catalysts
Article
Synthesis of Cu-Doped TiO2 Nanocatalyst for the Enhanced
Photocatalytic Degradation and Mineralization of Gabapentin
under UVA/LED Irradiation: Characterization and
Photocatalytic Activity
Roghieh Ahmadiasl 1 , Gholamreza Moussavi 2, *, Sakine Shekoohiyan 2 and Fatemeh Razavian 1
Citation: Ahmadiasl, R.; Moussavi,
G.; Shekoohiyan, S.; Razavian, F.
Synthesis of Cu-Doped TiO2
Nanocatalyst for the Enhanced
Photocatalytic Degradation and
Mineralization of Gabapentin under
UVA/LED Irradiation: Characterization
and Photocatalytic Activity. Catalysts
2022, 12, 1310. https://doi.org/
10.3390/catal12111310
Academic Editor: Giuseppina
Pinuccia Cerrato
Received: 18 September 2022
Accepted: 21 October 2022
Published: 25 October 2022
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Copyright: © 2022 by the authors.
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This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Catalysts 2022, 12, 1310. https://doi.org/10.3390/catal12111310
1 Department of Environmental Science and Engineering, West Tehran Branch, Islamic Azad University,
Tehran P.O. Box 1468763785, Iran
2 Department of Environmental Health Engineering, Tarbiat Modares University, Tehran P.O. Box 331-14115, Iran
* Correspondence: moussavi@modares.ac.ir; Tel./Fax: +98-21-82884580
Abstract: Light-harvesting of titanium oxide (TiO2 ) was enhanced by copper (Cu) doping, and its
performance was evaluated by gabapentin (GBP) degradation under UVA-LED irradiation. The
morphology and structure of TiO2 and Cu-TiO2 were characterized using XRD, FTIR, FE-SEM, EDX,
TEM, PL, DRS, and BET analysis. The complete degradation of 10 mg/L GBP was obtained in the
developed photocatalytic process under the optimal conditions: catalyst loading, 0.4 g/L; pH solution,
8; and reaction time, 20 min. The reactive species trapping was studied to identify the degradation
mechanism in this system. Among the water matrix experiments, phosphate (PO4 3− ) anion indicated
an inverse effect in increasing efficiency. Finally, the main intermediates generation during the GBP
degradation was investigated based on LC-MS analysis, and a decomposition pathway was proposed.
Accordingly, doping TiO2 with Cu resulted in the development of a UVA-activated photocatalyst for
efficiently degrading and mineralizing GBP as a model of a pharmaceutical compound.
Keywords: emerging contaminant; advanced oxidation process; photocatalysis; TiO2 modifica-
tion; copper
1. Introduction
Nowadays, emerging pollutants are widely consumed, but despite their beneficial
effects, their adverse efficacy on human health and the environment cannot be denied [1].
The pharmaceutical industries produce a large number of medicinal materials for the
prevention and therapy of human illnesses, and thus water resources are polluted by
industrial wastewater. Additionally, the disposal of these therapeutic materials from the
human body into the sewage will be another way of entering these micro-pollutants into
aqueous environments [2,3]. Gabapentin (GBP) is widely used as an analgesic for kidney
disorders and for treating neuropathic pain and epilepsy [4,5]. GBP has been detected
at concentrations of up to 10 ηg/L, along with other drugs in raw wastewater, but the
noteworthy point is that its destruction does not take place entirely, and no-metabolite
structure can be dispersed in various solutions [6,7]. Additionally, this drug is ranked as
an emerging micro-pollutant with adverse effects on human health [6,8]. Hence, the main
issue is developing an effective method for treating contaminated water with different
pharmaceutical pollutants. The selection of the heterogeneous photocatalytic oxidation
(PCO) method based on the advanced oxidation technique is an attractive technology that
has been applied in the degradation of various recalcitrant organic pollutants [9,10]. In
the PCO process, photo-generated intermediates, such as electron/hole pairs, can enhance
photoreaction under light irradiation. Many PCO processes have been studied to find
effective photocatalysts for the decomposition of a wide range of contaminants [11]. Among
https://www.mdpi.com/journal/catalysts
Catalysts 2022, 12, 1310 2 of 18

the various semiconductors as photocatalysts, TiO2 has been most highlighted due to its
remarkable properties, including great oxidation potential, chemical durability, nontoxicity,
a high proportion of surface to volume, and economical trait [12,13]. Nevertheless, the
high recombination rate of photo-induced charge carriers and poor ionic and electrical
transmission are the significant intrinsic disadvantages of unmodified TiO2 [14]. As a
solution, doping semiconductors with transition metal and nonmetal or coupling with
other materials have been proposed in previous studies [2,15–18]. Doping TiO2 with metals
has shown high photocatalytic activity that enhanced the separation capability of e− /h+
pairs and reduced the band gap energy compared to pure TiO2 [14,19]. For instance, the
application of copper (Cu2 O, Cu2+ , CuO, etc.) as a dopant to improve the photocatalytic
activity of TiO2 has been efficiently practiced for the degradation of contaminants and is
applicable due to its cost-effectiveness and abundance [20,21]. It has been reported that
when a semiconductor is doped with copper, it can create an extra energy level, leading
to increasing photocatalytic activity [22,23]. Moreover, Vaiano et al. reported that when
Cu was introduced to ZnO, the band gap energy decreased from 3.2 to 2.92 eV, resulting
in decreasing the recombination rate of e- /h+ pairs, thus the photocatalytic performance
improved [24].
In this context, the Cu-TiO2 material was prepared and characterized as an improved
form of TiO2 catalyst for the degradation and mineralization of Gabapentin under UVA
irradiation emitted from LEDs. LEDs are environmentally benign, have a long life span,
and provide flexibility in designing the photoreactor; therefore, they are considered an
appropriate source of UV photons to drive the PCO [25]. Accordingly, the effect of the main
experimental parameters of pH, catalyst concentration, water anions, radical scavengers,
and reaction time was investigated on the degradation of Gabapentin. A pathway was
also proposed for the degradation of Gabapentin in the developed photocatalytic process
operated under optimal conditions.

2. Results and Discussion

2.1. Characterization of As-Prepared TiO2 and Cu-TiO2
The crystal structure of plain TiO2 and Cu-TiO2 products are shown in Figure 1a
using XRD analysis. The characteristic peaks of (101), (004), (200), (105), (211), (204),
(116), (220), and (215) planes are identified in the XRD pattern of both TiO2 and Cu-TiO2
products that can be attributed to the anatase phase of TiO2 based on (JCPDS Card No.
73–1764). Additionally, the diffraction peaks of (101), (110), (111), and (220) planes are
observed in the XRD pattern of the Cu-TiO2 materials, which corresponds to the rutile
phase of the TiO2 structure (JCPDS Card No. 78–1510). On the other hand, Cu-TiO2
with mixed phases (anatase and rutile) was prepared through the designed synthesizing
method. Any characteristic peak is observed in the XRD pattern of Cu-TiO2 product for
CuO, suggesting that Cu might be doped in the lattice of the TiO2 [26]. After Cu doping,
the peak broadening in the XRD pattern qualitatively described the change in particle size
and lattice expansion [27]. The crystallite size of TiO2 and Cu-TiO2 was estimated from
the XRD pattern achieved using the Scherrer equation. The crystallite size of pure TiO2
and Cu-TiO2 was 29.3 and 45.6 nm. This matter indicates that introducing Cu into TiO2
increased the crystallite size of Cu-TiO2 . The literature review [27,28] reported that the
crystallite size of Cu-TiO2 was slightly increased due to the presence of Cu2+ and CuO
species. The different ionic radii of Cu and Ti ions caused lattice distortion and strain field,
changing the size of particles of Cu-TiO2 .
 3 of 18
Catalysts 2022, 12, 1310 3 of 18

(b)

C=O O−H
C=C
Transmittance (%)

