(AgNO3) (99.9999% purity)
and salicylic acid (99.5% purity) were purchased from
Chemical Company (Iasi, Romania). Ultrapure water (­ H2O)
was prepared by using the Barnstead Thermo Scientific
(USA) device. Graphene powder was GP500 Graphene Nan-
oplatelets from Graphenetech (Zaragoza, Spain). Polylactic
acid (PLA) Ingeo™ Biopolymer 4043D has been supplied
from NordiTech (Minessota, USA).
Synthesis of Ag‑TiO2‑graphene Composite
A volume of 5 mL Ti(OC 3H 7) was homogenized with
20.66 mL ­C2H5OH, 1.08 mL ultrapure H ­ 2O and 0.09 mL
­HNO3 63 wt% solution, under magnetically stirring. The
obtained sol was mixed with 0.02 g graphene powder before
gelification. The obtained gel was allowed to age 4 weeks.
Then the 20 g black gel was introduced in 50 mL A ­ gNO3
0.015 M solution for 24 h. Then, the remained liquid was
removed and the resulted gel was dried in air at 60 °C in a
Binder oven. Finnally, the black calcined xerogel was milled
in a Retsch mill at 800 rpm for 2 min.
Obtaining of the Recovered Ag‑graphene‑TiO2‑PLA
Composite
The Ag–TiO 2 -g raphene composite prepared in
Sect. "Materials". was used to develop a modified PLA
film. The content of the composite into the film was 0.5%.
The film was designed to be used as food packaging mate-
rial during the curd storage, under refrigeration. The
detailed procedure of PLA film preparation and activa-
tion with composite is described in our previous study [6].
The composite-PLA film remained after the curd stor-
age was rinsed with distilled water and anhydrous ethanol
and dried and was subjected to composite recovery.
The Ag–TiO2-graphene composite was recovered from
the used Ag–TiO2-graphene-PLA packaging material by
calcination at 550 °C for 4 h, the heating rate being 2 °C/
min. The procedure is summarized in Fig. 1.
Characterization of the Newly Prepared
and the Recovered Composite
The morphology of the samples was evaluated by optical
and electronic microscopy. The macroscopic images were
obtained by using the optical microscope Bresser. The
electronic microscopy consisted in performing the Scan-
ning Transmission Electron Microscopy (STEM) by using
a Jeol ARM 200 CF STEM Cs-corrected system. Addi-
tionally, High-angle annular dark field (HAADF) images
were obtained with 68 mrad inner and 175 mrad outer
semi-angle and the convergence angle of 24 mrads. The
samples were applied directly to the lacey-carbon coated
Ni TEM grid. For the elemental analysis, the STEM sys-
tem was equipped with a Jeol Centurio energy—dispersive
X—ray (EDXS) SDD spectrometer. The operating voltage
was 80 kV. A Gatan Quantum ER Dual EELS system was
used to obtain the EELS spectra and to estimate the sample
thickness.
The structure of the samples was performed by FTIR
spectroscopy and X-ray diffraction analysis. The FTIR
measurement were achieved by using the Perkin Elmer
Spectrum BX FTIR system. The analysis was made on a
pill containing composite (2 wt%) and spectral KBr. The
X-ray diffraction was performed by using the X-Ray Pow-
der Diffractometer Siemens D5000.
The optical analysis was evaluated by recording the
UV–Vis diffuse reflectance spectra, by using the Perkin
Elmer Lambda 35 spectrometer equipped with an integrat-
ing sphere accessory, in the region 200–500 nm. The gap
energy of the composites was calculated from the diffuse
reflectance spectra by using the Kubelka–Munk equation
[9] as an indicator of theirs photoactivity.
The thermal stability was measured by thermo-gravi-
metric analysis (TGA)/differential scanning calorimetry
(DSC) (Mettler-Toledo, STARe system Mettler ther-
mobalance) under a nitrogen atmosphere (50 mL/min).
The samples were analyzed between 0 and 950 °C and the
heating rate was 10 °C/min.
13
 Journal of Polymers and the Environment

a Procedure for newly composite preparaon b Procedure for composite recovering from used PLA-based film
Soluon I Soluon II

~ 10 ml absolute ethanol ~ 10 ml absolute ethanol

(Chemical Company RO) (Chemical Company RO)
- 5 ml tanium tetraisopropoxide - 1 ml ultrapure water from
(Merck) Thermoscienfific BBarnstead
Thermoscienfic arnsteead EEasy Pure RoDi
(consumpon:
n: 0,06 W/g /g final composite)
~ 94 microL HNO3 63% (Merck)
TiO2 sol
0.02 g (~ 20 g) Used modified-PLA
graphene powder (~ 500 g)
(GN)
GN-TiO2 gel + 100 mLL ethanol 96% (Chemical Company R Romania)
(~ 20 g) Melng in air at ~ 250 degrees C
to reduce the volume of the PLAs
GN-TiO2 gel
(~ 20 gg))
aging 3 weeks (no equipment needed) Melted modified PLA
GN-TiO2 aged gel (~ 500g)
(~ 20 g) 25 mL soluon
immersion 24 h in dark AgNO3 (Merck) calcinaon in Nabertherm Controller B180 furnace 4 h at 5500C;
0.015 M temp increasing by 20C/min
GN-TiO2 aged gel immersed in Ag-NO3 consumpon: 14,4 W / 1 g final
al recovered
ed composite
(~ 20 g + 25 mL soluon)
drying in Binder oven 24 h at 600C
Recovered composite
consumpon 28,8 W/ 1 g final composite
xerogel Ag-GN-TiO2 (~ 2.5 g)
(~ 1.4 g)
calcinaon in Nabertherm Controller B180 furnace 2 h at
5000C; temp increasing by 20C/min
consumpon: 14,4 W / 1 g final composite
xerogel Ag-GN-TiO
iO2 thermal treated (Ž)
(~ 1 g)

