Desalination and Water Treatment 231 (2021) 425–435

August
www.deswater.com
doi: 10.5004/dwt.2021.27496

Solid state dispersion and hydrothermal synthesis, characterization and

evaluations of TiO2/ZnO nanostructures for degradation of Rhodamine B

Siamak Dolatabadia, Moslem Fattahia,*, Mohammad Nabatib

a
Department of Chemical Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Abadan, Iran,
email: fattahi@put.ac.ir (M. Fattahi), siamak1917@gmail.com (S. Dolatabadi)
b
Department of Basic Sciences, Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Abadan, Iran,
email: nabati@put.ac.ir

Received 4 January 2021; Accepted 1 June 2021

abstract
In this study, TiO2/ZnO nanostructures were synthesized by sol–gel solid-state dispersion method
and hydrothermal methods for degradation of Rhodamine B (RhB). The ZnO weight percentage,
calcination temperature and irradiation time were investigated for synthesizing the different cata-
lyst samples. Then, the X-ray diffraction, Brunauer–Emmett–Teller, Fourier-transform infrared spec-
troscopy and field emission scanning electron microscopy analysis was performed to characterize
the as-prepared catalysts. The experimental design was utilized for photocatalytic degradation of
RhB. The effects of operating parameters such as pH, irradiation time, initial RhB concentration
and catalyst concentration were investigated through this study. The degradation tests were per-
formed by UV of 24 W. The best degradation performance of 99.28% was obtained. The results
of characterization and degradation via two methods of preparation including the; sol–gel and
hydrothermal were analyzed and compared. Besides, the optimum conditions for reaching the
highest RhB degradation were reported.
Keywords: Hydrothermal; Sol–gel; Photocatalyst degradation; Rhodamine B; Experimental design;
Solid-state dispersion

1. Introduction such as TiO2, ZnO, MgO, ZrO2 have been attempted for
the photocatalytic degradation of a wide variety of envi-
Rhodamine B (RhB) is one of the dyes used in the tex-
ronmental contaminants [2,3]. TiO2 as a catalyst has sev-
tile, cosmetics, biotechnology laboratories and etc. It has
eral advantages but for more activation, ultraviolet (UV)
a highly complex organic compound and because of the
will be used and for better efficiency using another catalyst
complexity of its structure, it can be a good benchmark
such as ZnO besides TiO2 will be appropriate. It can reduce
for experiments. Advanced oxidation process (AOP) type
electron–hole recombination and cause increased efficiency.
procedures can become very promising technologies for
An ideal photocatalyst for photocatalytic oxidation is
treating wastewater containing non-biodegradable or hardly
characterized by the following attributes including photo-
biodegradable organic compounds with high toxicity [1].
stability, chemically and biologically inert nature, availabil-
Amongst AOPs methods photocatalytic degradation
ity and low cost. TiO2 is the most preferred one due to its
has proven to be a promising technology for degrading
chemical and biological inertness, high photocatalytic activ-
refractory organic matters. Metal oxide semiconductors
ity, photo-durability, mechanical robustness and cheapness.

* Corresponding author.

1944-3994/1944-3986 © 2021 Desalination Publications. All rights reserved.