TiO2
Cu-TiO2
Cu−O

Ti−O−Ti

500 1000 1500 2000 2500 3000 3500 4000

Wavenumber (cm−1)
Figure 1. XRD images (a) and FTIR patterns (b) of pure TiO2 and as-made Cu-TiO2 .
Figure 1. XRD images (a) and FTIR patterns (b) of pure TiO2 and as-made Cu-TiO2.
The FTIR spectra of TiO2 and Cu-TiO2 are displayed in Figure 1b. The FTIR spectrum
of the catalyst shows absorption peaks between 400 and 600 cm−1 , which is ascribed to
The FTIR spectra of TiO
Ti-O-Ti 2 and Cu-TiO2 are displayed in Figure 1b. The FTIR spectrum
stretching. In addition, other peaks of about 1623 and 2347 cm−1 are related to
of the catalyst shows absorption peaks
C = C and C = O functional between 400respectively.
groups, and 600 cmThe −1, which is ascribed to Ti-
medium peaks at about 3485 and
O-Ti stretching. In 3500
addition, − 1 other peaks
cm confirm of about
the presence of OH1623 andin2347
bands cm−1 are
the sample related
structure dueto
toC = C adsorb
surface
and C = O functional groups, respectively. The medium peaks at about 3485 and 3500 cm1250
water and hydroxyl agent. The vibration bands are observed between 1000 to −1 cm−1
confirm the presenceafterofCu-doped
OH bands TiO2inindicated latticestructure
the sample vibration of TiOto
due 2 [29–32].
surface adsorb water
The surface morphology of the as-prepared TiO2 and Cu-TiO2 materials was investi-
and hydroxyl agent. The vibration bands are observed between 1000 to 1250 cm−1 after
gated by FESEM, and the elemental distribution was evaluated based on EDX and mapping
Cu-doped TiO2 indicated
analyses; lattice vibration
the results of TiO2 [29–32].
are presented in Figure 2a–f for Cu-TiO2 and in Figure S1 for TiO2 .
The surface morphology of the as-prepared
FESEM images confirmed the almost TiO 2 and Cu-TiO
spherical materials
shape of2 the Cu-TiO2was investi-
product with uniform
gated by FESEM, and size the elementalTherefore,
distribution. distribution
dopingwaswithevaluated based
Cu affected the on EDX andofmap-
morphology TiO2 . Norris
ping analyses; the et al. [33]are
results reported that theinphotocatalyst’s
presented Figure 2a–f morphology,
for Cu-TiOsize,
2 andandinelectronic
Figure S1 structure
for could
be modified by doping with copper. The EDX analysis
TiO2. FESEM images confirmed the almost spherical shape of the Cu-TiO2 product with demonstrated the presence of
considerable percentages of Ti, O, and Cu in the structure of the as-prepared Cu-TiO2
uniform size distribution. Therefore, doping with Cu affected the morphology of TiO2.
Norris et al. [33] reported that the photocatalyst's morphology, size, and electronic struc-
ture could be modified by doping with copper. The EDX analysis demonstrated the pres-
ence of considerable percentages of Ti, O, and Cu in the structure of the as-prepared Cu-
alysts 2022, 12, x 4o

Catalysts 2022, 12, 1310 4 of 18

ping shows that the Cu-TiO2 seems to be homogenous. To further examine the morph
ogy ofcatalyst. In addition,
the prepared the distribution
materials, of elements
the TEM withwas
analysis colored dots in the and
conducted, mapping images
images of TiO2 a
(Figure 2d–f) confirms the presence of Cu in the Cu-TiO2 product. The EDX mapping shows
Cu-TiO 2 can be observed in Figure 2c. The average particle sizes of TiO2 and Cu-TiO2 d
that the Cu-TiO2 seems to be homogenous. To further examine the morphology of the
termined
preparedusing Digimizer
materials, the TEMsoftware
analysis based on the TEM
was conducted, images
and images were
of TiO around 35 and 47 n
2 and Cu-TiO2 can
respectively.
be observed The results2c.confirmed
in Figure The averagethat doping
particle TiO
sizes of TiO2 2with Cu increases
and Cu-TiO the size
2 determined usingof the p
Digimizer software based on the TEM images were around 35 and 47 nm,
ticles. Tasbihi et al. [34] reported that Cu-TiO2 was fully crystallized at lower doping co respectively.
The results confirmed that doping TiO2 with Cu increases the size of the particles. Tasbihi
centrations, but at higher concentrations of Cu (15 wt.%), the prepared catalyst had am
et al. [34] reported that Cu-TiO2 was fully crystallized at lower doping concentrations, but
phous at phases.
higher concentrations of Cu (15 wt.%), the prepared catalyst had amorphous phases.

Figure 2. FE-SEM
2. FE-SEM
Figure (a),(a),
EDXEDX(b),
(b), TEM
TEM (c),
(c),and
andelemental mapping
elemental (d–f) of(d–f)
mapping Cu-TiO .
of2Cu-TiO 2.

BET analysis estimated the surface areas of prepared TiO2 and Cu-TiO2 to be 52.1
BET
and 9.9 analysis estimated(Figure
m2 /g, respectively the surface areas
3). It can of prepared
be related to changesTiO and
in2the Cu-TiO2 to
morphology be 52.1 a
and
9.9 mcrystalline
2 /g, respectively
structure (Figure
of the TiO3). It can
2 after be related
doping with Cu to changes
[30]. in agreed
This result the morphology
with Tasbihi and cr
et al. [34] and Bensouici et al. [22], who reported a decrease
talline structure of the TiO2 after doping with Cu [30]. This result agreed in the surface area of TiOwith
2 after Tasbih
doping
al. [34] and with Cu. From
Bensouici the[22],
et al. pore who
size distribution
reported acurve, Figurein3a,b
decrease the(inset),
surfaceandarea
IUPAKof TiO2 af
categorization, both catalysts’ isotherms were observed to be type IV and mesoporous
doping with Cu.
structures [35].
From the pore size distribution curve, Figure 3a,b (inset), and IUPA
categorization, both catalysts’ isotherms were observed to be type IV and mesoporo
structures [35].
 talline structure of the TiO2 after doping with Cu [30]. This result agreed with Tasbihi et
al. [34] and Bensouici et al. [22], who reported a decrease in the surface area of TiO2 after
doping with Cu. From the pore size distribution curve, Figure 3a,b (inset), and IUPAK
categorization, both catalysts’ isotherms were observed to be type IV and mesoporous
Catalysts 2022, 12, 1310 5 of 18
structures [35].

Figure 3. BET analysis of TiO2 (a) and Cu-TiO2 (b) and the BJH plots (inset).
Figure 3. BET analysis of TiO2 (a) and Cu-TiO2 (b) and the BJH plots (inset).
The optical properties of pure TiO2 and Cu-TiO2 products were measured using the
UV-Vis DRS analyses, and the results are given in Figure 4. Based on Figure 4a, the role of
Cu doping on the spectra profile of Cu-TiO2 is visible by shifting the absorption edge of TiO2
to the higher wavelengths upon doping with Cu. It can be related to the surface plasmon
resonance properties of copper [36], resulting in increased light absorption potential of
the product and therefore in the accelerated generation of electron-hole pairs under light
irradiation. Moreover, the band gap energy (Eg ) of TiO2 and Cu-TiO2 was determined
using the Tauc/David–Matt method [37]. According to Figure 4b, the Eg values of TiO2
and Cu-TiO2 were estimated to be about 3.2 and 2.9 eV, respectively. The results indicate
that doping TiO2 with Cu could decrease its band gap energy, reconfirming the higher
light absorption potential and thus the photocatalytic activity in the Cu-TiO2 material
compared to that in the plain TiO2 . Tasbihi et al. [34] observed that pure TiO2 exhibited
Eg of 3.05 eV, while the Eg of Cu/TiO2 was lower due to the presence of Cu2+ ions in
the structure of TiO2 lattice. Additionally, they [34] reported that low Cu concentration
(0.2 wt.%) could not decrease the Eg of Cu-TiO2 . Sahu and Biswas [27] reported that the Eg
of TiO2 decreased from 3.31 to 2.51 eV with increasing the Cu concentration at the highest
dopant concentration (15 wt.%). This change in Eg was related to incorporating Cu2+ ions
into the TiO2 structure and forming CuO as a layer on the TiO2 particle surface [27]. The
change in the optical absorption of Cu-TiO2 was attributed to the defect centers created
by the replacement of Ti4+ by Cu2+ atoms in the TiO2 crystal lattice. A previous study [38]
showed that doping TiO2 with aliovalent ions could change the local lattice symmetry
and defect characteristics, changing the absorption properties. In Cu-TiO2 , when Cu+2
ions are located inside or on the surface sites of TiO2 , a rearrangement of the neighbor
atoms to compensate for the charge deficiency is caused by lattice deformation. The lattice
deformation influences the electronic structure of Cu-TiO2 and shifts the Eg . Therefore,
these Cu-doped materials can be applied for diverse photocatalytic applications, which
have been reported in numerous other studies.
 located inside or on the surface sites of TiO2, a rearrangement of the neighbor atoms to
compensate for the charge deficiency is caused by lattice deformation. The lattice defor-
mation influences the electronic structure of Cu-TiO2 and shifts the Eg. Therefore, these
Cu-doped materials can be applied for diverse photocatalytic applications, which have
Catalysts 2022, 12, 1310 6 of 18
been reported in numerous other studies.