The procedures are lack of wastes

Fig. 1  Preparation procedures for newly and recovered composites

Photocatalytical Activity
The photocatalytic activity was peformed during the sali-
cylic acid (SA) photodecomposition, according to Peter et al.
[9]. An UV–Vis reactor system equipped with a medium
pressure Hg lamp (150 W) was used. A volume of 400 mL
salicylic acid (SA) 0.1 mM solution was recirculated by
0.875 mL/min. The SA decomposition was assessed by
measuring the intensity of the electronic absorption band at
297 nm. A Perkin Elmer, Lambda 35 Spectrophotometer was
used for spectrophotometric determination of SA concentra-
tion. The mass of composite catalyst was 0.1 g. The working
temperature was of 20–22 °C. The adsorption–desorption
equilibrium was reached (in dark) before the photocatalytic
investigation.
The photodegradation results were fitted on first order
kinetic model:
C0
ln = kapp t
C tory scale point of view. The LCA analysis was performed by
where: C0—SA concentration at 0 min, C—SA concentra-
tion time t, t—the irradiation time (min), kapp—apparent rate
constant ­(min−1) given by the slope of the graph of ln (C0/C)
versus t.
Statistical Analysis
The photocatalytical experiments were performed in tripli-
cates and the results were presented as average. The percent-
age of standard deviation (RSD) was lower than 5%. Statistica
7.0 software (StatSoft, Inc., Tulsa, USA) using via one-way
ANOVA (confidence level as p ≤ 0.05, Tukey’s test) was used
to statistically process the experimental data.
Environmental Impact of the Newly Prepared
and Recovered Composites
For this purpose, Simapro software (V. 8.5.2.0) was used. This
software is widely used in the calculation of life cycle analysis
(LCA) of materials, being able to provide information on the
(1) toxicity. The compounds have been studied from the labora-
considering 1 kg of composite.

13
Journal of Polymers and the Environment

Results and Discussion
Morphology of the Newly and Recovered
Composites
The newly prepared Ag-graphene-TiO2 composite appears
as black and homogeneous powder containing uniform-
sized particles (Fig. 2a). After the recovering, the
remained composite was also a material in the form of a
black powder (Fig. 2b). So, from the macroscopic point of
view, there is no difference between the newly and recov-
ered composite.
Figure 3 illustrates STEM/BF and HAADF images of
the newly and recovered Ag-graphene-TiO2 composites.
The elements with high atomic number (A) appear lighter
in STEM/HAAD images, whereas those with low A value
are dark. The uniform distribution of the Ag nanoparticles
can be also observed in Fig. 3. The STEM/HAADF images
of the newly and recovered Ag-graphene-TiO2 composites
are quite similar. The nanocomposites contain particles
with equiaxed morphology and their clusters appear as
sphere-like morphology. The graphene nanosheets (up to

Fig. 2  Macroscopic view of newly a and recovered b composite (magnification 10X)

Ag 2-5 nm

TiO2
20-50 nm

a b c d

Ag 10 nm
TiO2
80-100 nm

GN

e f g
1 0 0 n m 2 0 n m 2 0 n m

1 0 n m
h

Fig. 3  STEM/BF (a), (b),( e), (f)) and HAADF (c), (d), (g), (h)) micrographs with different magnifications of newly Ag-graphene-TiO2 compos-
ite (a–d) and recovered Ag-graphene-TiO2 composite (e–h)