426 S. Dolatabadi et al. / Desalination and Water Treatment 231 (2021) 425–435

The titanium photocatalytic efficiency might be enhanced reduction ability under visible light irradiation compared
by metals and non-metals doping. Therefore, combining to pure ZnO. The introduction of WS2 as a co-catalyst can
TiO2 with other suitable semiconductors such as ZnO, Fe3O4, prolong the charge carrier lifetime that enhancing the
CuO, MgO can be reduced electron–hole recombination catalytic activity of CaIn2S4 for efficient Cr(VI) reduction [23].
of photo-electrons and improved efficiency [4–9]. In the current study, sol–gel via solid-state disper-
Although numerous researches on the removal of sion (SSD) method and hydrothermal for the synthesis of
different organic pollutants from wastewater using TiO2/ TiO2/ZnO nanostructures were utilized. The efficiency of
ZnO as photocatalyst nanocomposite has already been per- synthesized nano TiO2/ZnO investigated for degradation
formed, however, the interfacial ZnO charge transfer rate is of RhB. The characteristics of the synthesized nano TiO2/
low and both of the aforementioned photocatalysts alone ZnO determined by X-ray diffraction (XRD), field emission
have a large bandgap and high electron-hole recombina- scanning electron microscopy (FESEM), Brunauer–Emmett–
tion rate. Furthermore, both of them have a great tendency Teller (BET) and Fourier-transform infrared spectroscopy
to aggregation, especially at high concentrations. Hence, (FTIR). The efficiency of these two methods of synthesis
to enhance the photocatalytic activity and to solve the was compared. Moreover, the operating parameters of pH,
aggregation problem, the addition of different compounds irradiation time, initial RhB concentration as well as catalyst
such as various biopolymers and carbon materials to the dosage were studied through this study.
semiconductors as solid supports is a suitable approach
[10–12]. Recycling and separation of photocatalysts are 2. Experimental
considerable problems in the practical approach. Solid
supports played a significant role in facilitating catalyst’s 2.1. Materials
immobilization [11]. It was also reported that supported
Titanium tetrachloride (TiCl4) and zinc nitrate hexahy-
materials can increase the surface area of catalytic systems
drate Zn(NO3)2·6H2O from Merck Company, (Germany) was
and thus improve in hydrophobicity, thermal, hydrolytic,
purchased and utilized as the titanium and zinc precursors.
and chemical stability of the catalysts occurred [13].
Besides, ethanol (Merck Company, Germany) and deionized
Pei et al. [14] studied TiO2/ZnO nanofibers that have
water as the solvent and NH4OH as the pH adjuster was utilized.
been synthesized with a small diameter having 10 nm
poly-crystallites of large surface area by electrospinning
followed by calcination. The photocatalytic activities of 2.2. Catalyst preparation
nanofibers have been studied systematically by the degra-
2.2.1. Sol–gel and SSD synthesis of nano TiO2/ZnO
dation of RhB dye under the 420 nm visible-light irradia-
tion (degradation is 90%). Chen et al. [15] investigated novel Pristine TiO2 was prepared through sol–gel method.
titanium dioxide (TiO2) and zinc oxide (ZnO) hybrid pho- 8 mL TiCl4 was slowly added dropwise into 80 mL ethanol
tocatalysts in the form of nanofibers that have been fabri- solution at room temperature (sol of TiO2) in which a large
cated by a facile method using electro-spinning followed by amount of HCl gas was exhausted during the mixing pro-
a calcination process. The photocatalytic performances have cess. Then, a light yellow solution was obtained and gela-
been evaluated via the photo-degradation of RhB under tinized for 5 h at 80°C in the oven to form sol–gel and for
irradiation with UV light (degradation is 90%). Zha et al. aging, it remained at room temperature for 40 h. Finally,
[16] have used nanostructured TiO2/ZnO heterojunctions the gel was dried in the oven at 110°C for 12 h, ground into
with the morphologies of hedgehogs and fan blades have a fine powder, and calcined at 500°C for 2 h. In addition,
been synthesized by a solvothermal method (97% MO deg- the ZnO was prepared by the co-precipitation technique.
radation under UV light within 30 min). Pozan and Kambur 25 g of zinc nitrate hexahydrate was dissolved in 100 mL
[17] studied ZnO-TiO2 binary oxide catalysts that have been deionized hot water and the resulting solution was heated
successfully prepared by a solid-state dispersion. Xu et al. up to 65°C. This mixture was precipitated by gradually
[18] focused on the composite powder of TiO2/ZnO with an adding NH4OH solution (6 mol L–1) until the pH value
atomic ratio of Ti to Zn of 3/1 has been prepared through reached 10. The resultant solution was slowly stirred for
sol–gel process followed by hydrothermal and post-heat 2 h at 65°C (sol of ZnO). The precipitate was then filtered,
treatments. washed with deionized water and dried at 100°C for 16 h
Zhuge et al. [19] showed that Ti3C2Tx promoted the and then calcined at 500°C for 5 h.
photocatalytic efficiency of pure CaIn2S4 for degradation Since the time of gelatinization of two catalysts not equal,
of different hazardous contaminants. Besides, the hybrid ZnO-TiO2 binary oxide catalysts were prepared by the SSD
of CaIn2S4-Ti3C2Tx showed a higher photocurrent density method. SSD method initially involves mixing TiO2 and ZnO
than pure CaIn2S4. Liu et al. [20] showed that the catalysts thoroughly using ethanol. The solvent was then removed by
of Cu2In2ZnS5 and Gd2O2S:Tb by providing more active sites evaporation while mixing. Samples prepared by this method
improved the photocatalytic reduction activity for Cr(VI) were dried at 110°C and calcined at 350°C, 550°C and 750°C
and CO2. Liu et al. [21] showed photocatalytic and photo- for 6 h to obtain ZnO-TiO2 binary oxide catalysts. ZnO
electrochemical activity of pure ZnIn2S4 by UiO-66 addition amount of the catalysts was nominally 20 and 33 wt% and
attributed more active sites for pollute adsorption. Based reported as the weight percentage. The different conditions
upon band-edge levels constructed in the ZU hybrids, the of prepared catalysts through SSD method was provided in
UiO-66 could enhance the separation of photo-induced Table 1. For instance, 1:4 ZnO-TiO2 and 1:2 ZnO-TiO2 mean
charge carriers and prolong their lifetime. Ren et al. [22] that the catalyst contained nominally 20% and 33% ZnO by
showed MoSe2/ZnO/ZnSe hybrids improved photocatalytic weight [17,24].
 S. Dolatabadi et al. / Desalination and Water Treatment 231 (2021) 425–435 427