x 6 of 18

Figure 4. DRS (a) and Tauc’s plots analysis (b) of as-made plain TiO2 and Cu-TiO2 materials.
Figure 4. DRS (a) and Tauc’s plots analysis (b) of as-made plain TiO2 and Cu-TiO2 materials.
The PL spectra of the pure TiO2 and Cu-TiO2 samples were investigated to comprehend
the separation of e− /h+ pairs and the charge–carrier transfer efficiency. Figure 5 shows
The PL spectra of the pure TiO2 and Cu-TiO2 samples were investigated to compre-
a significant peak at around 388 nm in pure TiO , which is assigned to the band-to-band
−/h+ pairs and the charge–carrier 2transfer efficiency. Figure 5
hend the separation of e
recombination because it is near-band-edge luminescence. The peak in PL spectra of
shows a significant peak2atisaround
Cu-TiO observed 388
at nm
376 in
nm, pure
but TiO
with2,awhich
drop in is intensity.
assignedThis to the band-to-
intensity reduction
band recombination because
refers to the itinhibition
is near-band-edge luminescence.
of the recombination of the The peak in PL spectra
photo-generated electron of
from the
Cu-TiO2 is observed conduction
at 376 nm, bandbut(CB)
withtoathe valence
drop band (VB)
in intensity. of TiO
This 2 . The reduction
intensity higher PL peak intensity
refers
in pure TiO
to the inhibition of the recombination
2 refers to of the photo-generated electron from the conduction to the
the reduction of the lifetime of the electron-hole pairs due
fast recombination rate. Reda et al. [39] reported the highest reduction in PL intensity of
band (CB) to the valence band (VB) of TiO2. The higher PL peak intensity in pure TiO2
doped-TiO2 with Cu and N, revealing the examined samples’ efficacy in reducing photo-
refers to the reduction of the
generated lifetime of recombination
electron-hole the electron-hole pairs with
compared due pure
to theTiOfast. recombina-
2 The intensity of the
tion rate. Reda et al.
light absorption of TiO2 was also decreased upon doping with Cu, implying2 with
[39] reported the highest reduction in PL intensity of doped-TiO that the rate
Cu and N, revealing the examined
of electron-hole samples’ decreased
recombination efficacy ininreducing
the dopedphoto-generated elec- in the
product. It might result
formation
tron-hole recombination of higher reactive
compared with pureradical
TiOspecies
2. Theand, thus, higher
intensity of the degradation performance in
light absorption
the developed photocatalytic process [40]. Therefore, it can
of TiO2 was also decreased upon doping with Cu, implying that the rate of electron-hole be concluded that doping with
copper significantly modified the properties of TiO2 , which increased its photoactivity [41].
recombination decreased in the doped product. It might result in the formation of higher
reactive radical species and, thus, higher degradation performance in the developed pho-
tocatalytic process [40]. Therefore, it can be concluded that doping with copper signifi-
cantly modified the properties of TiO2, which increased its photoactivity [41].
 of TiO2 was also decreased upon doping with Cu, implying that the rate of el
recombination decreased in the doped product. It might result in the formatio
reactive radical species and, thus, higher degradation performance in the deve
tocatalytic process [40]. Therefore, it can be concluded that doping with cop
Catalysts 2022, 12, 1310 7 of 18
cantly modified the properties of TiO2, which increased its photoactivity [41].

Figure 5. Photoluminescence of as-made plain TiO2 and Cu-TiO2 materials.

Figure 5. Photoluminescence of as-made plain TiO2 and Cu-TiO2 materials.
2.2. The Photocatalytic Activity of Cu-Doped TiO
2
2.2.1. Effect of Initial pH Solution
The solution pH is an essential factor effective in GBP removal in the photocatalytic
process. Moreover, the solution pH affects photocatalytic activity through two mechanisms.
Firstly, the solution pH influences the extent of pollutant ionization and, therefore, the
ionizable compounds’ adsorption on the photocatalyst’s surface. On the other hand,
the ionizable compound’s absorption rate could control the photocatalytic degradation
amount [42]. The removal of pollutant compounds affected by pH in photocatalytic
processes depends on the solution pH, compound pKa, and catalyst pHpzc. The interaction
between these factors promotes or inhibits the removal rate of the desired compound.
Additionally, the literature review showed that change in the solution pH had altered the
adsorption capacity of pollutants on the photocatalyst surfaces [43]. The experiment was
evaluated under various pH levels (4–9), while the GBP concentration, catalyst dosage,
and reaction time were considered to be 10 mg/L, 0.5 g/L, and 20 min, respectively. As
shown in Figure 6a, the complete photo-activity was obtained at pH 8 and 9 while it
was reduced at acidic pH. Additionally, it is interesting that in all pH values, the GPB
degradation was higher than GBP adsorption. GBP is a compound with an isoelectric point
at pH 7.14 and has two pKa values of 3.68 for the carboxylic acid and 10.7 for the primary
amine [44]. On the other hand, the pHpzc value of prepared Cu-TiO2 was estimated at
about 7.32, which depicts that the catalyst surface had a negative charge higher than pHpzc.
As a result, at pH 8 and 9, electrostatic attraction between GBP molecules (positive) and
Cu-TiO2 photocatalyst (negative) enhanced the destruction efficiency. Therefore, pH 8 was
selected for the subsequent reaction. Nevertheless, at a pH value lower than 7, electrostatic
repulsion is boosted due to the positive charge of GBP and as-made catalyst, resulting in
low photocatalytic activity [45]. Ahmad and Yasin [46] investigated the Cu/TiO2 /bentonite
composite for the photocatalytic degradation of deltamethrin. The results show that a
maximum degradation rate was observed at pH 12. They concluded that modifying pH is
an effective strategy to improve photocatalytic performance. Sharma et al. [47] observed
that the degradation rate of tetracycline with Cu2 O-TiO2 nanotube was complete under
acidic, neutral, and alkaline conditions, and it is related to the adsorption of pollutants on
the surface catalyst.
Catalysts 2022, 12, x 8 of 18

Catalysts 2022, 12, x 8 of 18

Catalysts 2022, 12, 1310 8 of 18

Figure 6. Effect of solution pH on GBP degradation in the Cu-TiO2-UVA system (GBP = 10 mg/L,
catalyst = 0.5 g/L, reaction time = 20 min).

The6.6.
Figure
Figure number
Effectofofof
Effect activepH
solution
solution sites
pHon onon
GBP the
GBP catalyst surface
degradation
degradation ininthe increased,
theCu-TiO
Cu-TiO which,
2 -UVA
2-UVA system
system in(GBP
turn,
(GBP=boosted
=1010mg/L,
mg/L,
the formation
catalyst ==
catalyst 0.50.5
g/L,of reaction
g/L, main reactive
reactiontimetime =species,
= 20 min). such as electron-hole pairs or radical hydroxyl
min).
20
during the photo process. Additionally, catalyst concentrations higher than 0.5 g/L tend
2.2.2. Effect
The number of Cu-TiO 2 Concentration
of active sites on
to accumulate in a system where thethe catalyst surface
penetration of light increased,
decreases, which,
resulting in inturn, boosted
no change
inthe Catalyst
theformation concentration
of main reactive
removal efficiency directly
[48]. It isspecies, influences
such as
worth saying the
that degradation
electron-hole
adsorption was efficiency.
pairs Figure
or radical
evaluated 7 depicts
hydroxyl
along with
GBP
during
GBP degradation
the photo process.
photo-degradation, under reaction
and conditions
Additionally, of pH
catalystloading
increasing catalyst = 8, reaction
concentrations time
reduced higher = 20 min and
than 0.5 rate,
the adsorption pollutant
g/L tend
in-
toconcentration
accumulate
dicating the roleinof 10 mg/L
a light
system with
onwhere different
the Cu-TiO catalystofdosages
the penetration
2 activation lightReda
[49]. (0.1–0.5
decreases,
et al. [38] g/L)
resultingin Cu-TiO
reported in no /UVA
change
that 20.14
inprocess.
g/L the
of Cu-TiOWithout
removal 2 was
the
the Cu-TiO
efficiency [48]. 2It,concentration
optimal the removal
is worth efficiency
saying forthat was about
dyeadsorption
removal. 21%,
was
By but after
evaluated
increasing the the
along addition
amountwith
of
ofGBP the catalyst,
photo-degradation,
photocatalyst the degradation
up to theand rate
increasing
optimal was enhanced.
level, catalyst
the reaction In
loading general,
ratereduced the
due to the degradation
more adsorption
active sites efficiency
rate, in-
was
of GBP the
dicating
increased. is enhanced
role of light
Additionally, withonan
when theincreased
the Cu-TiO
Cu-TiO 2concentration
activation
2 dosage was [49].ofReda
Cu-TiO
increased 2 . As
et beyond
al. [38]can beoptimal
reported
the seen, removal
that 0.14
con-
efficiencies
g/L of Cu-TiO
centration, thewere was obtained
the optimal
2aggregation
to
of be 49.8, 56.2, 69.3,
theconcentration
suspended 100,dye
for
particles andremoval.
100%place,
took forBy0.1, 0.2,this
0.3,phenomenon
increasing
and 0.4,
theand 0.5 g/L
amount
of
reduced the as-prepared
of photocatalyst
the amount catalyst,
upoftolight respectively.
the reaching
optimal level, These
the reaction
the active results
sites of the prove
rate that
due toand
catalyst, the
more degradation
active sites the
subsequently, yield
was
enhanced
increased.
rate with increasing
Additionally,
of degradation Cu-TiO
when the Cu-TiO
decreased. 2 loading to 0.4 g/L. Therefore, the optimal
2 dosage was increased beyond the optimal con-
concentration
of Cu-TiO 2 for the following
centration, the aggregation of the suspended experiments was chosen took
particles as 0.4place,
g/L. and this phenomenon
reduced the amount of light reaching the active sites of the catalyst, and subsequently, the
rate of degradation decreased.