13

few micrometers) are covered with 20–50 nm sized titanium
dioxide (in crystallographic form of anatase) in the newly
composite (Fig. 3a). The silver nanocrystals (2–5 nm) are
homogeneously distributed over T ­ iO2 surfaces (Figs. 3b–d).
Thus, from micro-structural point of view, the newly pre-
pared Ag-graphene-TiO2 is a homogeneous composite with
uniformly distributed T
­ iO2 anatase crystals and silver nano-
particles. The graphene level is very low in the recovered
composite (Fig. 3e and Table 1). Ag and T ­ iO2 particles
became bigger. The size of the T­ iO2 in the new composite
was 20–50 nm and in the recovered one was 80–100 nm.
The size of nano-Ag in the new composite was 2–5 nm and
is was around 10 nm after recovering.
Elemental Analysis of the Newly and Recovered
Composites
The EDXS mapping of newly and recovered composites
(Fig. 4a, b) revealed the presence of Ti, O and low levels of
C and Ag in the newly and recovered composites. The con-
tent of C in the recovered composite was low, explained by
the graphene transformation during the recovery procedure.
Gupta et al. [10], who investigated the behavior of graphene
oxide annealed at 500 °C and 600 °C, respectively, showed
that a highly organized structure of the interlayer spacing is
obtained as the annealing temperature increases. Wang et al.
[11] showed by XPS investigations, the reduced level of car-
bon in composites based on ZnO and graphene obtained by
annealing at 500 °C. The signals for graphene were absent in
the XRD spectra. The oxygen content in the recovered com-
posite is lower as compared with the newly one (Table 1).
This is due to the second procedure of annealing at 500 °C
occurred during the recovery procedure. It is already known
that the annealing leads to the reducing of the oxygen func-
tional groups [10]. The content of Ti from the recovered
sample was almost unchanged in comparison with that from
the new composite. The amount of silver increased during
calcination from 0.82 ± 0.072 wt% in the newly composite to
13.4 ± 1.1 wt% in the recovered material. This behavior can
be explained probably as a concentration of the recovered
sample, as long as the reduction of the other elements took
place. The reaction mechanism occurred during the recov-
ery procedure is illustrated in Fig. 4c. The new composite
Table 1  Elemental analysis of newly and recovered composites
Element NEWLY RECOVERED
Composition (wt%)
O 50.5 ± 2.2 38.2 ± 2.8
Ti 42.5 ± 2.9 45.3 ± 3.1
C 2.2 ± 0.7 0.95 ± 0.02
Ag 0.82 ± 0.072 13.4 ± 1.1
13
Journal of Polymers and the Environment
is predominantly consisted in anatase ­TiO2 nanoparticles
fixed on graphene sheet and coated with silver nanoparticles.
The anatase ­TiO2 phase turns into rutile and a part from the
graphene phase is carbonized during the recovery.
Structure of the Newly and Recovered Composites
The selected area electron diffraction patterns (SAED), the
X-Ray diffraction patterns and the FTIR spectra of the newly
and recovered composites are shown in Figs. 5, 6, 7.
The spotty SAED ring patterns (Fig. 5) and the FWHM of
the peaks from the XRD patterns (Fig. 6) indicated the pres-
ence of crystallized particles in both newly and recovered
samples. The newly composite consisted anatase as predomi-
nant crystalline phase, but the recovered sample is contain-
ing both anatase and rutile phases. According to the XRD
results (Fig. 6), the newly prepared sample contains crystal-
lized particles highlighted by the strong signal at 25.4° (2
theta) given by the anatase and by the weaker signal at 27.4°
corresponding to the rutile. The anatase phase is predomi-
nant (88 wt%), while the rutile is in a lower percentage (12
wt%), The corresponding signal of Ag is difficult to observe
because is superimposed over the anatase`s signals. The
content of graphene in the new prepared Ag-graphene-TiO2
composite is low, so there is no obvious diffraction peak of
graphene in the XRD pattern.
The XRD profiles of the new and recovered composites
are illustrated in Fig. 6. In the XRD pattern of the new com-
posite appears peaks at 2θ 25.3, 31, 37.8, 48.12, 54 and 55
degrees corresponding to anatase planes (101), (112), (020)
and also peaks at 2θ 27.4, 36.1, 41.2, 44 and 54.3 degrees
corresponding to rutile planes (110), (011), (111), (120),
and (121) [12]. The same peaks can be observed in the XRD
profile of the recovered composite. The intensities of the
anatase peaks are high and those of the rutile are low in the
new composite. However, the variation is reverse in the case
of the recovered composite. The crystalline phase of rutile
predominates in the recovered composite. The anatase and
rutile content was 88 wt% and 12 wt% in the new composite
and 29 wt% and 71 wt% in the recovered composite. This is
due to the heat treatment applied to recover the composite
from the active-PLA film. The calcination temperature was
the same as that used to obtain the newly prepared com-
posite, but a second series of heat treatment was applied
for recovery and this procedure led to the transformation
of anatase into rutile [13]. According to Baia et al. [13],
the transformation rutile-to-anatase of the T ­ iO2 begins at
about 360 °C and the reverse anatase-to-rutile transforma-
tion takes place at 600 °C or by increasing the calcination
period at 500 °C.
Small peak corresponding to graphene was found at
22,4 2θ degrees in the XRD pattern of the new composite
and shifted to 24,7 2θ degrees in the XRD profile of the
Journal of Polymers and the Environment

a b
) Ag

TiO
2

Ti
Ti

Ag
O O Ag

c Anatase TiO2
Graphene rule TiO 2
Graphene
Ti
C
Thermal treatment during recovery at
5000C