2.2.2. Hydrothermal synthesis of nano TiO2/ZnO to evaluate and optimize the performance of complex
systems by considering the relative significance of sev-
The prepared ZnO sol was then directly incorporated
eral affecting factors even in the presence of complicated,
into the TiO2 sol at an atomic molar ratio of Zn to Ti of 1:4
multi-dimensional interactions [2]. To investigate the effect
and 1:2 to achieve the ZnO/TiO2 composite sol. The mix-
of operating parameters including the; pH, time, initial
ture of TiO2/ZnO sol was aged for a period of time at room
RhB concentration and catalyst concentration, Design-
temperature until it became gel. The gel was dried and pul-
Experts software (Ver. 7.0.0) was employed for the design of
verized to be powder. The gel powder was then transferred
experiments and mathematical modeling.
into a Teflon-lined autoclave and heated at various tempera-
The effect of pH in the range of 3, 6 and 9; time in the
tures for different times (200°C and 150°C for 12 and 24 h).
range of 3, 4 and 5 h; initial RhB concentration in the
After hydrothermal treatment, the powder was washed with
range of 1, 2 and 3 mg L–1 and catalyst concentration in
distilled water and dried. The powder was finally post-
the range of 0.2, 0.3 and 0.4 g L–1 were investigated.
heat treated by calcination in the air for 8 h at 550°C in a
muffle oven [18]. The condition of synthesized catalysts
through hydrothermal method was summarized in Table 2. 2.5. Photocatalytic activity tests
The photocatalytic activity of nano TiO2/ZnO with dif-
2.3. Characterization
ferent operational parameters for degradation of RhB in
The crystal structure and phase of nanomaterials were aqueous solution was carried out using a setup that consists
characterized by XRD (Model: Philips, PW 1730 diffractom- of a cylindrical quartz reactor (for better UV transmission)
eter, Netherlands) using Cu Kα radiation (λ = 0.15,406 nm) with magnetic stirring and six 4W-UVC lamps that cov-
by scanning in angular range (2θ) from 10° to 80°. The ered it also an opaque plastic cover was placed outside to
particle size and morphology of TiO2/ZnO were stud- isolate other light sources. The pH value of the solution
ied with scanning electron microscopy (FESEM-TESCAN was adjusted by adding a small amount of 0.1 M NaOH or
MIRA3, Kohoutovice, Czech Republic) which was equipped HCl and monitoring with a digital pH meter. For each test,
with energy-dispersive X-ray spectroscopy (EDXS). FTIR various amount of catalyst was added into a quartz-reactor
spectra were recorded between the wavenumber of 400 containing 30 mL of the RhB with defined concentration.
and 4,000 cm–1 (Bruker, Model: VERTEX 70, Germany). The mixture was stirred for 10 min in the dark to adsorp-
The specific surface area (BET method), specific pore vol- tion and desorption equilibrium. After desired time sam-
ume and average pore diameter (Barrett, Joyner, Halenda ples were centrifuged for 15 min at a rate of 12,000 rpm
method) were determined by using nitrogen adsorption to separate photocatalysts and obtain a transparent solu-
at 77 K (Model: BELSORP MINI 3, Czech Republic). tion. The final concentration of RhB was determined by a
UV-vis spectrophotometer at λmax = 554 nm.
2.4. Experimental design Finally, for calculation of the degradation rate of RhB
Response surface methodology (RSM) is a powerful the following equation was used:
mathematical and statistical design tool that can be used
C 0 − Ct
Degradation (%) = × 100 (1)
Table 1 C0
The prepared catalysts via the SSD method in this research
where C0 is the initial concentration of RhB (mg L–1)
Catalyst Weight percentage Calcination temperature and Ct is the final concentration of RhB (mg L–1) after
sample of ZnO (%) and time (T, °C/time, h) degradation time.
S1 20 350/6
S2 20 550/6 3. Results and discussion
S3 20 750/6 3.1. XRD analysis
S4 33 350/6
XRD analysis in Fig. 1 indicates the formation of the
S5 33 550/6
pure anatase phase of TiO2 and zincite phase of ZnO in all
S6 33 750/6
samples S1, S2 and S5 that synthesized by sol–gel method