Figure 7. Effect of catalyst concentration on GBP degradation in the Cu-TiO2 -UVA system
(GBP = 10 mg/L, pH = 8, reaction time = 20 min).
Catalysts 2022, 12, 1310 9 of 18

The number of active sites on the catalyst surface increased, which, in turn, boosted
the formation of main reactive species, such as electron-hole pairs or radical hydroxyl
during the photo process. Additionally, catalyst concentrations higher than 0.5 g/L tend to
accumulate in a system where the penetration of light decreases, resulting in no change
in the removal efficiency [48]. It is worth saying that adsorption was evaluated along
with GBP photo-degradation, and increasing catalyst loading reduced the adsorption rate,
indicating the role of light on the Cu-TiO2 activation [49]. Reda et al. [38] reported that
0.14 g/L of Cu-TiO2 was the optimal concentration for dye removal. By increasing the
amount of photocatalyst up to the optimal level, the reaction rate due to more active sites
was increased. Additionally, when the Cu-TiO2 dosage was increased beyond the optimal
concentration, the aggregation of the suspended particles took place, and this phenomenon
reduced the amount of light reaching the active sites of the catalyst, and subsequently, the
rate of degradation decreased.

2.2.3. Catalytic Activity and Mechanism of GBP Degradation in the Cu-TiO2 /UVA Process
The catalytic activity of TiO2 and Cu-TiO2 materials were studied after selecting
the optimal conditions, and the results are presented in Figure 8a. As-made Cu-TiO2
catalyst exhibited poor adsorption toward GBP molecules under dark conditions. When no
catalyst was introduced into the reactor, the GBP removal was increased by 21% under light
irradiation. In addition, the pure TiO2 indicated poor degradation efficiency of about 41%
under the UVA-LED system compared to Cu-TiO2 . By utilizing the as-prepared Cu-TiO2
catalyst, the degradation of GBP molecules significantly improved and complete removal
was achieved. In addition, the kinetics of the removal of GBP in the selected processes was
evaluated based on the pseudo-first-order (PFO) reaction model [50], and the plots are

C0
ln = k obs t (1)
Ct

in which C0 and Ct are the initial and residual concentrations of GBP at time t (min) of the
reaction, and kobs is the observed PFO rate constant values for each initial concentration
that was obtained from the slope of plotting ln (C0 /Ct ) vs. reaction time.
The PFO rate constants of GBP removal in the UVA, TiO2 /UVA, and Cu-TiO2 /UVA
processes were 0.004, 0.029, and 0.122 min−1 , respectively. It is seen that the degradation
by direct photolysis was inefficient for the removal of GBP under the selected conditions.
In addition, the removal rate of GBP in the photocatalytic process with Cu-TiO2 was
over four times that with plain TiO2 , implying that doping TiO2 considerably improved
its photocatalytic activity for the removal of GBP. The improvement of photocatalytic
activity of TiO2 upon doping with Cu can be related to the decrease in band gap and the
recombination rate of the electron/hole. Indeed, Cu dopant as a free electron trap could
reduce the recombination rate of electron-hole pairs, improve the light-harvesting capacity,
and accelerate the photo-activity of modified TiO2 , which is consistent with DRS and PL
analysis. Additionally, in the presence of an appropriate light source, electrons are excited
from the VB to the CB of TiO2 to create VB holes (positive charge carriers) and CB electrons
(negative charge carriers). By scavenging the oxidizing species, these electron-hole pairs
produce different reactive oxygen (ROS), further degrading the GBP on the surface of the
Cu-TiO2 [47].
 0
𝑙𝑛 = 𝑘𝑜𝑏𝑠 𝑡 (1)
𝐶𝑡
in which C0 and Ct are the initial and residual concentrations of GBP at time t (min) of the
reaction, and kobs is the observed PFO rate constant values for each initial concentration
Catalysts 2022, 12, 1310 10 of 18
that was obtained from the slope of plotting ln (C0/Ct) vs. reaction time.

(a)
100

Cu-TiO2/UVA

Gabapentin removal (%)

80 Cu-TiO2
UVA
TiO2/UVA
60

40

20

0
0 5 10 15 20
Reaction time (min)

(b)
2.0

y=0.122 x
Cu-TiO2/UVA R2=0.992
1.5
LED
TiO2/UVA
ln (C0/Ct)

1.0

y=0.029 x
0.5
R2=0.995

y=0.004 x
0.0
R2=0.971

0 5 10 15
Reaction time (min)

Figure 8. The degradation percentage (a) and rate (b) of GBP by various processes (GBP = 10 mg/L,
Figure 8. The degradation percentage (a) and rate (b) of GBP by various processes (GBP = 10 mg/L,
pH = 8, catalyst = 0.4 g/L, reaction time = 0–20 min).
pH = 8, catalyst = 0.4 g/L, reaction time = 0–20 min).
To understand the mechanisms involved in the removal of GBP in the Cu-TiO2 /UVA
process, the GPB removal was compared in the absence and presence of several scavengers,
and the related results are reported in Figure 9. The radical scavengers were tert-butanol
(TBA) as the scavenger of HO• , p-benzoquinone (pBQ) as the scavenger of HO• and O2•− ,
sodium azide as the scavenger of HO• and 1 O2 , and oxalate as the scavenger of h+ [34]. As
seen in Figure 9, the removal of GBP was less affected in the presence of TBA, pBQ, and
sodium azide, but it was strongly suppressed in the presence of oxalate. It indicates that
photo-generated holes played the main role in GBP oxidation, which could be quenched by
water molecules or oxygen atoms to enhance the formation of hydroxyl and superoxide
radicals, respectively [51].
 and O•− •
2 , sodium azide as the scavenger of HO and O2, and oxalate as the scavenger of h
1 +

[34]. As seen in Figure 9, the removal of GBP was less affected in the presence of TBA,
pBQ, and sodium azide, but it was strongly suppressed in the presence of oxalate. It indi-
cates that photo-generated holes played the main role in GBP oxidation, which could be
quenched by water molecules or oxygen atoms to enhance the formation of hydroxyl and
Catalysts 2022, 12, 1310 11 of 18
superoxide radicals, respectively [51].