Ag
O

Fig. 4  a EDXS elemental mapping of newly composite; b EDXS elemental mapping of the recovered composite; c) reaction mechanism occured
during recovery

recovered composite as a result of the annealing during the
recovery.
The FTIR spectra of the newly and recovered composites
­ iO2 are illustrated in
in comparison with that of the pristine T
Fig. 7. Additionally, the description of the signals recorded
as a function of the wavenumber is included in Table 2.
The specific FTIR signals corresponding to the presence
of titanium dioxide can be found at 674 ­cm−1, 1060 ­cm−1,
1390 ­c m −1 , 1620–1720 ­c m −1 , 2900–3000 ­c m −1 and
3400–3750 ­cm−1 [1, 13, 14]. These signals can be observed
in the FTIR spectrum of the newly composite as well as
in that of the recovered sample. The signal at 744 ­cm−1
appeared only in the FTIR spectrum of the recovered com-
posite is assigned by the stretching of Ti–O–C bonds and
shows the presence of the graphene traces cross-linked with
the ­TiO2 matrix. The peak at 1060 ­cm−1 from T­ iO2`s FTIR
spectrum corresponding to the stretching of Ti–O bonds also
appear in those of the composites, but a little bit shifted
to right in the FTIR spectrum of the newly composite and
a bit more shifted to left in that of the recovered sample,

13
 Journal of Polymers and the Environment

Fig. 5  SAED patterns of newly

(line (a)) and recovered com-
posite (line (b)) (a—anatase,
r—rutile)

2000
new recovered 121 - r

1800
110 - r
1600 101 - a

1400

1200
011 - r
intensity

1000
020 - a
800
111 - r r
002 - a a
600 a
112 - a
400
120 - r
graphene a
200

0
20 25 30 35 40 45 50 55 60
2 theta (degrees)

Fig. 6  XRD patterns of newly (a) and recovered (b) composites (a-anatase, r-rutile)

13
Journal of Polymers and the Environment

744 cm-1
transmitance (%)

674 cm-1 1390 cm-1

1620 – 1720 cm-1
2800 – 3000 cm-1
3400-3750 cm-1
1060 cm-1 2352 cm-1

newly recovered TiO2

600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000
wavenumber (cm-1)

Fig. 7  FTIR spectra of the newly and recovered composites in comparison with pristine ­TiO2

Table 2  FTIR signals corresponding to newly prepared and recovered composites

Wavenumber ­(cm−1) Composite TiO2 Description
Newly prepared Recovered

674 ✓ – – Symetrical stretching vibration of Ti–O bond [11]

744 – ✓ – Stretching of Ti–O and Ti–O–C and Ti–O–Ti bridging
stretching modes [1, 14, 17]
1020–1060 ✓ ✓ ✓ Stretching of Ti–O bonds [18, 19] and C–O (alkoxy)
from graphene [16]
1390 ✓ ✓ ✓ Signal of anatase [9]
(low signal) Stretching of C=C from graphene [16]
1514 ✓ ✓ – Streching of Ti–O bonds from Ti-alkoxi structures [20]
(low signal)
1620–1720 ✓ ✓ ✓ Stretching of Ti–O bonds from amorphous phase [14]
(low signal) (low signal) Stretching of C–O (epoxy) from graphene [16]
2352 ✓ ✓ ✓ Stretching of O=C bond from ­CO2 [9]
(low signal)
2900–3000 ✓ – ✓ Streching of Ti–O bonds from anatase [9]
3462–3624 – ✓ ✓ Vibration of Ti–O bonds in rutile structure [15]
(low signal)
3630–3738 ✓ – ✓ Vibration of Ti–O bonds in anatase structure [15]

explained by the bonds heterogeneity from the composite
networks. The signals at 1390 ­cm−1 and 2900–3000 ­cm−1
(high intensity in FTIR spectra of newly composite and
­TiO2 and almost absent in that of the recovered composite)
are assigned to the vibration of Ti–O bonds from anatase
network, showing the reduced anatase content in the recov-
ered sample, confirmed by the XRD results [9]. The peaks at
1620–1720 ­cm−1 assigned to the vibration of the Ti–O bonds
from the amorphous phase [14] are well defined in the FTIR
spectrum of T­ iO2, but not in those of the composites. The