Table 2
The prepared catalysts via hydrothermal method in this investigation

Catalyst Weight percentage Hydrothermal temperature Calcination temperature

sample of ZnO (%) and time (°C/h) and time (°C/h)
H1 20 200/12 550/8
H2 20 150/24 550/8
H3 33 200/12 550/8
H4 33 150/24 550/8
428 S. Dolatabadi et al. / Desalination and Water Treatment 231 (2021) 425–435

Fig. 1. XRD analysis pattern of the synthesized materials by sol–gel and hydrothermal methods in this research.

and the formation of pure rutile phase of TiO2 and zincite where D is the average crystallite size, K the constant which
phase of ZnO in both samples H1 and H4. The average size is taken as 0.89 here, λ = 0.15406 nm is the wavelength
of TiO2/ZnO crystallites was estimated by means of the of the X-ray radiation, β is full width at half-maximum
Debye–Scherrer’s equation on the main peak: (FWHM), and θ is the diffraction angle [25]. The crystal-
lite sizes, for samples S1, S2 and S5 are 19.17 nm, 16.77 nm
Kλ and 14.90 nm, and for samples, H1 and H4 are 26.94 nm
D= (2)
βcosθ and 11.18 nm. It seems that in sol–gel method by increasing
 S. Dolatabadi et al. / Desalination and Water Treatment 231 (2021) 425–435 429

the calcination temperature, the size of particles has been isotherm, and for samples, H2 and H3 fitted type V iso-
reduced but in a hydrothermal method the calcination therm according to the IUPAC nomenclature is presented
temperature is the same, by increasing the hydrothermal in Fig. 2. Adsorption on mesoporous solids proceeds via
time and hydrothermal temperature reduction, the size of multilayer adsorption followed by capillary condensation,
particles has been reduced. resulting in Type IV isotherm. Characteristic features of
the type IV isotherm are its hysteresis loop, which is asso-
3.2. BET analysis ciated with capillary condensation taking place in meso-
pores, and the limiting uptake over a range of high P/P0.
The surface area, pore-volume, and pore diameter of This isotherm is used for porous materials and often be seen
samples were measured using the N2 adsorption method for industrial catalysts. Its hysteresis indicates mesopores
[3]. The surface area, total pore volume and mean pore structure’s existence in the material. The reversible type III
diameter of samples are shown in Table 3. isotherm indicates an unrestricted multilayer formation
As will be seen in FESEM analysis, it seems that by
increasing the calcination temperature, aggregation of par-
ticles has been occurred and caused a reduction in surface Table 3
area and total pore volume for sample S6 than sample S2. The surface area, total pore volume and mean pore diameter of
prepared samples
Moreover, the weight (%) of ZnO in sample S6 is more
than S2 that might be effective in this reduction. Besides,
Sample Surface area Total pore Mean pore
the calcination temperature of samples H2 and H3 is the
same, the total pore volume of the two samples is very near (m2 g–1) volume (cm3 g–1) diameter (nm)
together but the difference in hydrothermal temperature S2 36.138 0.1602 17.732
and time caused the surface area of sample H2 to be greater S6 6.4853 0.0207 12.793
than H3 probably.
H2 39.514 0.3771 38.173
The N2 adsorption–desorption isotherms for sample
H3 25.957 0.3916 60.364
S2 fitted type IV isotherms, for sample S6 fitted type III

S2

Fig. 2. N2 adsorption/desorption isotherm of samples S2, S6, H2 and H3.

