catalysts

Article
Solar Chlorine Activation for Efficient Rhodamine B Removal
in Strong Basic pH: Processing Conditions, Radicals Probing,
and TiO2 Nanocatalyst Effect
Hana Bouchoucha 1 , Salim Bekkouche 1 , Slimane Merouani 1, *, Aissa Dehane 1 and Oualid Hamdaoui 2

1 Laboratory of Environmental Process Engineering, Faculty of Process Engineering, University Constantine 3

Salah Boubnider, P.O. Box 72, Constantine 25000, Algeria; [email protected] (H.B.);
[email protected] (S.B.); [email protected] (A.D.)
2 Chemical Engineering Department, College of Engineering, King Saud University,
P.O. Box 800, Riyadh 11421, Saudi Arabia; [email protected]
* Correspondence: [email protected]

Abstract: In recent years, there has been growing interest in the application of UV/chlorine advanced
oxidation processes for wastewater treatment. However, few studies have investigated this process in
a strongly basic medium (pH > 10), which is a common characteristic of many industrial effluents. In
addition, the use of artificial UV lamps in these processes can be costly. To address these challenges,
we investigated the use of solar light (referred to as Solar-L) in the Solar-L/chlorine process for the
degradation of Rhodamine B (RhB) in a strongly basic medium (pH 11). We found that separate
solar light or chlorination showed no degradation after half an hour, but the Solar-L/chlorine process
effectively degraded RhB, with complete removal achieved in only 30 min, using 1000 µM ClO− . The
process also resulted in a significant reduction of TOC, i.e., 60% after 120 min and 80% after 240 min.
Our results indicate that both • OH/O•− and reactive chlorine species (RCS) were involved in the
degradation process, while O3 played no role. The process performance improved with the decreasing
initial contaminant concentration and increasing temperature (up to 55 ◦ C). The addition of a TiO2
Citation: Bouchoucha, H.; nanocatalyst to the Solar-L/chlorine system significantly improved the RhB degradation efficiency
Bekkouche, S.; Merouani, S.; Dehane, by more than 30%. It was found that neither adsorption (on TiO2 ) nor Solar-L/TiO2 photolysis
A.; Hamdaoui, O. Solar Chlorine
contributed to the dye removal by the Solar-L/chlorine/TiO2 system. Instead, the improvement
Activation for Efficient Rhodamine B
associated with the Solar-L/chlorine/TiO2 system was related to the involvement of hypochlorite
Removal in Strong Basic pH:
in the photocatalytic reaction at the catalyst surface. A detailed discussion of the effect of TiO2
Processing Conditions, Radicals
was carried out based on the physicochemical properties of RhB and TiO2 catalyst with respect to
Probing, and TiO2 Nanocatalyst
Effect. Catalysts 2023, 13, 942.
the solution’s pH. In conclusion, this study highlights the potential of solar light as a sustainable
https://doi.org/10.3390/ and efficient technology for the treatment of polluted water in strong basic media in the presence
catal13060942 of chlorine and chlorine/TiO2 as additives. These valuable findings provide a basis for the future
research and development of this promising technology for water treatment applications.
Academic Editor: Vincenzo Vaiano

Received: 26 April 2023 Keywords: solar light; chlorine activation; strong basic pH; TiO2 /chlorine photocatalysis; rhodamine B;
Revised: 18 May 2023 degradation
Accepted: 20 May 2023
Published: 27 May 2023

1. Introduction
Copyright: © 2023 by the authors.
Water utilities face the challenge of treating drinking water sources contaminated
Licensee MDPI, Basel, Switzerland.
with organic pollutants, such as pharmaceuticals, insecticides, and textile dyes, that are
This article is an open access article released into the environment from a variety of sources, including industrial manufacturing,
distributed under the terms and agricultural runoff, and municipal wastewater [1–4]. Unfortunately, conventional water
conditions of the Creative Commons treatment methods are ineffective at removing these contaminants [5]. While UV irradiation
Attribution (CC BY) license (https:// alone may not completely remove these micropollutants, combining UV with oxidants such
creativecommons.org/licenses/by/ as H2 O2 , S2 O8 2− , IO4 − , and chlorine (HOCl/ClO− ) can produce highly reactive radicals
4.0/). (e.g., • OH, SO4 •− , iodine, and reactive chlorine species) that enhance the removal efficiency

Catalysts 2023, 13, 942. https://doi.org/10.3390/catal13060942 https://www.mdpi.com/journal/catalysts

Catalysts 2023, 13, 942 2 of 15

of these micropollutants [6–9]. For effective water treatment, UV-assisted processes such as
UV/H2 O2 , UV/S2 O8 2− , and UV/chlorine are used. Although H2 O2 and persulfate-based
AOPs can only utilize light in the UV-C interval due to their limited molar absorptivity,
chlorine photolysis can be used for solar treatment because it absorbs light at longer
wavelengths [10,11]. Additionally, chlorine photolysis uses a common disinfectant that
is less expensive and easier to transport than hydrogen peroxide and persulfate [12]. In
contrast to the UV/H2 O2 and UV/persulfate processes, the UV/chlorine system does not
necessitate a residual chlorine quenching step to remove the rest of the chlorine [5]. The
disinfection and oxidation mechanism of the UV/chlorine AOP treatment process is also
enhanced in the presence of chloramines, which are formed from ammonia, a common
contaminant in wastewater.
The chemistry of chlorine photolysis is complex due to the pH- and wavelength-
dependent photolysis of chlorine and the subsequent pathways for oxidant production [13].
The pKa of HOCl/OCl− is 7.5, and HOCl dominates at pH 3–5, while OCl− dominates at
pH > 9 [13]. HOCl absorbs maximally at 220 nm, while OCl− absorbs at about 290 nm [13].
The photolysis of chlorine can produce a group of highly reactive oxidants, including • OH
and chlorine-reactive species (RCS: ClO• , Cl• , and Cl2 •− ), which are capable of degrading
organic water contaminants [11]. For example, the photolysis of HClO can primarily
produce • OH and Cl• radicals via HOCl + hν → • OH + Cl• [14]. • OH and RCS are expected
to be the main oxidants that play a significant role in the UV/chlorine system, especially
at natural water pHs (pH 6–9) [11]. These radicals react with organic compounds at rates
of about 102 –106 M−1 s−1 for Cl2 •− , about 107 –109 M−1 s−1 for ClO• , and 108 –1011 M−1 s−1
for • OH and Cl• [11,13]. The photolysis of chlorine is therefore a promising approach for
the degradation of organic water contaminants, although its complex chemistry requires
careful consideration to optimize its use in water treatment applications.
Although the UV/chlorine process has demonstrated its efficiency for the degradation
of refractory organic pollutants in acidic to slightly basic media (3 ≤ pH ≤ 10), its efficiency
in strongly basic media has rarely been addressed. The first flash photolysis experiments
by Buxton and Subhani [14] showed that the hypochlorite ion (ClO− ) produces chloride
ion, • OH/O•− , Cl− , and O(3 P) as its primary photoproducts at 253.7, 313, and 365 nm
when the medium is basic. While O(1 D) was produced at 253.7 nm and 313 nm, it was not
observed at 365 nm [14]. Once formed, primary photoproducts of ClO− begin to degrade
into unstable, transient species such as ClO• , Cl2 •− , Cl2 O, and Cl2 O2 , as well as stable
by-products such as O2 , Cl− , ClO2 − , ClO3 − , and ClO4 − , with secondary oxidants such
as O3 , H2 O2 , and ClO2 also being formed. Buxton and Subhani [14] proposed a series of
reactions to explain how Cl− , O2 , ClO2 − , ClO3 − , and O3 are produced by the photolysis of
ClO− (Reactions 1–24). The reactive species generated as primary photoproducts of ClO−
initiate the chain reaction. The hypochlorite ion is oxidized by • OH/O•− and Cl• to form
ClO• (Reactions 4–6), which rapidly dimerizes to form Cl2 O2 (Reaction 7).
Considering that the majority of AOPs are inefficient in strong basic media [15], we
would like to investigate the viability of the UV/chlorine process under these conditions.
In fact, several industrial processes generate strong alkaline effluents that require specific
neutralization treatment prior to oxidation [16]. Furthermore, the use of solar light (Solar-L)
as an energy source for the UV/chlorine process offers several advantages over traditional
artificial light sources. Solar light is abundant and renewable, and its use can significantly
reduce operating costs and environmental impact. Therefore, investigating the effectiveness
of the UV/chlorine process under solar irradiation in strong alkaline media can have
important implications for the development of sustainable and cost-effective wastewater
treatment technologies.
ClO− + hv → O(3 P) + Cl− (1)
ClO− + hv → O•− + Cl• (2)
ClO− + hv → Cl− + O(1 D) (3)
OCl− + • OH → ClO• + OH− (4)
Catalysts 2023, 13, 942 3 of 15