13

signals in the range 3462 − 3624 ­cm−1 appeared only in the
FTIR spectrum of the recovered composite are correspond-
ing to the vibration of the Ti–O bonds from the rutile phase
[15]. The peaks from 3630 to 3738 ­cm−1 appeared only
in the FTIR spectra of the newly composite and T ­ iO2 and
are assigned to the vibration of Ti–O bonds in the anatase
phase [15]. These results are in agreement with those from
XRD analysis, namely the newly composite is crystalized
in anatase phase while the predominantly crystalline phase
in the recovered sample is rutile. Gayathri Menon et al. [7]
also recovered by calcination a composite based on T ­ iO2
and ZnO and showed that the recalcination led to a more
significant Ti–O–Ti stretching and bending, while the other
attributes were almost unchanged.
The signals corresponding to the stretching vibration of
the specific bonds from graphene can be found at 1062 ­cm−1
(C–O alkoxy), 1385 ­cm−1 (skeletal C=C) and 1625 ­cm−1
(C–O etoxy) [16]. These peaks are overlapped with those
corresponding to the Ti–O stretching from anatase phase in
the Fig. 7 and Table 2.
UV–Vis Spectroscopy of the Newly and Recovered
Composites
The optical properties of semiconductors are relevant for
theirs photocatalytic activity.
Figure 8 illustrates the UV–Vis absorbance spectra of
the materials and allows to compare the optical response
1.4000
1.2000
1.0000
absorption (a.u.)
0.8000
0.6000
0.4000
0.2000
TiO2 newly composite
0.0000
200 250
Fig. 8  UV–Vis absorbance spectra of the newly and recovered composites
13
Journal of Polymers and the Environment
of the newly composite with that of recovered composite
and of pristine ­TiO 2. Unmodified ­TiO 2 is responsive to
the UV light only, because of its large Eg, having its char-
acteristic exciton absorption band maxima in the range
250 nm–287 nm [21]. The total absorption intensity of the
newly and recovered composites is higher than that of the
pristine ­TiO2 and the absorption edge is redshifted. The
absorbance at 350 nm is 1.0507 a.u. for both composites.
This observation is in good agreement with the dark gray
color of the nanocomposite powders and suggest that these
might be photocatalytically active under visible radiation
[22]. The enhanced optical absorption in the visible region
displayed by the composites is explained by the three phe-
nomena: (1) the local surface plasmon resonance (LSPR)
effect generated by the Ag nanoparticles originated from
the electrons oscillations, (2) the formation of Ti–O–C
bonds and electronic interactions between graphene and
­TiO 2 (in the newly prepared composite) [11, 23]. The
enhanced absorbance in the visible ranging as a result of
the graphene inclusion is showed also by Wang et al. [11],
who obtained composites with ZnO-CdS and graphene
with high absorbance in visible range (400–700 nm).
The higher absorbance in the visible range
(400 nm–500 nm) of the recovered composite (0.7465 a.u.)
in comparison with the newly composite (0.4376 a.u.) can
be explained by an intense effect of local surface plasmon
resonance (LSPR) generated by the Ag nanoparticles, as a
result of the increase in the Ag content (14% in the recovered
recovered composite
300 350 400 450 500
wavelenght (nm)
Journal of Polymers and the Environment
composite, in comparison with 0.87% in the newly prepared
sample).
The absorbance of the composites in the range
235–265 nm is higher in comparison with that of T ­ iO2. This
is explained by the fact that when graphene is combined
with ­TiO2, there is a potential for interference between the
absorption peaks of graphene and of ­TiO2, leading to the
increase of the UV light absorption capacity. Graphene,
known for its unique electronic and optical properties, can
exhibit absorption peaks in the mentioned wavelength range.
These peaks may overlap or interfere with the absorption
peaks of T­ iO2, which typically occur in the range of 250–300
[10, 11, 16]. The same results were obtained by Harrum
et al. [12] who characterized ­TiO2–ZnO/graphene compos-
ites. They have demonstrated that the absorbance intensity
of the composite, in the UV range, is higher in the presence
of graphene as a result of the improvement of the light-har-
vesting efficiency [12].
The correlation between the absorption coefficient (a) and
incident photon energy can be expressed according to the
Lambert–Beer law:
2.303 ⋅ Abs(𝜆)
𝛼(𝜆) = (2)
d third region (400-950 °C) related to carbon combustion
where: Abs(α)—the highest absorbance; d- thickness of the
composite layer (m).
Then, the Eg was determined by using the Tauc`s relation:
𝛼 ⋅ h 𝜈 = A(h𝜈 − Eg)n (3)
where: h ν—photon energy, A—constant (band param-
eter), Eg—gap energy, n—transition factor, depending on
the material`s structure on the transition type. The photon`s
transition from the valence band (VB) into the conduction
band (CB) is indirectly (through material`s defects) for the
amorphous materials (n = 2). In contrast, the photon`s tran-
sition occurs directly from VB into CB in the case of the
crystallized materials and n = 1/2. Eg(eV) was obtained by
intercept of the linear part of the representation (α x hν)1/2
vs hν, in the direction of the axe representing the energy.
Table 3 illustrates the Eg values of the composites, in
comparison with that of pristine ­TiO2. The Eg value of the
Table 3  Eg of the newly and the recovered composite and of the pris-
tine ­TiO2 as reference
Sample Eg (eV) Error (%)
Newly composite 2.0082* 0.8755
Recovered composite 1.4343* 0.0714
Pristine ­TiO2—reference 3.3272** 17.4351
* Determined from indirect transitions; ** Determined from direct
transitions
newly composite was 2.0082 eV, while that of the recov-
ered composite and T ­ iO2 were 1.4343 eV and 3.3272 eV,
respectively. It can be observed that the Eg values decreases
in order: T
­ iO2 > new composite > recovered composite. The
Eg value of the recovered composite lower than that of the
newly composite is explained by the different crystalline
phase composition of the two types of composite, resulting
in adjusted bandgap and wide visible-light response [13].
Thermogravimetrical Analysis (TGA) and Differential
Scanning Calorimetry (DSC)
TGA/DSC characterization was performed to assess the
thermal behavior and stability of newly and recovered
composites under heating processing conditions used for
its inclusion into the polymeric matrix (PLA). The newly
and recovered composite thermograms (TGA/DSC) are
shown in Fig. 9a, b. The analyses were performed in the
temperature range from 0 to 950 °C. Three main tempera-
ture regions with specific mass loss steps were observed
in the TGA graphs: the first region (< 100 °C) related to
water evaporation, the second region (100-400 °C) related
to the decomposition of oxygen containing groups and the
[24]. As a result, it was observed that newly and recovered
composites are thermally very stable, showing a total mass
loss at 950 °C of 1.3% and 2.4%, respectively. The weight
loss in the range 100-400 °C attributed to the degradation
of remained organic compounds appeared in TGA of both
newly and recovered composite [25]. Besides, it is worth
noting that above 450-500 °C it was observed a stabilization
or slight increase of weight, which can be attributed to a pos-
sible rearrangement of the ­TiO2 composites structure, lead-
ing to some oxygen inclusion, what justifies the slight weight
increase. The aforementioned processes can be observed in
the DSC thermograms. Thus, endothermic peaks between
150 and 250 °C should be attributed to the decomposition
of organic wastes and the loss of adsorbed water, while the
exothermic peaks at 544 °C and 575 °C corresponds to the
rearrangement phenomena and the crystallinity increase of
composites. The TGA profile of GP500 graphene nanoplate-
lets used for the composite preparation (provided by the sup-
plier GrapheneTech) is displayed in Fig. 9c. The graphene is
decomposed at 621.9 °C in a percent > 99 wt% and a residual
mass of 0.6 wt% remained at 900 °C. The mass loss appears
in the TGA profiles of the new and recovered composite at
700 °C and 690 °C, respectively. This delay of the decom-
position can be explained by the crosslinking between the
graphene sheets with the nano-TiO2 network. Farivar et al.
[24] reported the T ­ max value 703.9 °C for graphene which
is similar with that seen in TGA of newly and recovered
composite, 740 °C and 695 °C, respectively. They argued
that the ­Tmax values can be correlated to the large number
13
 Journal of Polymers and the Environment