430 S. Dolatabadi et al. / Desalination and Water Treatment 231 (2021) 425–435

process. It forms because lateral interactions between peak at ~1,634.00 cm–1 is corresponds to Zn–O stretching and
adsorbed molecules are strong in comparison to interactions deformation vibration [29]. In all samples, the 1,600 cm–1
between the adsorbent surface and adsorbate. Nonporous assigned to the hydroxyl groups and the ~600 cm−1 band
systems have this isotherm. Type V isotherm is very similar was associated with the Ti–O–Ti stretching vibration [30–35].
to type III and is seen in porous materials including meso-
pores [26]. The N2 adsorption–desorption isotherms for all 3.4. FESEM analysis
samples are shown in the following Fig. 2:
To determination of pore size distributions, the Barrett, In order to investigate the surface morphology of the
Joyner, Halenda (BJH) method was used. The classification materials, samples S1, S2, S4, S6 and samples H1, H2 and
of pore sizes: micropores (<2 nm) mesopores (2~50 nm) H3 were analyzed by FESEM. The results are shown in Fig. 5.
macropores (>50 nm) [26]. According to BJH plots in Fig. 5 shows that synthesized samples by the hydro-
Fig. 3, all samples are mesopores but in sample S6 some pore thermal method are more uniform than samples prepared
sizes are micro and in sample H3 some pore sizes are macro. by sol–gel method. Moreover, synthesized samples by the
hydrothermal method are rod-like in shape. Sample S4 is
mainly a sphere-like shape and sample S6 is not uniform
3.3. FTIR analysis
and not a sphere or rod-like shape. The crystal size distri-
FTIR spectroscopy can identify the positions at which bution is from 13.51 to 27.69 nm which is not very different
the functional groups are attached. The reason is that from the XRD calculated sizes. Calcination temperature in
vibrational frequencies differ when functional groups are sample S2 is greater than S1 that caused more aggregation
attached at different sides in molecules [2]. FTIR analysis of particles also great calcination temperature in sample
for all samples is shown in Fig. 4. S6 caused complete aggregation and as was seen in BET
Several peaks related to TiO2 are observed in all sam- analysis, the surface area and total pore volume of sam-
ples. The broadband centered at 500–600 cm–1 is likely due ple S6 are very low. In samples H1, H2 and H3 that their
to the vibration of the Ti–O bonds in the TiO2 lattice [27]. For calcination temperature and time are the same, aggrega-
all samples in the study, two strong absorption bands were tion of particles are similar but an aggregation of particles
observed at ~430 and ~520 cm–1. While the band at ~430 cm–1 in sample H1 is less than H2 and H3. Less aggregation
corresponds to the E2 model of hexagonal ZnO, the band at caused more surface area and more total pore volume.
~520 cm–1 may be associated with oxygen deficiency and/or The PL and UV-Vis absorption spectrum analy-
oxygen vacancy (VO) defect complex in ZnO [28]. Also the sis for TiO2/ZnO has been done by Zhang et al. [4].

Fig. 3. BJH plots of samples S2, S6, H2 and H3.

 S. Dolatabadi et al. / Desalination and Water Treatment 231 (2021) 425–435 431

H1

Fig. 4. FTIR spectra of the prepared catalysts in this investigation.