OCl− + O•− → ClO• + O2− (5)

Cl• + OCl− → Cl− + ClO• (6)
2 ClO• Cl2 O2 (7)
− − +
Cl2 O2 + H2 O → ClO2 + ClO + 2H (8)
Cl2 O2 + H2 O → Cl− + O2 + ClO− + 2H+ (9)
Cl2 O2 + ClO2 − → ClO3 − + Cl2 O (10)
Cl2 O + H2 O 2 HOCl (11)
•
OH + ClO2 − → ClO2 + HO− (12)
O•− + ClO2 − → ClO2 + O2 − (13)
•
OH + ClO3 − → Products (14)
•− −
O + ClO3 → Products (15)
O(1D) + H2 O → H2 O2 (16)
ClO− + H2 O2 → O2 + Cl− + H2 O (17)
O(3 P) + ClO− → ClO2 − (18)
O(3 P) + ClO− → Cl− + O2 (19)
O(3 P) + ClO2 − → ClO3 - (20)
O(3 P) + ClO2 − → Cl− + O2 + O(3 P) (21)
3
O( P) + O2 → O3 (22)
O•− + O2 O3 •− (23)
ClO• + O3 •− → O3 + ClO− (24)
Rhodamine B (RhB), a basic dye, is a fluorescent organic compound that is used
for many applications, including biological stains, pH indicators, and tracers [17]. It has
also been used as a colorant in the textile and food industries. However, RhB poses a
significant environmental threat due to its toxicity and persistence in water [18,19], as well
as causing phototoxic and photoallergic reactions. It has been experimentally shown to be
carcinogenic, a reproductive and developmental toxicant, a neurotoxicant, and a chronic
toxicant to both humans and animals [1]. Consequently, several studies have focused on
the removal of RhB from wastewater and environmental matrices [20–24]. However, there
was no previous study on applying UV/chlorine to degrade this effective water pollutant,
especially with using solar light.
The main objective of this work was to investigate the effectiveness of the Solar-L/chlorine
process for the degradation and mineralization of Rhodamine B (RhB) under strong al-
kaline conditions. The experimental conditions and radical scavenger assays were inves-
tigated to determine the primary reactive species involved in the degradation process
(Solar-L/chlorine at strong basic pH). In addition, the performance of the process was
evaluated by introducing a TiO2 photocatalyst to determine the potential enhancement of
pollutant degradation by combining Solar-L/chlorine photolysis and TiO2 photocatalysis
under strong basic conditions.

2. Results and Discussion

2.1. Solar-Light/Chlorine Process Efficiency in Basic Medium
The degradation of RhB at pH 11 was studied using solar irradiation alone, chlorine
alone (as hypochlorite ions), and a combination of solar irradiation and chlorine. The
Catalysts 2023, 13, 942 4 of 15

degradation kinetics were followed as a function of time for 30 min. The results are
shown in Figure 1a–c. No degradation occurred with solar light and chlorine (different
doses) separately, but complete removal was achieved by combining the two systems (with
1000 µM chlorine) in 30 min, with an exponential decay of the dye concentration over time,
reflecting a pseudo-first-order kinetic law (C/C0 = e−kt ). The t1/2 for the combined system
was 4 min and 13 min for 500 and 1000 µM chlorine, respectively, with pseudo-first-order
rate constants of k = 0.077 and 0.174 min−1 , respectively. However, the combined system
was insignificant at low doses of chlorine (below 300 µM), where maximum RhB removal
of less than 20% was achieved. This suggests that the system depends on a threshold
concentration of chlorine to achieve the efficient degradation of RhB. The beneficial effect
of the combined solar light/chlorine system was certainly attributed to the formation
of reactive species (hydroxyl and RCS) upon chlorine photolysis by the UV portion of
the solar spectrum. The Suntest modulator used in this study generates UV radiation
with wavelengths between 290 and 400 nm (UVB and UVA part of the solar spectrum),
Catalysts 2023, 13, x which represents about 7% of the global solar spectrum. Overall, these results demonstrate
5 of 16
the potential of the solar UV/chlorine process for the degradation of RhB (and similar
persistent textile dyes) in a strong alkaline medium.