Fig. 9  TGA/DSC of newly a and recovered b composite and of GP500 graphene nanoplatelets used for the composite preparation (provided by
the supplier GrapheneTech) (c)

of graphene layers, C defects, covalent and van der Waals Photocatalytical Activity
bonds, thus more energy is needed to degradation [24].
Salicylic acid has been completely decomposed in 120 min
over the newly prepared composite used as catalyst

13
Journal of Polymers and the Environment

a
2.5

kapp = 0.0218 min-1

R2 = 0.9777
2

1.5
kapp = 0.0066 min-1
l n C o /C

R2 = 0.9855

kapp = 0.0029 min-1

R2 = 0.9967
0.5

0
0 20 40 60 80 100 120 140 160 180 200
period (minutes)

newly prepared recovered commercial TiO2

b 120
newly recovered TiO2

100
97.63
100
88.43
85.56
remained salycilic acid (microM %)

78.99
80 75.76 75.15 73.37
68.32 66.57
64.19
61.54
57.18 57.58 58.28
60
50.41
43.99 42.15
40 35.48 34.44
28.15

20
12.02

0.00 0.00 0.00

0
0 20 40 60 80 100 120 140 160 180 200
me (minutes)

Fig. 10  The amount of the remained salicylic acid after photocatalytical decomposition over the investigated composites (a) and photocatalytic
activity of newly prepared and recovered composites and of pristine ­TiO2 determined from the photodegradation of salicylic acid (b)

(Fig. 10a), whereas when recovered composite and pris- concluded that the phototocatalytic activity of the recov-
tine ­TiO2 were used, the remaining nondegraded salicylic ered composite decreased by only 34.44% compared to
acid was 34.44% and 58.28% respectively. Thus, it can be that of the newly prepared one. Also, the apparent rate