Figure 9. Effect of scavengers on GBP degradation in the Cu-TiO2 /UVA process (GBP = 10 mg/L,
FigurepH9.=Effect of scavengers
8, catalyst on GBP
= 0.4 g/L, degradation
scavenger (wheninadded)
the Cu-TiO 2/UVA
= 1 M, process
reaction time(GBP
= 20=min).
10 mg/L, pH
= 8, catalyst = 0.4 g/L, scavenger (when added) = 1 M, reaction time = 20 min).
Regarding the FTIR curve given above, the presence of the functional group (TiO2 -
O-Cu) confirmed the CuO formation that we expected: the CuO-TiO2 heterojunction led
to the best performance of modified TiO2 [13,51]. Therefore, the low band gap of CuO
(1.7 eV) compared to TiO2 (3.2 eV) is a reason for driving photo-generated electrons from
the CB of metallic copper to TiO2 , and at the same time, photo-induced holes jumped from
the VB TiO2 to VB CuO [13]. On the other hand, the synergistic role between anatase–
rutile heterophase in the as-prepared catalyst induced the separation of electron–hole
pairs accelerated for the greater transfer of photo agents in the CB and VB of Cu-TiO2
nanoparticles (Equations (2)–(5)) [30].
− +


Photocatalyst (Cu-TiO2 ) + hν → Photocatalyst eCB +hVB (2)
−
eCB +O2 → O2•− (3)
+
hVB + H2 O → HO• (4)
+
GBP + hVB /HO• /O2•− → degradation products (5)
Sharma et al. [47] reported that the main reactive species involved in tetracycline
degradation in the photocatalytic process using Cu2 O-TiO2 was the superoxide radical
(O2 •− ), followed by HO• and valence band holes (VBh+ ). The effect of radical scavengers
on carbamazepine (CBZ) degradation was investigated in the CuWO4 -TiO2 process [52].
The results showed that the mechanism for the degradation of CBZ was the surface charge
process driven by HO• , O2 •− , the generation of VBh+ , and CBe− . Under an appropriate
light source, the excitation process can generate holes in the VB and electrons in the
CB accompanied by redox reactions such as Cu+2 /Cu+ . The generated electrons of the
CB of TiO2 drift into the CB of CuWO4 . This phenomenon suppresses electron-hole
recombination and enhances CBZ degradation. Besides electron-hole generation, ROS
production, including O2 •− and HO• , becomes available to drive the photodegradation
activity [52].
 Catalysts 2022, 12, 1310 12 of 18

2.2.4. Effect of Water Matrix on GBP Photo-Degradation

To investigate the as-prepared catalyst in practical applications, the presence of com-
mon water anions, such as chloride (Cl− ), nitrate (NO3 − ), carbonate (CO3 2− ), phos-
phate (PO4 3− ), and sulfate (SO4 2− ), were evaluated on the GBP decomposition in the
Cu-TiO2 /UVA process. Most studies have reported that anions have an inhibitory role
in the photocatalytic processes due to (1) the competition between the anions and the
target pollutant toward the available active sites on the catalyst surface; (2) the radicals’
scavenging properties of the anions, which caused the formation of ionic radicals such as
Cl•− , NO3 •− , and HCO3 •− with less degradation potential; and (3) the hole scavenging
proprieties of anions [52]. Therefore, the experiment was conducted with no anion sample.
As can be seen in Figure 10, the addition of PO4 3− and SO4 2− decreased the efficiency to
49 and 91%, respectively, under conditions of pH = 8, catalyst concentration = 0.4 g/L,
GBP concentration = 10 mg/L, and anions = 1 mM, during 20 min. Based on the results
shown in Figure 10, a negligible negative impact was observed after adding Cl− , NO3 − ,
and CO3 2− compared with the control sample on the GBP removal in the Cu-TiO2 /UVA
photocatalytic process, indicating no considerable interaction between these anions, and
the reactive species contributed in removing GBP under the selected conditions. PO4 3−
and SO4 2− at the higher levels had a limiting effect on GBP removal in the Cu-TiO2 /UVA
photocatalytic process. It can be related to the interaction of these anions with the surface
of the catalyst and occupying the active sites of the catalyst, resulting in a decrease in the
GBP degradation rate (Equations (6)–(8)) [53,54]. The introduction of SO4 2− decreased CBZ
degradation, and a possible reason was the adherence of SO4 2− to the surface of TiO2 via
Catalysts 2022, 12, x Van der Waals forces and hydrogen bonds and perhaps the displacement of12the of 18surface
hydroxyl group of TiO2 via the ligand exchange mechanism. Additionally, SO4 2− , due
to the double charge, has a high adsorption ability onto the surface of the catalyst and a
high scavenging affinity to HO• , and these reasons decreased the GBP degradation rate as
HO• , and these reasons decreased the GBP degradation rate as compared to the other ani-
onscompared
[52]. to the other anions [52].
3− 2− 2− − −
PO43−
𝑃𝑂 𝐻H
4 ++ 2O →
2 O→ 𝐻𝑃𝑂
HPO 4 +OH
4 +𝑂𝐻 (6) (6)
𝐻𝑃𝑂242− •
− +𝑂𝐻 → 𝑂𝐻 − +𝐻 •−
−2 +𝐻𝑃𝑂4 (7)
HPO4 +OH → OH + H2 + HPO4•−
•
(7)
+
𝑆𝑂42−2+−ℎ𝑉𝐵 → •−
+ 𝑆𝑂4 (8)
SO4 +hVB → SO4•− (8)

Figure 10. Effect of different water anions on GBP degradation in the Cu-TiO2 /UVA process
Figure 10. Effect of different water anions on GBP degradation in the Cu-TiO2/UVA process (GBP =
(GBP = 10 mg/L, pH = 8, catalyst = 0.4 g/L, anion = 1 mM, reaction time = 20 min).
10 mg/L, pH = 8, catalyst = 0.4 g/L, anion = 1 mM, reaction time = 20 min).

2.2.5. Mineralization and Pathway Study of GBP Degradation in the

Cu-TiO2/UVA Process
To evaluate the mineralization efficiency of GBP molecules in the Cu-TiO2/UVA pho-
 Catalysts 2022, 12, 1310 13 of 18

2.2.5. Mineralization and Pathway Study of GBP Degradation in the Cu-TiO2 /UVA Process
To evaluate the mineralization efficiency of GBP molecules in the Cu-TiO2 /UVA pho-
tocatalytic process, the TOC concentration was measured when the process was operated
under optimum conditions. According to the obtained result (Figure 11a), the removal of
TOC increased with the reaction time and reached 63% at the reaction time of 60 min. In
addition, the PFO removal rate of TOC under the selected condition was determined to
be 0.016 min−1 (Figure 11b). These results clearly indicate that the developed process effi-
x ciently mineralized GBP. The high degree of TOC removal at 60 min can be13demonstrated
of 18
that the GBP molecules were changed to simple materials, which might be completed by
continuing the reaction time. The mineralization of adsorbed GBP on Cu-TiO2 is possible
either by direct oxidation of GBP on the catalyst surface or by produced hydroxyl radicals
the release of nitrite and nitrate
(Equation (9)). ions, and desulfurization are the main steps in the miner-
alization of antibiotic compounds.
HO• + RH → R• + H2 O → CO2 + H2 O + mineral acids (9)

70

(a)
60

50
TOC removal (%)

40

30

20

10

0
0 10 20 30 40 50 60
Reaction time (min)

1.0 (b)

0.8
-ln (TOCt/TOC0)

0.6

R2=0.994
0.4
y=0.016 x

0.2

0.0

0 10 20 30 40 50 60
Reaction time (min)

Figure 11. Mineralization percentage (a) and rate (b) of GBP in the Cu-TiO2 /VUA process
Figure 11. Mineralization =percentage
(GBP (a)= and
10 mg/L, pH rate (b)
8, catalyst ofg/L).
= 0.4 GBP in the Cu-TiO2/VUA process (GBP = 10
mg/L, pH = 8, catalyst = 0.4 g/L).

The difference between GBP degradation and mineralization rate proved the for-
mation of some intermediates identified in the reaction solution. For this purpose, the
degradation intermediates of the GBP were conducted by LC-MS spectra under the opti-
Catalysts 2022, 12, 1310 14 of 18

RH and R• are organic substances and organic radicals, respectively. Evgenidou

et al. [55] examined the mineralization of a mixture of eight antibiotics using Cu-TiO2
photocatalysts. Against complete degradation of antibiotic compounds, the reduction
in TOC after 30 min was not more than 20%, indicating the formation of intermediate
products. There is a need for a long time in photocatalyst processes to achieve complete
mineralization, approving the formation of recalcitrant intermediates. In their study,
defluorination, the release of nitrite and nitrate ions, and desulfurization are the main steps
in the mineralization of antibiotic compounds.
The difference between GBP degradation and mineralization rate proved the formation
of some intermediates identified in the reaction solution. For this purpose, the degradation
intermediates of the GBP were conducted by LC-MS spectra under the optimal condition at
60 min. Accordingly, four transformation intermediates were measured based on the m/z
values, and the degradation pathway was proposed in Figure 12. Gabapentin is unstable
and can be spontaneously converted to gabapentin lactam (m/z 154) during dehydra-
tion [56]. Then, the deoxygenation of the C-O bond resulted in forming an intermediate
with m/z 128. The recorded fragment of an intermediate, such as cyclohexane (m/z 84) and
isopropyl radical (m/z 43), is related to the presence of reactive species (hVB +
/HO• /O2•− )
that destroyed the N-C, C-C, and N-H bonds to low molar mass. Finally, simple products,
such as CO2 and NH4+ , were observed in this reaction, confirming the effective mineral-
ization of GBP in the photocatalytic process with an as-made Cu-TiO2 catalyst. Dal Bello
et al. [57] investigated GBP degradation in the presence of a TiO2 photocatalyst. The degra-
dation of GBP (m/z 172) consisted of several stages. Firstly, the loss of a water molecule at
Catalysts 2022, 12, x
m/z 154; secondly, simultaneous loss of NH3 (m/z 137) and carbon monoxide (m/z14126); of 18

and finally, losses of water and carbon monoxide.