Figure
Figure 1. RhBRhB degradation
degradation uponupon (a) solar
(a) solar light irradiation
light irradiation (Solar-L),
(Solar-L), (b) chlorine,
(b) chlorine, and
and (c) Solar-
L/chlorine systems (C = 10 µM, pH 11, and temp. 25 ± 2 °C).
(c) Solar-L/chlorine systems (C0 = 10 µM, pH 11, and temp. 25 ± 2 C).
0 ◦

The
The degradation
degradation of of RhB
RhB waswas confirmed
confirmed by analyzing
analyzing the UV-Vis
UV-Vis spectra
spectra and
and TOC
TOC
reduction during the treatment of RhB
reduction during the treatment of RhB (5 mg/L) (5 mg/L) at pH 11. The changes in UV-Vis
UV-Vis spectra
spectra
and
and TOC
TOCremoval
removalresults
resultsare
areshown
shown in in
Figure 2a 2a
Figure (60(60
minmin
treatment) andand
treatment) Figure 2b (250
Figure 2b min
(250
treatment), respectively.
min treatment), The initial
respectively. RhB RhB
The initial spectrum (t = 0)
spectrum (t =showed twotwo
0) showed bands with
bands maxima
with max-
at
ima550atand
550290
andnm.290During treatment,
nm. During the 550
treatment, thenm550 band
nm disappeared after 30
band disappeared min,30while
after min,
the absorbance at 290 nm decreased from 0.6 to 0.164 (72% decrease)
while the absorbance at 290 nm decreased from 0.6 to 0.164 (72% decrease) and continued and continued to
decrease to 0.084 for more than 45 min. From Figure 2b, the TOC decreased
to decrease to 0.084 for more than 45 min. From Figure 2b, the TOC decreased by 6% at 15 by 6% at
15 min, 16% at 30 min, 43% at 60 min, 60% at 120 min, 73% at 180
min, 16% at 30 min, 43% at 60 min, 60% at 120 min, 73% at 180 min, and 80% at 240 min. min, and 80% at
The disappearance of the 550 nm band is attributed to the degradation of the chromo-
phoric group. The 290 nm band is associated with the aromatic or naphthenic group, and
its disappearance is explained by the formation of intermediates that can absorb at this
wavelength or by the formation of smaller molecules that do not have this chromophore.
Catalysts 2023, 13, 942 5 of 15

240 min. The disappearance of the 550 nm band is attributed to the degradation of the
chromophoric group. The 290 nm band is associated with the aromatic or naphthenic group,
and its disappearance is explained by the formation of intermediates that can absorb at this
wavelength or by the formation of smaller molecules that do not have this chromophore.
The decay of the 290 nm band was slower than that of the 550 nm band due to the preference
of • OH/O•− and RCS to react primarily with the chromophoric group rather than with the
aromatic rings of the dye. However, the decay of the 290 nm band strongly indicates RhB
degradation (destruction), not just decolorization, and provides evidence of mineralization,
which is confirmed by the TOC results in Figure 2b. However, the removal of TOC took
Catalysts 2023, 13, x a longer time because it is related not only to the degradation of the dye molecules but
6 of 16
also to the degradation by-products existing along with the dye present in the solution
(degradation by-products).

Figure 2. Change
Change in
in (a)
(a) RhB’s
RhB’s UV-Vis
UV-Vis spectra and (b) TOC
TOC abatement during the treatment
treatment with the
Solar-L/chlorine
Solar-L/chlorineprocess
process(C (C00==1010µM,
µM,pH
pH11,
11,and
andtemp.
temp.25
25±± 2 ◦ C).
2 °C).

2.2. Probing
2.2. Probing the
the Reactive
Reactive Species
Species Involved
Involved in in RhB
RhB Degradation
Degradation by by Solar-L/Chlorine
Solar-L/Chlorine Process
Process
As described in Section 2, when aqueous hypochlorite is
As described in Section 2, when aqueous hypochlorite is exposed to irradiation withexposed to irradiation with
wavelengths between
wavelengths between 300 300 and
and 400400 nmnm atat aa basic
basic pH,
pH, this
this leads
leads toto the
the formation
formation of
of reactive
reactive
species such as • OH/O•− , RCS (Cl• , ClO• , Cl •− ), and O by photolysis. These species play
species such as OH/O , RCS (Cl , ClO , Cl2 ), and O3 by photolysis. These species play
• •− • • 2
•− 3
aa critical
critical role
role in
in the
the degradation
degradation of of water
water contaminants
contaminants by by the
the UV/chlorine
UV/chlorineprocess
process[11,13].
[11,13].
To determine the specific roles of these radicals, radical scavengers
To determine the specific roles of these radicals, radical scavengers such as ascorbic acid, such as ascorbic acid,
benzoic acid (BA), tert-butanol (TBA), and N saturation were
benzoic acid (BA), tert-butanol (TBA), and N22 saturation were used. N22 saturation was used. N saturation was
used to remove dissolved O , which is responsible for O production
used to remove dissolved O22, which is responsible for O33production via Reactions 22–24. via Reactions 22–24.
Thus, N
Thus, N22 saturation
saturation provides
provides information
information on on the
the role
role of
of ozone
ozone in in the
the overall
overall degradation
degradation
rate of the dye. Ascorbic acid is well-known as a common reductant (scavenger) of all
rate of the dye. Ascorbic acid is well-known as a common reductant (scavenger) of all
oxidants [25,26]. It was used to confirm the free radical pathway in the degradation of RhB.
oxidants [25,26]. It was used to confirm the free •− radical pathway in the degradation of
TBA, on the other hand, can scavenge • OH/O (k = 6.0 × 108 /5.0 × 108 M−1 s−1 ), Cl•
RhB. TBA, on8 the−1other hand, can scavenge •OH/O•− (k = 6.0 × 108/5.0 × 108 M−1s−1), Cl• (k =
(k = 3.0 × 10 M s−1 ), and ClO• (k = 1.3 × 107 M−1 s−1 ), with a negligible effect on Cl •−
3.0 × 108 M−12 s−1),−1and − 1 ClO• (k = 1.3 × 107 M−−13s−1),−with 1 − 1 a negligible effect on Cl2•− (k = 7 × 2102
(k = 7 × 10 M s ) and O (k ≤ 3 × 10 M s ), providing insight into the•−plausible
M−1s−1) and•− O3 (k ≤ 3 × 10−3 M3−1s−1), providing insight into the plausible role of Cl2 [27]. BA
role of Cl2 [27]. BA is capable of scavenging • OH/O•− (k~1.8 × 109 M−1 s−1 ) and Cl•
is capable of scavenging − −
•OH/O•− (k~1.8 × 109 M−1s−1) and Cl• (k = 3.0 ×1010 M−1s−1), but it
10 1 1
(k = 3.0 × 10 M s ), but• it has a negligible effect on ClO• [k = (0.2–1.8) × 108
has−1a −negligible effect on ClO [k = (0.2–1.8)×10 8 M−1s−1] and Cl2•− (k < 3.0 × 106 M−1s−1),
M s 1 ] and Cl2 •− (k < 3.0 × 106 M−1 s−1 ), allowing determination of the contribution of
allowing determination of the contribution of {ClO• + Cl2•−} [27]. Finally, the contributions
{ClO• + Cl2 •− } [27]. Finally, the contributions were calculated by comparing the−1pseudo-
were calculated by comparing the pseudo-first-order degradation constants (min ) in the
first-order degradation constants (min−1 ) in the absence and presence of scavengers. These
absence
constants and
arepresence
calculated of as
scavengers.
follows: These constants are calculated as follows:
(25)
kCl2 •−
kCl2 •− = kTBA
= kTBA (25)
kO3 = kcontol − kN2 (26)
kO3 = kcontol − kN2 (26)
k(ClO•+ Cl2•−) = kBA (27)
k •+ Cl2•−) = kBA (27)
k(•OH/O•− +(ClO
Cl•) = kcontol − kBA − kO3 (28)
k OH/O •− + Cl )=k − kBA − kO3 (28)
where kCl2•−, kO3, k(ClO•+ Cl2•−),(•and k(•OH/O•−• + Cl•) contol
are the specific degradation rate constants
(min−1) of RhB with Cl2•−, O3, {ClO•+ Cl2•−}, and {•OH/O•− + Cl•}, respectively; kBA, kTBA, and
kN2 are the degradation rate constants calculated in the presence of BA, TBA, and N2 purg-
ing. The radicals’ contributions are calculated as follows:

Cl2•− contribution (%) = 100 × kCl2•/kcontol (29)

 Catalysts 2023, 13, 942 6 of 15

where kCl2 •− , kO3 , k(ClO•+ Cl2•−) , and k(•OH/O •− + Cl•) are the specific degradation rate con-
stants (min−1 ) of RhB with Cl2 •− , O3 , {ClO• + Cl2 •− }, and {• OH/O•− + Cl• }, respectively;
kBA , kTBA , and kN2 are the degradation rate constants calculated in the presence of BA, TBA,
and N2 purging. The radicals’ contributions are calculated as follows:
Cl2 •− contribution (%) = 100 × kCl2 • /kcontol (29)

O3 contribution (%) = 100 × kO3 /kcontol (30)

ClO• contribution (%) = 100 × [k(ClO•+ Cl2•−) - kCl2 •− ]/kcontol (31)
{• OH/O•− + Cl• } contribution (%) = 100 × k(•OH/O •− + Cl•) /kcontol (32)
Catalysts 2023, 13, x 7 of 16
The photodegradation of RhB using the Solar-L/chlorine process was studied in the
presence and absence of ascorbic acid, BA, and TBA, with 1000 µM chlorine and fixed
concentrations
concentrations wereofin1 high
mM for ascorbic
excess acid and
compared BA10
to the and
µM100RhBmM for TBA.
used. These scavenger
The results, which
concentrations were in high excess compared to the 10 µM RhB used.
are shown in Figure 3, indicate that the scavengers significantly reduced the rate The results, which
of dye
removal, with complete quenching observed with ascorbic acid, confirming the radicaldye
are shown in Figure 3, indicate that the scavengers significantly reduced the rate of
removal, with complete quenching observed with ascorbic acid, confirming the radical
pathway for RhB. The quenching rate increased from BA to TBA, but degradation was not
pathway for RhB. The quenching rate increased from BA to TBA, but degradation was not
affected by N2 saturation. BA reduced RhB degradation to a lesser extent than TBA. The
affected by N2 saturation. BA reduced RhB degradation to a lesser extent than TBA. The
calculated pseudo-first-order rate constants were kcontol = 0.0174 min−1, −k1N2 = 0.173 min−1, −1
calculated pseudo-first-order rate constants were kcontol = 0.0174 min , kN2 = 0.173 min ,
kBA = 0.045 min−1, and kTBA = 0.009 min−1. These−1 values suggest an insignificant role for O3,
kBA = 0.045 min−1 , and kTBA = 0.009 min . These values suggest an insignificant role for
a 5% contribution for Cl2 , 20.7%•−
•− for ClO , and a 74.3% contribution for OH/O•− and Cl•
• •
O3 , a 5% contribution for Cl2 , 20.7% for ClO• , and a 74.3% contribution for • OH/O•−
together. Therefore, both hydroxyl and reactive chlorine radicals are involved in the effi-
and Cl• together. Therefore, both hydroxyl and reactive chlorine radicals are involved in
cient degradation process of RhB using Solar-L photoactivated hypochlorite.
the efficient degradation process of RhB using Solar-L photoactivated hypochlorite.

Figure 3. Scavenger tests using BA, TBA, ascorbic acid, and N2 -saturation during the degrada-
Figure
tion3.of
Scavenger tests
RhB by the using Solar-L/chlorine
system BA, TBA, ascorbicatacid,
pH 11and N2-saturation
(conditions: C0 during the[TBA]
= 10 µM, degradation
0 = 100 µM,
of RhB by the system Solar-L/chlorine at pH 11 (conditions: C0 = 10 µM, [TBA]0 = 100 µM, [Asc.A]0
[Asc.A]0 = [BA] = 1 mM, N2 saturation 10 min before the run up to run completion (30 min), temp.
= [BA] =◦ 1 mM, N2 saturation 10 min before the run up to run completion (30 min), temp. 25 °C).
25 C).
2.3. 2.3.
Process Efficiency
Process withwith
Efficiency Variation of Initial
Variation Dye Dye
of Initial Concentration
Concentration
The The
effect of the
effect initial
of the RhBRhB
initial concentration on the
concentration on efficiency of the
the efficiency of combined Solar-
the combined Solar-
L/chlorine process
L/chlorine at pHat11pH
process was11investigated. The initial
was investigated. TheRhB concentration
initial ranged from
RhB concentration ranged
2 to from
25 µM, while
2 to the chlorine
25 µM, while theconcentration was kept constant
chlorine concentration was keptat 1000 µM. The
constant degrada-
at 1000 µM. The
tion kinetics and the initial degradation rate vs. initial RhB concentration were plotted in
Figure 4a,b, respectively. The results showed that the degradation kinetics of RhB de-
creased with the increasing initial RhB concentration (Figure 4a). The degradation rate
constant (k) decreased from 0.309 min−1 at 5 µM to 0.174 min−1 at 10 µM, 0.072 min−1 at 15
µM, 0.043 min−1 at 20 µM, and 0.033 min−1 at 25 µM. The t1/2 also decreased from 21 min at
 in the reaction mixture, resulting in a filter effect. This effect occurs when the dye mole-
cules block incident solar radiation from reaching the hypochlorite ions, thereby reducing
the rate of hypochlorite ion photolysis and consequently the production of reactive spe-
cies. Furthermore, competition between dye molecules and their degradation intermedi-
ates for available radicals may also contribute to the observed effect. At higher concentra-
Catalysts 2023, 13, 942 7 of 15
tions of RhB, a greater number of intermediates are formed, increasing the competition
for reaction with radicals.
The increase in the initial RhB degradation rate with the increasing initial RhB con-
degradation
centration kinetics
is the second and the of
effect initial degradation
the initial rate vs. initial
RhB concentration RhB concentration
(Figure 4b). This effect were
is
plotted
due to theinhigher
Figureconcentration
4a,b, respectively.
of RhBThe results showed
molecules availablethat
for the degradation
a reaction with thekinetics
gener-of
RhBradicals
ated decreased withcombined
in the the increasing initial
system. RhB RhB
At low concentration (Figurethere
concentrations, 4a). The
are degradation
fewer RhB
rate constant (k) decreased from 0.309 min −1 at 5 µM to 0.174 min−1 at 10 µM, 0.072 min−1
molecules available for a reaction, resulting in a slower degradation rate. However, as the
at 15 µM, 0.043 min −1 at 20 µM, and 0.033 min−1 at 25 µM. The t also decreased
RhB concentration increases, more RhB molecules are available for a1/2reaction, resultingfrom
in
21 min at 25 µM to 16, 8, 5, and 2 min at 20, 15, 10, and 5 µM, respectively.
a faster degradation rate. The plateau observed in Figure 4b suggests that the reaction has However, the
initial RhB
reached degradation
its maximum rate
rate, and versus
furtherinitial RhB concentration
increases (Figure 4b)
in RhB concentration increased
do not from
result in a
0.4 µM/min
further increase at in
2 µM to 0.79 µM/min
degradation at 5 µM
rate. Similar and have
trends reached a plateau
been reportedoffor
1 µM/min at 10,
several con-
15, 20, and
taminants 25 µM RhB.
degraded These observations
by different AOPs, such indicate that the
as sonolysis, combined Solar-L/chlorine
UV/persulfate, UV/periodate,
process is more effective at
UV/chlorine, and others [8,18,28–32]. lower initial concentrations of RhB and can efficiently degrade
RhB at concentrations as low as 2 µM.