13

Table 4  Overall LCA for Environment component
newly prepared and recovered
composites Human health (DALY ) *
Ecosystem quality (PDF ** x ­m2 x year)
Climate change (kg ­CO2 eq)
Resorces (MJ primary)
* DALY (Disability−Adjusted Life Year): a measure of the overall severity of a disease, expressed as the
number of years lost due to illness, usability or premature death
** PDF (Potential Damage Fraction): the fraction of species that have a high probability of not surviving in
the affected area due to the unfavorable living conditions
constant corresponding to the process in which recovered
composite ­(k app = 0.066 ­m in−1) was used was found to
be lower in comparison with the newly prepared catalyst
­(kapp = 0.0218 ­min−1) (Fig. 10b). Gayathri Menon et al. [7]
also reported a reduced decrease in the photoactivity of the
recalcinated nanocomposite based on ZnO and ­TiO2 by
20–25% in comparison with the newly prepared catalyst.
Bento et al. [14] showed a significant decrease in the photo-
catalytic activity of ­TiO2 modified with S when was reused
for 12 cycles.
The explanation for the reduced photocatalytic activity
of the recovered composite is given by the different struc-
ture between the recovered composite and the new prepared
one. This variation was demonstrated by the different results
above discussed: morphology, elemental composition (the
level of graphene is lower in the recovered composite that
in the new one), structure (the recovered composite contain
rutile as the major T
­ iO2 phase, which is a weak photocatalyst
that anatase [13]), UV–Vis absorbance, thermogravimetry.
All these differences are reflected in the 30% lowest photo-
catalytic activity of the recovered composite in comparison
with that of the new composite and are the result of the mul-
tiple annealing during processing (at 500 °C for 2 h during
the preparation of the new composite and at 550 °C for 4 h
during the recovery).
Environmental Impact of the Newly Prepared
and Recovered Composites
The preparation procedures for newly and recovered com-
posites underlying the LCA analysis are shown in Fig. 1.
The overall results of the LCA analysis (Table 4) shows
the impact on the human health, ecosystem quality, climate
change and resources. The obtained values reveal a marked
environmental impact decrease concerning ecosystem
quality, Kg ­CO2 eq emissions and resources consumption,
which is in accordance with the use of recycled materials
obtained through non-pollutant and eco-friendly recycling
procedures. Besides, recycled composites showed a lower
human health impact as result of avoiding solvents and syn-
thetic procedures. The results presented in Table 4 have been
13
Journal of Polymers and the Environment
Newly prepared composite Recovered composite
0.000149 0.0000164
50.17 1.81
152.60 2.01
3186.34 78.80
analyzed in more depth (Table 5) and show that the recover-
ing procedure has a significant lower environmental impact
than the preparation of the new composite. The values cor-
responding to all the monitored environmental components
are reduced in the case of the recovered composite as for the
newly prepared one.
Conclusions
The study evaluates morpho-structure, photoactivity and
environmental impact of the Ag-graphene-TiO2 compos-
ite new and recovered from the composite-polylactic acid
(PLA) film. The recovered composite was quite similar from
the macroscopic and morphological point of views with the
new one. However, the carbon content is very low in the
recovered sample, because of the multiple steps of calcina-
tion occurred during the recovery procedure and contains
mainly rutile crystalline phase, in comparison with the
newly prepared composite structured in anatase form (the
major crystalline phase). The higher optical response of the
recovered composite in comparison with the newly one is
due to an intense effect of local surface plasmon resonance
(LSPR) generated by the Ag nanoparticles, as a result of the
high Ag content. The photocatalytic activity of the recovered
sample was only 30% lower than that of the newly prepared
composite. According to the LCA results, the environmental
impact achieved by the composite`s recovery is consider-
ably lower in comparison with the preparation of the new
composite.The practical application of the study consists in
the recovering potential of the inorganic compounds from
the organic matrix, which can be, subsequently, included in
new materials. This strategy will limit the toxic raw mate-
rials needed for preparation and implicitly, the amount of
waste disposed.
The future research activity will be focused on the includ-
ing the recovered composite in packaging films based on
biomaterials (polylactic acid, polyvinyl alcohol, starch) and
to test their preservation activity during the food storage
in comparison with biofilms modified with new prepared
composites.
Journal of Polymers and the Environment

Table 5  Substances emission corresponding to newly prepared and recovered composites