Their results showed that the composite materials reduce on RhB degradation, experiments were performed by
the recombination probability. The unique heterostruc- Design-Expert® 7.0.0 software for samples S1 and H1.
ture photocatalyst of TiO2/ZnO has a positive effect on the The best degradation of RhB by sample S1 was 99.28%
effective separation of photogenerated carriers during the and by sample, H1 was 98.57% (time: 5 h, initial RhB
photocatalytic reactions charge carriers. The visible light concentration: 2 mg L–1, catalyst dosage: 0.3 g L–1).
absorption intensity of TiO2/ZnO improved compared
in compare to ZnO or TiO2. Moreover, according to the 3.6. Optimum conditions
valence band position of TiO2 and conduction band posi-
tion of ZnO, TiO2/ZnO nanocomposite is formed typical Optimum conditions for sample S1, to maximize the
Type-II [4]. degradation of RhB by maximum initial RhB concentration
and minimum concentration of catalysts were obtained at
this conditions: pH = 5.54, time = 5 h, initial RhB concen-
3.5. Experimental results
tration = 3 mg L–1, Catalyst dosage = 0.2 g L–1. Degradation
The photocatalytic powers of all samples for RhB at these optimum conditions correlated 94.98% com-
degradation were compared together under the same condi- pared with the experimental result of 95.75% which illus-
tions. The photocatalytic tests were performed at the condi- trated the good accuracy.
tions including; pH = 6, time = 4 h, initial concentration of Besides, for sample H1, optimum conditions in
RhB = 2 mg L–1, catalyst concentration = 0.2 g L–1, solution vol- maximum degradation of RhB by maximum initial RhB
ume of 30 mL and power of UV 24 W (all mixture was stirred concentration and minimum concentration of catalyst
for 10 min in the dark to reach the adsorption–desorption were obtained at the conditions: pH = 5.74, time = 5 h,
equilibrium) in Figs. 6 and 7 to select the suitable catalyst. initial RhB concentration = 3 mg L–1, Catalyst concen-
Sample S1 (96.43% degradation) and H1 (92.39% degra- tration = 0.2 g L–1. Degradation at these optimum condi-
dation) were selected for photocatalytic degradation tests tions correlated 91.96% compared with the experimental
of RhB. To investigate the effects of operational parameters result of 92.91% which illustrated the good accuracy.
432 S. Dolatabadi et al. / Desalination and Water Treatment 231 (2021) 425–435

S1 S2

S4 S6

H1 H2

H3

Fig. 5. FESEM analysis of synthesized samples.

 S. Dolatabadi et al. / Desalination and Water Treatment 231 (2021) 425–435 433

3.7. Mechanism 4. Conclusions

Based on researches in the open literature [10,36] regard- TiO2/ZnO nanostructures were synthesized by sol–
ing photocatalysis a probable mechanism and photodeg- gel (sol–gel and SSD) and hydrothermal methods in
radation reactions of organic RhB using TiO2-ZnO oxide various wt%, calcination temperatures, hydrothermal
materials as proposed below: temperatures and hydrothermal times. XRD, BET, FTIR,
and FESEM analyses were performed to characterize the
TiO2/ZnO photocatalysts + hv → e– + h+ (3) catalysts. Combining TiO2 with other suitable semicon-
ductors such as ZnO might be reduced electron–hole
h+ + H2O → H+ + OH• (4) recombination of photo-electrons and improved effi-
ciency. All samples synthesized by sol–gel method have
h+ + OH– → OH• (5) an anatase phase, however, samples synthesized by the
hydrothermal method have a rutile phase. Synthesized
samples by the hydrothermal method are more uniform
h+ + Rhodamine B → oxidation products (6)
than synthesizes samples by sol–gel method. Moreover,
synthesized samples by the hydrothermal method are
e– + O2 → •O2 (7)
more rod-like in shape. The total pore volume and surface
area of samples prepared by the hydrothermal method
O2– + 2H+ → H2O2
•
(8) are larger than sol–gel method.
The results of degradation tests for all samples have
e– + H2O2 → OH• + OH– (9) been reported, from these results, it will be concluded that
samples prepared by the hydrothermal method are better
e– + Rhodamine B → reduction products (10) for degradation of RhB, although the best degradation has
been obtained by sample S1 that synthesized by sol–gel
Rhodamine B + OH• + O2 → CO2 + H2O method. The best degradation of RhB by sample S1 was
+ other decomposition products (11) 99.28% and by sample, H1 was 98.57%.

(a) (b)

(d)

(c)

Fig. 6. Plots of (a) residual vs. predicted response for degradation, (b) predicted responses vs. actual experimental values
for degradation, (c) one factor and (d) 3D surface for sample S1.
434 S. Dolatabadi et al. / Desalination and Water Treatment 231 (2021) 425–435

(a)
(b)

(c)
(d)

Fig. 7. Plots of (a) residual vs. predicted response for degradation, (b) predicted responses vs. actual experimental values for
degradation, (c) one factor and (d) 3D surface for sample H1.

Optimum conditions for experiments were obtained by nanorods heterojunction, Nanomaterials (Basel), 10 (2020) 2096,
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