InitialRhB
Figure4.4.Initial
Figure RhBconcentration
concentrationeffect
effectononitsitsdegradation:
degradation:(a)(a)removal
removalkinetics
kineticsand
and(b)
(b)initial
initialrate
rate
degradation,r0r(C
ofofdegradation, 0 =0 5–25 µM, pHpH11,11,
and temp. 2525 ◦
± 2±°C).
0 (C = 5–25 µM, and temp. 2 C).

ItThe decrease in
is important to the
notedegradation
that the firstrate constant
effect with in
(decrease therate
increasing
constantinitial
with RhB concen-
increasing
tration (Figure 4a) indicates that the system follows pseudo-first-order
initial RhB concentration) and the second effect (increase in initial RhB degradation rate kinetics. According
to this
with kinetic initial
increasing model,RhB theconcentration)
reaction rate is areproportional to the The
not contradictory. concentration
first effect isofathe dye.
result
ofTherefore, as thesites
limited active initial
forconcentration
the reaction and of dye increases,
a filter the number
effect due of active
to the higher sites available
concentration of
dye molecules, whereas the second effect is due to the higher concentration of RhB mole-as
for the reaction becomes limited, resulting in a decrease in the reaction rate. In addition,
the initial
cules concentration
available for reaction of with
RhB increases,
generatedthe dye molecules
radicals. Together,become more concentrated
these effects contribute toin
the reaction mixture, resulting in a filter effect. This effect occurs
the overall degradation kinetics observed in the system. Both scenarios, with when the dyerespect
molecules
to
block incident solar radiation from reaching the hypochlorite ions,
the initial contaminant concentration, have been reported for several AOPs [8,18,25,28– thereby reducing the
rate
34]. of hypochlorite ion photolysis and consequently the production of reactive species.
Furthermore, competition between dye molecules and their degradation intermediates for
available radicals may also contribute to the observed effect. At higher concentrations of
RhB, a greater number of intermediates are formed, increasing the competition for reaction
with radicals.
The increase in the initial RhB degradation rate with the increasing initial RhB con-
centration is the second effect of the initial RhB concentration (Figure 4b). This effect is
due to the higher concentration of RhB molecules available for a reaction with the gener-
ated radicals in the combined system. At low RhB concentrations, there are fewer RhB
molecules available for a reaction, resulting in a slower degradation rate. However, as the
RhB concentration increases, more RhB molecules are available for a reaction, resulting
in a faster degradation rate. The plateau observed in Figure 4b suggests that the reaction
has reached its maximum rate, and further increases in RhB concentration do not result in
a further increase in degradation rate. Similar trends have been reported for several con-
taminants degraded by different AOPs, such as sonolysis, UV/persulfate, UV/periodate,
UV/chlorine, and others [8,18,28–32].
It is important to note that the first effect (decrease in rate constant with increasing
initial RhB concentration) and the second effect (increase in initial RhB degradation rate
with increasing initial RhB concentration) are not contradictory. The first effect is a result of
Catalysts 2023, 13, 942 8 of 15

limited active sites for the reaction and a filter effect due to the higher concentration of dye
molecules, whereas the second effect is due to the higher concentration of RhB molecules
Catalysts 2023, 13, x available for reaction with generated radicals. Together, these effects contribute to9 of the16

overall degradation kinetics observed in the system. Both scenarios, with respect to the
initial contaminant concentration, have been reported for several AOPs [8,18,25,28–34].
2.4. Process Efficiency Dependence of Liquid Temperature
2.4. Process Efficiency Dependence of Liquid Temperature
The effect of liquid temperature on the Solar-L/chlorine degradation of RhB (10 µM)
was The effect of liquid
investigated temperature
at temperatures on the
of 25, 35, Solar-L/chlorine
45, and 55 °C, usingdegradation
chlorine at of1000
RhB µM.
(10 µM)
The
was investigated at temperatures of 25, 35, 45, and 55 ◦ C, using chlorine at 1000 µM.
degradation results are shown in Figure 5a, while the effect of the same temperature val-
The degradation results are shown in Figure 5a, while the effect of the same temperature
ues on dye chlorination (without light) is shown in Figure 5b. The results of Figure 5a
values on dye chlorination (without light) is shown in Figure 5b. The results of Figure 5a
showed that the degradation rate increased with increasing temperature. Comparing the
showed that the degradation rate increased with increasing temperature. Comparing the
degradation rate constants at different temperatures with that at 25 °C, we find that the
degradation rate constants at different temperatures with that at 25 ◦ C, we find that the
increase in the degradation rate constant is quite significant, especially between 45 and 55
increase in the degradation rate constant is quite significant, especially between 45 and
°C.◦ The degradation rate constant increased from 0.174 min−1−at 1 at25 °C◦ to 0.184 min−1−at1 35
55 C. The degradation rate constant increased from 0.174 min 25 C to 0.184 min at
°C (5.7% increase), 0.218 min−1 at 45 °C (25.3% increase), and 0.33 min−1 at 55 °C (89.6%
35 ◦ C (5.7% increase), 0.218 min−1 at 45 ◦ C (25.3% increase), and 0.33 min−1 at 55 ◦ C (89.6%
increase). The effect of the beneficial temperature was more pronounced at the beginning
increase). The effect of the beneficial temperature was more pronounced at the beginning
of the treatment. In addition, t1/2 decreased significantly with the increasing temperature.
of the treatment. In addition, t1/2 decreased significantly with the increasing temperature.
Moreover, the t1/2 value decreased from 5 min at 25 °C◦to 3, 1.8, and 1.2 min at 35, 45, and
Moreover, the t1/2 value decreased from 5 min at 25 C to 3, 1.8, and 1.2 min at 35, 45,
55 °C,
and 55 respectively. These
◦ C, respectively. results
These highlight
results highlight the the
significant effect
significant of solution
effect heating
of solution on the
heating on
Solar-L/chlorine treatment of RhB. It should be noted that the contribution
the Solar-L/chlorine treatment of RhB. It should be noted that the contribution of direct of direct chlo-
rination to the
chlorination high
to the temperature
high temperature effect
effectis ismarginal
marginalup uptoto45
45°C,
◦ C, as
as no effect of
no effect of chlorine
chlorine
alone on RhB removal was observed (Figure 5b). However, at 55
alone on RhB removal was observed (Figure 5b). However, at 55 C, direct chlorination◦°C, direct chlorination
mayhelp
may helptotoaccelerate
accelerateRhB
RhBremoval
removalinin the
the combined
combined system,
system, as as
thethe chlorination
chlorination process
process of
of micropollutants can be enhanced at higher temperatures. In our
micropollutants can be enhanced at higher temperatures. In our case, approximately 35% case, approximately
35%
of theofRhodamine
the RhodamineB wasBremoved
was removed
after theafter the chlorination
chlorination treatment
treatment (Figure (Figure
5b). 5b).