Figure 12.
Figure 12.Proposed
Proposedpathway
pathwayfor forGBP
GBPdegradation
degradationininthe
theCu-TiO
Cu-TiO 2/UVAprocess
2 /UVA process(GPB
(GPB==10
10mg/L,
mg/L,
pH== 8,
pH 8, catalyst
catalyst == 0.4
0.4 g/L,
g/L, reaction
reaction time
time ==60
60min).
min).

3.
3. Materials
Materials and
and Methods
Methods
3.1. Chemicals
3.1. Chemicals
Gabapentin (molecular formula: C9 H17 NO2 ) was obtained from Local Pharmaceutical.
Gabapentin (molecular formula: C9H17NO2) was obtained from Local Pharmaceuti-
Titanium isopropoxide (C12 H28 O4 Ti), isopropyl alcohol (CH3 O8 ), acetic acid (CH3 COOH),
cal. Titanium isopropoxide (C12H28O4Ti), isopropyl alcohol (CH3O8), acetic acid
copper acetate Cu(CH3 COO)2 , potassium dihydrogen phosphate (KH2 PO4 ), dipotassium
(CH3COOH), copper acetate Cu(CH3COO)2, potassium dihydrogen phosphate (KH2PO4),
dihydrogen phosphate (K2 HPO4 ), HPLC grade water and acetonitrile were purchased from
dipotassium dihydrogen phosphate (K2HPO4), HPLC grade water and acetonitrile were
the local market. In this work, all solutions were supplied with deionized water.
purchased from the local market. In this work, all solutions were supplied with deionized
water.

3.2. Synthesis and Characterization of Cu-TiO2 Nanoparticles

First, 10 mL of isopropyl alcohol and 3 mL of acetic acid were mixed in a glass con-
tainer, and then 2.5 mL of titanium isopropoxide as a precursor was added dropwise into
Catalysts 2022, 12, 1310 15 of 18

3.2. Synthesis and Characterization of Cu-TiO2 Nanoparticles

First, 10 mL of isopropyl alcohol and 3 mL of acetic acid were mixed in a glass container,
and then 2.5 mL of titanium isopropoxide as a precursor was added dropwise into the
above solution. The reaction was carried out at an ambient temperature and stirred at
80 rpm for 30 min. Then 2 mL of distilled water was added drop by drop to the mixture
under the hood. Finally, after 3 to 5 min mixing, the obtained gel was dried at 100 ◦ C and
calcined at 500 ◦ C for 2 h under an air atmosphere. To prepare the Cu-doped TiO2 , 0.319 g
copper acetate was dissolved in 10 mL of distilled water; the obtained solution was added
dropwise to the titanium dioxide gel under mixing, and the prepared gel was calcined
under conditions similar to the plain TiO2 .
The crystalline phase of the prepared catalyst was detected based on the X-ray diffrac-
tion (XRD) analysis in the 2θ scanning range from 10 to 80◦ , and Cu as anode material
with L radiation of 1.54 Å. The surface functional groups were identified by a Fourier trans-
form infrared spectroscopy (FTIR) in the frequency range of 400–4000 cm−1 . The surface
structure and elemental distribution of as-the prepared catalyst were determined by field
emission scanning electron microscopy (FE-SEM) coupled with energy-dispersive X-ray
spectroscopy (EDX). The actual size of Cu-TiO2 was obtained with transmission electron
microscopy (TEM) using Philips CM30. The specific surface area was characterized by
Brunauer–Emmett–Teller (BET) in the condition of nitrogen adsorption/desorption at 77 ◦ k.
Energy band gap and photoelectronic quality were evaluated by differential reflectance
spectroscopy (DRS) and photoluminescence (PL) methods, respectively. Finally, the identi-
fication of the intermediate through the gabapentin photodegradation was conducted by
liquid chromatography-mass spectrometry (LC-MS) analysis.

3.3. Experimental and Analytical Procedures

The photodegradation efficiency of the as-prepared catalyst for gabapentin removal
was examined under UVA-LED irradiation in a batch-quartz photoreactor with an inner
diameter and volume of 10 cm and 50 mL, respectively. A setup equipped with 18 LEDs
(3 W, SUN LED, Seoul Semiconductor, Korea) and emitted UVA photons (365 nm) was
applied as a light source. Generally, a given range of catalysts was dispersed into the reactor
with GBP solution (10 mg/L in all tests) at the target pH, stirred at an interval determined
times for degradation of Gabapentin by Cu-TiO2 under UVA-LED irradiation. Then 5 mL
of sample was filtered through a 0.2-micron syringe filter and the residual concentration
of the contaminant was monitored by high-performance liquid chromatography (HPLC,
Eclipse Plus C18 column; 3.5 µm, 4.6 × 100 mm, Agilent) with UV detection at 210 nm. The
mobile phase consisting of phosphate buffer (20 mM, pH = 6.2) and 25% acetonitrile, was
conducted at a 1 mL/min flow rate [5]. The removal efficiency of the GBP was calculated
using the following equation:

C0 − Ct
Removal efficiency (%) = × 100 (10)
C0

which C0 and Ct are the initial and final concentrations of GBP, respectively. All the
experiments were conducted in duplicate, and the mean of the results was reported. The
standard deviation was within ±5%.

4. Conclusions
Doping Cu-TiO2 was successfully performed by the sol-gel approach for GBP de-
composition under the UVA-LED system. Based on the DRS technique, the band gap of
the as-made catalyst was calculated at about 1.48 eV, and the pL results indicated a low
recombination rate of charge carriers compared to pure TiO2 nanoparticles. The Cu-TiO2
particles/UVA-LED system indicated high GBP removal efficiency with a reaction rate
constant of about 0.122 min−1 under optimal conditions. In addition to investigating the
common parameters (catalyst concentration, solution pH, and reaction time), the effect
of scavengers and water matrix were also checked on the trend of GBP removal under
Catalysts 2022, 12, 1310 16 of 18

the photocatalytic process. The order of the negative effect of the water matrix on GBP
degradation was PO4 3− > SO4 2− , and other anions did not affect the reaction. Scavenger
experiments revealed that the h+ and HO• had a significant role in the reaction mecha-
nism of the Cu-TiO2 particles/UVA-LED system. Finally, the mineralization rate by TOC
measurement was obtained at about 63% at 60 min reaction time, and the identified in-
termediates suggested that the pollutant converted to simple compounds. As a result,
the as-made Cu-TiO2 nanocomposite showed high photocatalytic properties under UVA
irradiation; thus, the Cu-TiO2 /UVA process was confirmed under the bench-scale condition
as a promising and efficient method for the removal of pharmaceutical compounds from
the contaminated water and wastewater.

Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/catal12111310/s1, Figure S1: FE-SEM (a), EDX (b), Elemental
mapping (c,d), and TEM (e) of TiO2 .
Author Contributions: R.A.: Investigation, Writing—original draft, Writing—review & editing,
Visualization. G.M., S.S. and F.R.: Conceptualization, Methodology, Resources, Writing—original
draft, Writing—review & editing, Supervision, Project administration. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: Data is available on request.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Choi, Y.; Lee, J.H.; Kim, K.; Mun, H.; Park, N.; Jeon, J. Identification, quantification, and prioritization of new emerging pollutants
in domestic and industrial effluents, Korea: Application of LC-HRMS based suspect and non-target screening. J. Hazard. Mater.
2021, 402, 123706. [CrossRef] [PubMed]
2. Cheshmeh Khavar, A.H.; Moussavi, G.; Mahjoub, A.R. The preparation of TiO2 @rGO nanocomposite efficiently activated with
UVA/LED and H2 O2 for high rate oxidation of acetaminophen: Catalyst characterization and acetaminophen degradation and
mineralization. Appl. Surf. Sci. 2018, 440, 963–973. [CrossRef]
3. Akbari, S.; Moussavi, G.; Giannakis, S. Efficient photocatalytic degradation of ciprofloxacin under UVA-LED, using S, N-doped
MgO nanoparticles: Synthesis, parametrization and mechanistic interpretation. J. Mol. Liq. 2021, 324, 114831. [CrossRef]
4. Goswami, A.; Jiang, J.Q.; Petri, M. Non-parametric regression analysis of diuron and gabapentin degradation in lake Constance
water by ozonation and their toxicity assessment. Water 2019, 11, 852. [CrossRef]
5. Ragham, P.K.; Chandrasekhar, K.B. Development and validation of a stability-indicating RP-HPL C-CAD method for gabapentin
and its related impurities in presence of degradation products. J. Pharm. Biomed. Anal. 2016, 125, 122–129. [CrossRef] [PubMed]
6. Goswami, A.; Jiang, J.Q.; Petri, M. Treatability of five micro-pollutants using modified Fenton reaction catalysed by zero-valent
iron powder (Fe (0)). J. Environ. Chem. Eng. 2021, 9, 105393. [CrossRef]
7. Vymazal, J.; Březinová, T.D.; Koželuh, M.; Kule, L. Occurrence and removal of pharmaceuticals in four full-scale constructed
wetlands in the Czech Republic–the first year of monitoring. Ecol. Eng. 2017, 98, 354–364. [CrossRef]
8. Fundneider, T.; Alonso, V.A.; Wick, A.; Albrecht, D.; Lackner, S. Implications of biological activated carbon filters for micropollu-
tant removal in wastewater treatment. Water Res. 2021, 189, 116588. [CrossRef]
9. Kohantorabi, M.; Moussavi, G.; Mohammadi, S.; Oulego, P.; Giannakis, S. Photocatalytic activation of peroxymonosulfate
(PMS) by novel mesoporous Ag/ZnO@ NiFe2 O4 nanorods, inducing radical-mediated acetaminophen degradation under UVA
irradiation. Chemosphere 2021, 277, 130271. [CrossRef]
10. Chen, L.; Tang, J.; Song, L.N.; Chen, P.; He, J.; Au, C.T.; Yin, S.F. Heterogeneous photocatalysis for selective oxidation of alcohols
and hydrocarbons. Appl. Catal. B Environ. 2019, 242, 379–388. [CrossRef]
11. Kohantorabi, M.; Moussavi, G.; Oulego, P.; Giannakis, S. Radical-based degradation of sulfamethoxazole via UVA/PMS-assisted
photocatalysis, driven by magnetically separable Fe3 O4 @ CeO2 @ BiOI nanospheres. Sep. Purif. Technol. 2021, 267, 118665.
[CrossRef]
12. Thambiliyagodage, C.; Mirihana, S. Photocatalytic activity of Fe and Cu co-doped TiO2 nanoparticles under visible light. J. Sol-Gel
Sci. Technol. 2021, 99, 109–121. [CrossRef]
13. Thambiliyagodage, C.; Usgodaarachchi, L. Photocatalytic activity of N, Fe and Cu co-doped TiO2 nanoparticles under sunlight.
Curr. Res. Green Sustain. Chem. 2021, 4, 100186. [CrossRef]
14. Cheshmeh Khavar, A.H.; Moussavi, G.; Mahjoub, A.R.; Satari, M. Facile preparation of multi-doped TiO2 /rGO cross-linked 3D
aerogel (GaNF@TGA) nancomposite as an efficient visible-light activated catalyst for photocatalytic oxidation and detoxification
of atrazine. Sol. Energy 2018, 173, 848–860. [CrossRef]
Catalysts 2022, 12, 1310 17 of 18

15. Tang, T.; Yin, Z.; Chen, J.; Zhang, S.; Sheng, W.; Wei, W.; Xiao, Y.; Shi, Q.; Cao, S. Novel pn heterojunction Bi2 O3 /Ti3+ -TiO2
photocatalyst enables the complete removal of tetracyclines under visible light. Chem. Eng. J. 2021, 417, 128058. [CrossRef]
16. Gao, D.; Liu, W.; Xu, Y.; Wang, P.; Fan, J.; Yu, H. Core-shell Ag@ Ni cocatalyst on the TiO2 photocatalyst: One-step photoinduced
deposition and its improved H2 -evolution activity. Appl. Catal. B Environ. 2020, 260, 118190. [CrossRef]
17. Adnan, M.; Muhd Julkapli, N.; Amir, M.; Maamor, A. Effect on different TiO2 photocatalyst supports on photodecolorization of
synthetic dyes: A review. Int. J. Environ. Sci. Technol. 2019, 16, 547–566. [CrossRef]
18. Sun, Q.; Lv, K.; Zhang, Z.; Li, M.; Li, B. Effect of contact interface between TiO2 and g-C3 N4 on the photoreactivity of g-C3 N4 /TiO2
photocatalyst:(0 0 1) vs (1 0 1) facets of TiO2 . Appl. Catal. B Environ. 2015, 164, 420–427.
19. Jaiswal, R.; Bharambe, J.; Patel, N.; Dashora, A.; Kothari, D.; Miotello, A. Copper and Nitrogen co-doped TiO2 photocatalyst with
enhanced optical absorption and catalytic activity. Appl. Catal. B Environ. 2015, 168, 333–341. [CrossRef]
20. Cheng, C.; Fang, W.H.; Long, R.; Prezhdo, O.V. Water splitting with a single-atom Cu/TiO2 photocatalyst: Atomistic origin of
high efficiency and proposed enhancement by spin selection. J. Am. Chem. Sos. 2021, 1, 550–559. [CrossRef]
21. Čižmar, T.; Panžić, I.; Capan, I.; Gajović, A. Nanostructured TiO2 photocatalyst modified with Cu for improved imidacloprid
degradation. Appl. Surf. Sci. 2021, 569, 151026. [CrossRef]
22. Bensouici, F.; Bououdina, M.; Dakhel, A.; Tala-Ighil, R.; Tounane, M.; Iratni, A.; Souier, T.; Liu, S.; Cai, W. Optical, structural and
photocatalysis properties of Cu-doped TiO2 thin films. Appl. Surf. Sci. 2017, 395, 110–116. [CrossRef]
23. Raguram, T.; Rajni, K. Synthesis and analysing the structural, optical, morphological, photocatalytic and magnetic properties of
TiO2 and doped (Ni and Cu) TiO2 nanoparticles by sol–gel technique. Appl. Phys. A 2019, 125, 288. [CrossRef]
24. Vaiano, V.; Iervolino, G.; Rizzo, L. Cu-doped ZnO as efficient photocatalyst for the oxidation of arsenite to arsenate under visible
light. Appl. Catal. B Environ. 2018, 238, 471–479. [CrossRef]
25. Hossaini, H.; Moussavi, G.; Farrokhi, M. The investigation of the LED-activated FeFNS-TiO2 nanocatalyst for photocatalytic
degradation and mineralization of organophosphate pesticides in water. Water Res. 2014, 59, 130–144. [CrossRef] [PubMed]
26. Lin, C.-J.; Yang, W.-T. Ordered mesostructured Cu-doped TiO2 spheres as active visible-light-driven photocatalysts for degradation
of paracetamol. Chem. Eng. J. 2014, 237, 131–137. [CrossRef]
27. Sahu, M.; Biswas, P. Single-step processing of copper-doped titania nanomaterials in a flame aerosol reactor. Nanoscale Res. Lett.
2011, 6, 441. [CrossRef]
28. Colón, G.; Maicu, M.; Hidalgo, M.S.; Navío, J. Cu-doped TiO2 systems with improved photocatalytic activity. Appl. Catal. B
Environ. 2006, 67, 41–51. [CrossRef]
29. Sagadevan, S.; Vennila, S.; Singh, P.; Lett, J.A.; Oh, W.C.; Paiman, S.; Mohammad, F.; Al-Lohedan, H.A.; Fatimal, I.; Shahid, M.M.;
et al. Exploration of the antibacterial capacity and ethanol sensing ability of Cu-TiO2 nanoparticles. J. Exp. Nanosci. 2020, 15,
337–349. [CrossRef]
30. Ullattil, S.G.; Zavašnik, J.; Maver, K.; Finšgar, M.; Novak Tušar, N.; Pintar, A. Defective Grey TiO2 with Minuscule Anatase–Rutile
Heterophase Junctions for Hydroxyl Radicals Formation in a Visible Light-Triggered Photocatalysis. Catalysts 2021, 11, 1500.
[CrossRef]
31. Din, M.I.; Arshad, F.; Rani, A.; Aihetasham, A.; Mukhtar, M.; Mehmood, H. Single step green synthesis of stable copper oxide
nanoparticles as efficient photo catalyst material. Biomed. Mater. 2017, 9, 41–48.
32. Rajamannan, B.; Mugundan, S.; Viruthagiri, G.; Praveen, P.; Shanmugam, N. Linear and nonlinear optical studies of bare and
copper doped TiO2 nanoparticles via sol gel technique. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2014, 118, 651–656. [CrossRef]
[PubMed]
33. Norris, D.J.; Efros, A.L.; Erwin, S.C. Doped nanocrystals. Science 2008, 319, 1776–1779. [CrossRef] [PubMed]
34. Tasbihi, M.; Kočí, K.; Troppová, I.; Edelmannová, M.; Reli, M.; Čapek, L.; Schomäcker, R. Photocatalytic reduction of carbon
dioxide over Cu/TiO2 photocatalysts. Environ. Sci. Pollut. Res. 2018, 25, 34903–34911. [CrossRef] [PubMed]
35. Akbari, S.; Moussavi, G.; Decker, J.; Marin, M.L.; Bosca, F.; Giannakis, S. Superior visible light-mediated catalytic activity of
a novel N-doped, Fe3 O4 -incorporating MgO nanosheet in presence of PMS: Imidacloprid degradation and implications on
simultaneous bacterial inactivation. Appl. Catal. B Environ. 2022, 317, 121732. [CrossRef]
36. Mathew, S.; Ganguly, P.; Rhatigan, S.; Kumaravel, V.; Byrne, C.; Hinder, S.J.; Bartllet, J.; Nolan, M.; Pillai, S. Cu-doped TiO2 :
Visible light assisted photocatalytic antimicrobial activity. Appl. Sci. 2018, 8, 2067. [CrossRef]
37. Kohantorabi, M.; Giannakis, S.; Moussavi, G.; Bensimon, M.; Gholami, M.R.; Pulgarin, C. An innovative, highly stable Ag/ZIF-
67@ GO nanocomposite with exceptional peroxymonosulfate (PMS) activation efficacy, for the destruction of chemical and
microbiological contaminants under visible light. J. Hazard. Mater. 2021, 413, 125308. [CrossRef]
38. Li, L.; Liu, J.; Su, Y.; Li, G.; Chen, X.; Qiu, X.; Yan, T. Surface doping for photocatalytic purposes: Relations between particle size,
surface modifications, and photoactivity of SnO2 : Zn2+ nanocrystals. Nanotechnology 2009, 20, 155706. [CrossRef]
39. Reda, S.; Khairy, M.; Mousa, M. Photocatalytic activity of nitrogen and copper doped TiO2 nanoparticles prepared by microwave-
assisted sol-gel process. Arab. J. Chem. 2020, 13, 86–95. [CrossRef]
40. Etacheri, V.; Di Valentin, C.; Schneider, J.; Bahnemann, D.; Pillai, S.C. Visible-light activation of TiO2 photocatalysts: Advances in
theory and experiments. J. Photochem. Photobiol. C Photochem. Rev. 2015, 25, 1–29. [CrossRef]
41. Park, H.S.; Kim, D.H.; Kim, S.J.; Lee, K.S. The photocatalytic activity of 2.5 wt% Cu-doped TiO2 nano powders synthesized by
mechanical alloying. J. Alloys Compd. 2006, 415, 51–55. [CrossRef]
Catalysts 2022, 12, 1310 18 of 18