Compartment Unit Newly Recovered composite
prepared
composite

Carcirogens DALY* 8.51 × ­10–6 3.074 × ­10–8

Hydrocarbons, aromatic Air DALY* 7.26 × ­10–6 1.21 × ­10–9
Arsenic Water 4.83 × ­10–7 3.64 × ­10–9
Air 1.01 × ­10–7 8.50 × ­10–9
2,3,7,8-tetrachlorodibenzo-p-dioxin Air 2.07 × ­10–7 9.86 × ­10–9
Benzo(α) pyrene 1.58 × ­10–7 7.53 × ­10–9
Non-carcirogens DALY* 9.03 × ­10–7 1.158 × ­10–8
Zinc Water DALY* 5.93 × ­10–7 5.34 × ­10–9
Soil 3.00 × ­10–7 6.24 × ­10–9
Respiratory inorganics DALY* 1.30 × ­10–4 1.51 × ­10–5
Particles < 2.5 µm Air DALY* 4.85 × ­10–5 4.98 × ­10–6
Sulfur dioxide 4.81 × ­10–5 8.60 × ­10–6
Nitrogen oxides 3.22 × ­10–5 1.14 × ­10–6
Ammonia 1.13 × ­10–6 3.97 × ­10–7
Respiratory organics DALY* 1.38 × ­10–7 1.44 × ­10–8
NMVOC, non-methane volatile organic compounds, unspecified origin Air DALY 7.55 × ­10–8 7.10 × ­10–9
Ethene 5.34 × ­10–8 5.66 × ­10–9
Xylene 1.76 × ­10–9 8.33 × ­10–10
Hydrocarbons, aromatic 1.53 × ­10–9 3.11 × ­10–10
1-Propanol 1.08 × ­10–9 4.68 × ­10–10
Ionizing radiations DALY* 1.10 × ­10–6 1.27 × ­10–6
Carbon-14 Air DALY* 5.29 × ­10–7 8.56 × ­10–7
Radon-222 5.01 × ­10–7 3.45 × ­10–7
Cesium-137 Water 7.03 × ­10–8 6.66 × ­10–8
Ozone layer depletion DALY* 1.12 × ­10–8 2.65 × ­10–9
Methane, bromotrifluoro-, Halon 1301 Air DALY* 3.40 × ­10–9 3.47 × ­10–10
Methane, bromochlorodifluoro-, Halon 1211 3.14 × ­10–9 7.86 × ­10–10
Methane, dichlorodifluoro-, CFC-12 1.55 × ­10–9 6.89 × ­10–10
Ethane, 1,2-dichloro-1,1,2,2-tetrafluoro-, CFC-114 1.16 × ­10–9 3.52 × ­10–10
Methane, tetrachloro-, CFC-10 1.09 × ­10–9 4.77 × ­10–10
Aquatic ecotoxicity PDF**m2 year 2.54 2.17 × ­10–2
Copper Water PDF**m2 year 1.34 2.54 × ­10–3
Aluminium Air 0.73 5.55 × ­10–3
Aluminium Soil 0.11 8.63 × ­10–3
Zinc Water 0.11 3.47 × ­10–3
Nickel 0.08 1.54 × ­10–3
Terrestrial ecotoxicity PDF**m2 year 41.62 4.52 × ­10–2
Aluminium Air PDF**m2 year 29.56 2.32 × ­10–2
Aluminium Soil 3.88 1.84 × ­10–3
Zinc 2.42 5.96 × ­10–3
Zinc Air 1.56 9.87 × ­10–3
Copper Soil 1.12 4.32 × ­10–3
Terrestrial acidification/nitrification PDF**m2 year 3.22 6.29 × ­10–2
Nitrogen oxides Air PDF**m2 year 2.06 2.36 × ­10–2
Sulfur dioxide 0.91 3.63 × ­10–2
Ammonia 0.20 2.55 × ­10–3
Nitrogen monoxide 0.03 4.12 × ­10–4
Land occupation PDF**m2 year 2.77 1.68

13
 Journal of Polymers and the Environment

Table 5  (continued)
Compartment Unit Newly Recovered composite
prepared
composite

Occupation, mineral, extraction site Raw PDF**m2 year 1.09 0.10

Occupation, forest, intensive 0.91 0.12
Occupation, dump site 0.27 0.46
Occupation, traffic area, road network 0.15 0.13
Occupation, traffic area, rail/road embankment 0.11 0.85
Global warming kg ­CO2 eq 152.60 2.01
Carbon dioxide, fossil Air kg ­CO2 eq 146.92 10.32
Methane, fossil 3.46 2.01
Non-renewable energy MJ primary 3118.26 78.80
Coal, brown Raw MJ primary 782.48 20.31
Oil, crude 762.81 18.96
Gas, natural/m3 703.70 16.94
Uranium 616.64 14.70
Coal, hard 246.91 8.00
Mineral extraction MJ primary 68.08 2.20 × ­10–6
Copper, Cu 0.38%, Au 9.7E-4%, Ag 9.7E-4%, Zn 0.63%, Pb 0.014%, in Raw MJ primary 62.05 1.24 × ­10–7
ore
Zinc 1.13 2.32 × ­10–7
Lead 1.13 2.81 × ­10–7
Copper, 0.99% in sulfide, Cu 0.36% and Mo 8.2E-3% in crude ore 0.54 9.63 × ­10–7
Lead, Pb 0.014%, Au 9.7E-4%, Ag 9.7E-4%, Zn 0.63%, Cu 0.38%, in ore 0.51 6.00 × ­10–7

* DALY (Disability−Adjusted Life Year): a measure of the overall severity of a disease, expressed as the number of years lost due to illness,
usability or premature death. ** PDF (Potential Damage Fraction): the fraction of species that have a high probability of not surviving in the
affected area due to the unfavorable living conditions

Acknowledgements This work was supported by the Technical Uni- References

versity of Cluj Napoca and Ceprohart Braila Romania (Unitatea execu-
tiva pentru finantarea invatamantului superior, cercetarii, inovarii—
UEFISCDI contract no 72/2017), National Institute of Chemistry
Ljubljana Slovenia (Ministry of Education, Science and Sport—MIZS
4126), University of Camerino and Synbiotec Srl, Italy (Ministero
dell'Istruzione e del Merito—MIUR-contract no. 1-2895) and Andaltec
Spain (Ministerio de Asuntos Económicos y Transformación Digital-
MINECO contract no PCIN-2017-037), in the frame of the GRAFOOD
project (M-ERANET program).
Author Contributions AP—conception; experimental deging; writing;
AMC—carrying out measurements; visualization; LMC—statistical
analysis; NC—methodology; visualization; GD, AP, SS—supervision;
Funding The authors have not disclosed any funding.
Data Availability Data are available on request.
Declarations
Competing interests The authors declare that they have no known
competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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