Figure5.5.Temperature
Figure Temperatureeffect
effecton
onRhB
RhBdegradation
degradationby
by(a)
(a)Solar-L/chlorine
Solar-L/chlorine and
and(b)
(b)chlorine
chlorineprocesses
processes
(C00 == 10
(C 10 µM,
µM, pH
pH 11,
11, and
and temp.
temp. 25–55
25–55 ◦°C).
C).

Theeffect
The effectofofliquid
liquidtemperature
temperatureisisrelatively
relativelycomplex.
complex.On Onthe
theone
onehand,
hand,the
thequantum
quantum
yield
yieldofofchlorine
chlorinephotolysis
photolysiscan canbebeaffected
affectedbybytemperature
temperature changes,
changes,although
althoughit is
it primarily
is primar-
pH
ily rather thanthan
pH rather temperature dependent.
temperature At a basic
dependent. pH, chlorine
At a basic photolysis
pH, chlorine occursoccurs
photolysis primarilypri-
by directby
marily photolysis, which involves
direct photolysis, the dissociation
which involves of hypochlorous
the dissociation acid into hypochlorite
of hypochlorous acid into hy-
and hydroxyl
pochlorite andand chlorineand
hydroxyl radicals.
chlorineThe quantum
radicals. yield
The of thisyield
quantum process is known
of this process toisbeknown
high,
typically
to be high,in typically
the rangeinofthe
0.3–0.7
rangeatofpH values
0.3–0.7 at above 8 [11].
pH values However,
above 8 [11]. Bendjama et al. [35]
However, Bendjama
reported
et al. [35]that the intensity
reported that theofintensity
the absorbed
of theUV254
absorbednmUV254
light innm
aqueous
light insolution
aqueous increased
solution
with the increasing
increased with the liquid temperature,
increasing providing evidence
liquid temperature, providingthat chlorinethat
evidence photolysis
chlorine(evenpho-
tolysis (even using Suntest UV-A and B) in basic media can be increased with liquid tem-
perature. Overall, our results show that liquid temperature plays a significant role in ac-
celerating the degradation of RhB by combining Solar-L photolysis and chlorine in a
strong basic medium.
 Catalysts 2023, 13, 942 9 of 15

Catalysts 2023, 13, x using Suntest UV-A and B) in basic media can be increased with liquid temperature. 10 of 16
Overall, our results show that liquid temperature plays a significant role in accelerating the
degradation of RhB by combining Solar-L photolysis and chlorine in a strong basic medium.
2.5. Effect of TiO2 Nanocatalyst
2.5. Effect of TiO2 Nanocatalyst
The effect of adding TiO2 nanocatalyst (average particle size: 30 nm) to the reacting
The effect of adding TiO2 nanocatalyst (average particle size: 30 nm) to the react-
system (Solar-L/chlorine/RhB) was evaluated at pH 11 and ambient temperature (25 °C).
ing system (Solar-L/chlorine/RhB) was evaluated at pH 11 and ambient temperature
The resulting Solar-L/TiO 2/chlorine system is a combination of several single and binary
(25 ◦ C). The resulting Solar-L/TiO2 /chlorine system is a combination of several single
systems, including Solar-L/TiO2, Solar-L/chlorine, TiO2/chlorine, and TiO2 alone. There-
and binary systems, including Solar-L/TiO , Solar-L/chlorine, TiO2 /chlorine, and TiO2
fore, in order to demonstrate the net effect of2 chlorine on the photolytic process (Solar-
alone. Therefore, in order to demonstrate the net effect of chlorine on the photolytic process
L/TiO2), a comparison of the different systems in terms of RhB removal is necessary, as
(Solar-L/TiO2 ), a comparison of the different systems in terms of RhB removal is necessary,
shown in Figure 6. Based on the results presented in Figure 6, it can be concluded that
as shown in Figure 6. Based on the results presented in Figure 6, it can be concluded that
neither TiO2 alone nor TiO2/chlorine can effectively degrade RhB, indicating that RhB ad-
neither TiO2 alone nor TiO2 /chlorine can effectively degrade RhB, indicating that RhB
sorption on TiO2 is insignificant. This can be attributed to the repulsive electrostatic forces
adsorption on TiO2 is insignificant. This can be attributed to the repulsive electrostatic
between RhB molecules and the TiO2 surface at a basic pH of 11. The point of zero charge
forces between RhB molecules and the TiO2 surface at a basic pH of 11. The point of zero
(pzc) of the
charge TiO
(pzc) used
of2 the in this
TiO study (Degussa P25) is at pH 6.8 [36], which means that the
2 used in this study (Degussa P25) is at pH 6.8 [36], which means that
TiO 2 surface is positively charged in acidic media (pH < pzc) and negatively charged in
the TiO2 surface is positively charged in acidic media (pH < pzc) and negatively charged in
alkaline
alkalineconditions
conditions (pH
(pH> pzc). RhB
> pzc). RhBexists inin
exists two forms,
two forms,cationic (RhB+)
cationic (RhB+) and
and zwitterionic
zwitterionic
(RhB±), as shown in Figure 7. At pH values higher than the pKa of RhB,
(RhB±), as shown in Figure 7. At pH values higher than the pKa of RhB, i.e., 3.70i.e., 3.70 [18], the
[18], the
zwitterionic form dominates, especially at a strongly basic pH (pH 11). Therefore,
zwitterionic form dominates, especially at a strongly basic pH (pH 11). Therefore, both both
TiO
TiO2 and RhB were predominantly negatively charged, which can explain the repulsive
2 and RhB were predominantly negatively charged, which can explain the repulsive
force
forcebetween
between them.
them.