42. Apiwong-ngarm, K.; Pongwan, P.; Inceesungvorn, B.; Phanichphant, S.; Wetchakun, K.; Wetchakun, N. Photocatalytic activities
of Fe–Cu/TiO2 on the mineralization of oxalic acid and formic acid under visible light irradiation. Powder Technol. 2014, 266,
447–455. [CrossRef]
43. Varma, K.S.; Tayade, R.J.; Shah, K.J.; Joshi, P.A.; Shukla, A.D.; Gandhi, V.G. Photocatalytic degradation of pharmaceutical and
pesticide compounds (PPCs) using doped TiO2 nanomaterials: A review. Water Energy Nexus 2020, 3, 46–61. [CrossRef]
44. Ciavarella, A.B.; Gupta, A.; Sayeed, V.A.; Khan, M.A.; Faustino, P.J. Development and application of a validated HPLC method
for the determination of gabapentin and its major degradation impurity in drug products. J. Pharm. Biomed. Anal. 2007, 43,
1647–1653. [CrossRef] [PubMed]
45. Chen, M.; Yao, J.; Huang, Y.; Gong, H.; Chu, W. Enhanced photocatalytic degradation of ciprofloxacin over Bi2 O3 /(BiO)2 CO3
heterojunctions: Efficiency, kinetics, pathways, mechanisms and toxicity evaluation. Chem. Eng. J. 2018, 334, 453–461. [CrossRef]
46. Ahmad, S.; Yasin, A. Photocatalytic degradation of deltamethrin by using Cu/TiO2 /bentonite composite. Arab. J. Chem. 2020, 13,
8481–8488. [CrossRef]
47. Sharma, M.; Mandal, M.K.; Pandey, S.; Kumar, R.; Dubey, K.K. Visible-Light-Driven Photocatalytic Degradation of Tetracycline
Using Heterostructured Cu2 O–TiO2 Nanotubes, Kinetics, and Toxicity Evaluation of Degraded Products on Cell Lines. ACS
Omega 2022, 7, 33572–33586. [CrossRef]
48. Golshan, M.; Kakavandi, B.; Ahmadi, M.; Azizi, M. Photocatalytic activation of peroxymonosulfate by TiO2 anchored on cupper
ferrite (TiO2 @CuFe2 O4 ) into 2, 4-D degradation: Process feasibility, mechanism and pathway. J. Hazard. Mater. 2018, 359, 325–337.
[CrossRef]
49. Sarafraz, M.; Sadeghi, M.; Yazdanbakhsh, A.; Amini, M.M.; Sadani, M.; Eslami, A. Enhanced photocatalytic degradation of
ciprofloxacin by black Ti3+ /N-TiO2 under visible LED light irradiation: Kinetic, energy consumption, degradation pathway, and
toxicity assessment. Process Saf. Environ. Prot. 2020, 137, 261–272. [CrossRef]
50. Akbari, S.; Ghanbari, F.; Moradi, M. Bisphenol A degradation in aqueous solutions by electrogenerated ferrous ion activated
ozone, hydrogen peroxide and persulfate: Applying low current density for oxidation mechanism. Chem. Eng. J. 2016, 294,
298–307. [CrossRef]
51. Yang, X.J.; Shu, W.; Sun, H.m.; Wang, X.B.; Lian, J.S. Preparation and photocatalytic performance of Cu-doped TiO2 nanoparticles.
Trans. Nonferrous Met. Soc. China 2015, 25, 504–509. [CrossRef]
52. Anucha, C.B.; Altin, I.; Bacaksız, E.; Kucukomeroglu, T.; Belay, M.H.; Stathopoulos, V.N. Enhanced photocatalytic activity of
CuWO4 doped TiO2 photocatalyst towards carbamazepine removal under UV irradiation. Separations 2021, 8, 25. [CrossRef]
53. Wang, Q.; Rao, P.; Li, G.; Dong, L.; Zhang, X.; Shao, Y.; Gao, N.; Chu, W.; Xu, B.; An, N.; et al. Degradation of imidacloprid by
UV-activated persulfate and peroxymonosulfate processes: Kinetics, impact of key factors and degradation pathway. Ecotoxicol.
Environ. Saf. 2020, 187, 109779. [CrossRef]
54. Kohantorabi, M.; Moussavi, G.; Giannakis, S. A review of the innovations in metal-and carbon-based catalysts explored for
heterogeneous peroxymonosulfate (PMS) activation, with focus on radical vs. non-radical degradation pathways of organic
contaminants. Chem. Eng. J. 2021, 411, 127957. [CrossRef]
55. Evgenidou, E.; Chatzisalata, Z.; Tsevis, A.; Bourikas, K.; Torounidou, P.; Sergelidis, D.; Koltsakidou, A.; Lambropoulou, D.A.
Photocatalytic degradation of a mixture of eight antibiotics using Cu-modified TiO2 photocatalysts: Kinetics, mineralization,
antimicrobial activity elimination and disinfection. J. Environ. Chem. Eng. 2021, 9, 105295. [CrossRef]
56. Herrmann, M.; Menz, J.; Olsson, O.; Kümmerer, K. Identification of phototransformation products of the antiepileptic drug
gabapentin: Biodegradability and initial assessment of toxicity. Water Res. 2015, 85, 11–21. [CrossRef] [PubMed]
57. Dal Bello, F.; Medana, C.; Zorzi, M.; Kuck, B.; Fabbri, D.; Calza, P. Liquid chromatography/mass spectrometry analytical
determination of gabapentin transformation products by heterogeneous photocatalysis and environmental evaluation. Rapid
Commun. Mass Spectrom. 2020, 34, e8925. [CrossRef]