Figure 6. Comparison of different photolytic and photocatalytic processes on the degradation of RhB
Figure 6. Comparison of different photolytic
◦
and photocatalytic processes on the degradation of
(C0(C
RhB =0 10 µM,
= 10 pHpH
µM, 11,11,
and temp.
and 25–55
temp. 25–55C).
°C).

On the other hand, similar to the first results, photolysis with 100 mg/L TiO2 has no
significant effect on the degradation of RhB. This is probably due to the fact that the dye
molecules are far away from the catalyst surface (repulsive forces), where oxidizing radicals
are generated from the excitation of the catalyst surface. It was confirmed in [34] that solar
light can effectively generate photocatalytic activity on the TiO2 surface. However, the
effectiveness of this activity depends on various parameters, such as the pH of the solution
(a major influencing factor), the initial dye concentration, the amount of catalyst used, etc.
Catalysts 2023, 13, 942 10 of 15

In the case of 100 mg/L TiO2 , the absence of RhB degradation in the solar photocatalytic
process can be attributed to the fact that RhB molecules are positioned at a certain distance
from the catalyst surface (due to repulsive forces), where radicals are formed following the
Figure 6. Comparison
formation − ) and
of electronsof(edifferent photolytic
holes (h+and photocatalytic
) during processes on the
the photo-excitation degradation
(λ < 400 nm) ofof
CB
RhB (C 0 = 10 µM, pH 11, and temp. 25–55 °C).
the TiO2 semiconductor (Reactions 33–42).

Figure 7. Rhodamine B forms in water [18].

TiO2 + hv → h+ VB + e− CB (33)
OH− ads + h+ VB → • OHads (34)
H2 Oads + h+ VB → • OHads + H+ (35)
− •−
O2 + e CB → O2 (36)
•− + •
O2 + H → HO2 (37)
HO2 • + HO2 • → H2 O2 (38)
O2 •− + HO2 • → HO2 − + O2 (39)
HO2 − + H+ → H2 O2 (40)
H2 O2 + e− CB → • OH + OH− (41)
H2 O2 + O2 •− → • OH + OH− + O2 (42)
Note that, in the above reaction scheme, Equations (34) and (35) were proposed as the
main pathway for photogeneration of • OH radicals on the TiO2 surface [37].
Alternatively, as previously demonstrated (Figure 1a), solar light irradiation alone is
insignificant for the removal of RhB. However, when coupled with hypochlorite, it becomes
effective (Figure 1c); the dye was removed in 30 min with a pseudo-first-order reaction
rate of 0.174 min−1 . The reason for this trend is well explained in Sections 2.1 and 2.2.
The addition of TiO2 to the solar L/C system increased the RhB degradation rate, with
the ratio of the initial degradation rate (r0 , in µM/min) with and without TiO2 being
2.0/1.35 ≈ 1.48. The degradation rate constant (k) in the presence of TiO2 is 0.23 min−1
compared to 0.174 min−1 without TiO2 . The ratio of k is 0.23/0.174 ≈ 1.321. This means that
the addition of TiO2 improved the initial dye removal rate (r0 ) by 48% and the degradation
rate constant (k) by 32%.
The beneficial effect of the solar-L/ClO− /TiO2 ternary system could be attributed to
the involvement of hypochlorite in the photochemical reactions taking place at the catalyst
surface (Reactions 33–42). In fact, ClO• can reach the catalyst surface even in the presence
of repulsive forces between the catalyst surface (negative at pH 11) and hypochlorite anions
due to the too-high dosage of aqueous ClO• (1000 µM). At the catalyst surface, ClO• can
react with e− and • OH according to Reactions 43–44. A number of other subsequent
reactions may result, leading to the formation of other reactive species such as Cl• , Cl2
and Cl2 •− , as well as chlorinated products such as Cl2 O2 (Reactions 43–53). It should be
noted that these chlorine species, especially Cl• , ClO• , Cl2 , and Cl2 •− , can generate many
secondary reactions at the TiO2 surface, but what we are interested in is the reactivity of
Catalysts 2023, 13, 942 11 of 15

these reactive species with our substrate (RhB) under the operating conditions of a strongly
basic medium (pH 11).
ClO− + e− (TiO2 ) → O•− + Cl− (43)
•
OHad + ClO− → ClO• + OH− (44)
Cl− + h+ (TiO2 ) → Cl• (45)
Cl• + H2 O → HClO•− + H+ (46)
• − • •−
Cl + OH → ClO + O (47)
HClO•− •
OH + Cl− (48)
Cl• + ClO− → ClO• + Cl− (49)
Cl• + Cl− Cl2 •− (50)
Cl• + Cl• Cl2 (51)
2 Cl2 •− → Cl2 + 2Cl− (52)
ClO• + ClO• → Cl2 O2 (53)
The ultrafast recombination of electron/hole pairs (h+
VB + e−
CB → hv, 1 ps [38]) is a
major drawback in the application of TiO2 -based photocatalysis in water treatment. This is
because the recombination process limits the availability of radicals that can react with RhB
molecules. However, hypochlorite (ClO− ) can be used as an efficient electron acceptor to
prevent the e− /h+ recombination, as shown in Equation (43), and increase the concentration
of radicals in the bulk solution. Similar effects have been observed with other oxidants,
such as H2 O2 and persulfate [39–44]. In addition, Reaction 44 can replace inactive • OHad
with ClO• , which is likely to diffuse widely in the bulk solution to react with RhB molecules
and enhance their degradation. In fact, reactive chlorine species have longer lifetimes than
• OH (i.e., 5 µs for Cl• [45] and fractions of milliseconds for Cl •− [45] versus ~1 ns for • OH),
2
making them more efficient at degrading contaminants [46]. In addition, chloride ions,
the main product of hypochlorite photolysis in bulk solution [14], can act as h+ scavengers
(reaction 45), preventing e− /h+ recombination and generating an excess of chlorine radicals
in the reaction medium. Overall, hypochlorite can greatly enhance the reactivity of the
photocatalyst even in the presence of repulsive forces caused by the high basification of
the medium.
At the end of this section, it is important to emphasize that the effect of TiO2 was
evaluated for varying initial RhB concentrations (5–25 µM with 100 mg/L TiO2 ) and TiO2
loadings (up to 500 mg/L with 10 µM RhB). In all cases, the trends reported and discussed
earlier (and in Figure 6) were observed. The TiO2 -induced enhancement of RhB degradation
in Solar-L/chlorine at pH 11 was consistently between 30 and 35%, with no significant effect
of Solar-L/TiO2 on the degradation process. This suggests that the effect of electrostatic
repulsive forces between the catalyst surface (negative) and the zwitterionic form of RhB
was maintained even with varying TiO2 loading or initial RhB concentration. Therefore,
the only enhancement mechanism is the involvement of hypochlorite in the photocatalytic
reactivity at the photocatalyst surface, as discussed above.

3. Experimental
3.1. Reagent
Rhodamine B (abbreviation, RhB; C.I. number, 45170; and molecular formula, C28H31N2O3Cl,
MW: 479.01 gmol−1) was procured from Sigma-Aldrich (St. Louis, MO, USA) Sodium
hypochlorite (NaOCl) solution (available chlorine ~16%) was supplied by Henkel (Dély
Ibrahim, Algeria). P-25 TiO2 nonporous powder (80% anatase and 20% rutile, average
particle size of 30 nm, and specific surface area of 50 m2 g−1 ) was supplied by Degussa
Corporation (Düsseldorf, Germany) and used as received. All other reagents (tert-butanol,
Catalysts 2023, 13, 942 12 of 15

Benzoic acid, ascorbic acid, NaOH, and H2 SO4 ) were commercial products of the purest
grade available (Sigma-Aldrich).
Catalysts 2023, 13, x 13 of 16
3.2. Setup
The experimental setup, as shown in Figure 8, consisted of a water-jacketed Pyrex
glass reactor (250 mL) located in a chamber of a commercial Suntest simulator (Suntest
The experimental setup, as shown in Figure 8, consisted of a water-jacketed Pyrex
CPS+, Atlas, Mount Prospect, IL, USA). This simulator was equipped with an Xe arc lamp
glass reactor (250 mL) located in a chamber of a commercial Suntest simulator (Suntest
with
CPS+,anAtlas,
emission
Mountrange limited
Prospect, to wavelengths
IL,USA). This simulator between 280 andwith
was equipped 800 annm,Xeand
arc an
lampirradiance
of
with an emission range limited to wavelengths between 280 and 800 nm, and an irradiance 0.5% of
500 W was maintained. The lamp had a spectral distribution of approximately
the emitted
of 500 W wasphotons at wavelengths
maintained. The lamp hadshorter
a spectralthan 300 nm and
distribution about 7% between
of approximately 0.5% of 300 and
400
the nm. Thephotons
emitted emission spectrum between
at wavelengths shorter 400
thanand300 800 nm about
nm and followed the solar300
7% between spectrum.
and The
distance
400 nm. Thebetween
emissionthe solution
spectrum surface
between 400andandthe
800 light source the
nm followed was fixed.
solar The experiments
spectrum. The
distance
were between
carried out the solution
in the surface and
temperature range the of
light
25–55 ◦ C,was
source withfixed. The experiments
the temperature monitored
were carried out in the temperature range of 25–55 °C, with the temperature
by a thermocouple immersed in the reaction medium and maintained at the desired value monitored
by circulating
by a thermocouple immersed
water from ainthermostatic
the reaction medium and maintained
bath (RC6 at the desired
Lauda, Abcoude, value
The Netherlands)
by circulating water from a thermostatic bath (RC6 Lauda, Abcoude, The
through a jacket surrounding the cell. The pH of the solution was monitored during the Netherlands)
through a jacket surrounding the cell. The pH of the solution was monitored during the
reaction, using a pH meter (Jenway 3505- Keison Products, Chelmsford, UK).
reaction, using a pH meter (Jenway 3505- Keison Products, Chelmsford, UK).

Temp 25 °C
pH 6.2

SUNTEST CPS+

2 1

1
4
3

Temp 28°C
RPM 2500

Set Time
Set Temp

RC6 LAUDA

Figure 8.
Figure 8. Experimental
Experimental setup
setupscheme.
scheme.(1)(1)Solar
Solar simulator ‘Suntest
simulator CPS+’,
‘Suntest (2) irradiation
CPS+’, lamp,
(2) irradiation (3) (3) com-
lamp,
command
mand panel,panel, (4) water-jacketed
(4) water-jacketed glass
glass reactor,
reactor, (5)(5)magnetic
magneticstirring
stirring plate,
plate, (6)
(6) pH-meter,
pH-meter,(7)(7)ther-
thermostatic
mostatic bath (8) heat/flow rate controller, and (9) connection piping.
bath (8) heat/flow rate controller, and (9) connection piping.
3.3. Procedures
Catalysts 2023, 13, 942 13 of 15

3.3. Procedures
Deionized water was used to prepare all solutions. Batch degradation experiments
were performed under different conditions, using a constant solution volume of 200 mL.
Stock solutions of RhB (10 mM) and chlorine (10 mM) were prepared and stored in the
dark at 4 ◦ C. The desired operating concentrations were obtained by making appropriate
dilutions from these stocks. In all photocatalytic runs, TiO2 was added to the RhB solution,
and the suspension was allowed to stand in the dark with stirring for 15 min to ensure the
adsorption/desorption equilibrium of the pollutant. After this period, known amounts
of chlorine were added to the reactor, and the Suntest lamp (Suntest CPS+, Atlas, Mount
Prospect, IL, USA) was turned on to mark the start time of the reaction. The suspension was
continuously stirred at moderate speed (~300 rpm), using a magnetic stirrer. Aliquots (3 mL)
were removed from the photoreactor at different time intervals, filtered through 0.45 µm
Millipore filters (non-adsorber of RhB), and analyzed using a UV-Vis spectrophotometer
(Jasco V-730, Tokyo, Japan) equipped with 1 cm light-path quartz cuvettes. The concentra-
tion of RhB was measured at 550 nm, which is its maximum absorption wavelength in the
visible band. The pH of the solution was adjusted to pH 11, using sodium hydroxide. All
experiments were repeated three times to ensure the reproducibility of the experimental
results, and the data were averaged (error bars represent the 95% confidence interval).

4. Conclusions
The obtained results highlight the effectiveness of the Solar-L/chlorine process in
degrading Rhodamine B, emphasizing the cost-saving advantages of utilizing solar light
instead of artificial UV lamps. While solar light or chlorination alone did not exhibit a
noticeable impact on RHB removal, the combined Solar-L/chlorine process demonstrated
remarkable efficiency, achieving complete degradation within just 30 min of using 1000 µM
ClO− . The process also demonstrated an effective reduction of the total organic carbon
(TOC), with a 60% reduction observed after 120 min and 80% reduction after 240 min.
Notably, higher temperatures (55 ◦ C) resulted in an enhanced degradation performance.
Furthermore, the inclusion of a TiO2 nanocatalyst in the Solar-L/chlorine system sig-
nificantly improved the efficiency of RhB degradation, showcasing an enhancement of
over 30%.
To enhance the practical implementation of the Solar-L/chlorine process, it is crucial
for future research to identify the by-products generated during degradation and assess
their potential environmental impact. Furthermore, conducting a toxicity analysis of the
final effluent is essential to ensure the safety of the treated water for discharge. Additionally,
an economic cost evaluation of the process is necessary to evaluate its feasibility for large-
scale industrial applications. These important findings serve as a foundation for further
advancements and optimization of this promising technology in the field of water treatment,
offering valuable insights for its future development and application.

Author Contributions: H.B., experimentation and data collection; S.B., experimentation and data
collection; S.M., conceptualization, methodology, data analysis, writing—review and editing, and
project supervision; A.D., writing—review and editing; O.H., writing—review and analysis. All
authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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