Ceramics International 47 (2021) 27294–27304

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Enhanced photocatalytic degradation of Acid Blue 1 using Ni-Decorated

ZnO NPs synthesized by sol-gel method: RSM optimization approach
Lida Aeindartehran, S. Siamak Ashraf Talesh *
Department of Chemical Engineering, Faculty of Engineering, University of Guilan, Rasht, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: In this research, the synthesis of pure and Ni-decorated ZnO nanoparticles was carried out successfully by sol-gel
Photocatalysis method. The morphology, structure, chemical bonding, and absorption spectrum of the synthesized nanoparticles
ZnO nanoparticles were investigated using FESEM, TEM, XRD, EDX and elemental mapping, FT-IR, and UV–Vis techniques. After Ni
Ni decoration
decoration, the spherical structure of ZnO nanoparticles almost changed to uniform hexagonal nanoparticles. The
Dye degradation
Experimental design
synthesized nanoparticles were used for Acid Blue 1 dye degradation through a photocatalysis procedure under
UV light (6 w). The influence of four factors, including metal (Ni) percentage, dye concentration, catalyst dosage,
and pH, on the photocatalytic activity of the synthesized photocatalysts, was studied. The experiments were
evaluated by means of the response surface methodology (RSM) based on the central composite design (CCD).
The experimental results indicated dye concentration = 10 mg/L, pH = 7.77, Ni percentage = 1.117% and
catalyst dosage = 1.07 g/L as the optimum values for variables. At optimum conditions, CCD estimated the
degradation rate equal to 90.23% which is close to the experimental efficiency, 89.13%, (R2 = 0.9877 and
adjusted R2 = 0.9762). The results confirmed the reliability of the CCD to predict the amount of dye removal.
Additionally, the Ni-decorated ZnO nanoparticles had more activity in the visible area than the pure ZnO sample.
According to the UV–Vis spectra, the band gap decreased from 3.13 to 2.97 eV by adding Ni to ZnO. Furthermore,
the Ni-decorated ZnO sample represented a significant redshift compared to the pure sample.

1. Introduction C27H31N2NaO6S2 belongs to a dye group named triphenylmethane [7,

One of the major environmental problems is believed to be the
human access to clean water for different applications, especially for
drinking and agricultural objectives [1]. Generally, industrial develop­
ment is followed by increasing industrial waste and a noticeable incre­
ment in environmental pollution. Therefore, contaminated water
treatment is a controversial problem in the world today [2]. Among the
diverse components of wastewater, dyes play a major role in water
contaminations [3]. Dyes are widely used in many industries such as
printing ink, food colorings, biology, and textile production [4]. Dyes
used in these industries can be present in significant amounts in the
effluents of factories. Therefore, they are considered as a potential
source of pollution in rivers and waterways. Dye existence in drinking
water should be lower than the determined standard level. This level is
not the same for all categories of dyes [5]. Higher volumes of dyes in
wastewaters can certainly lead to serious health hazards, the most
important of which are respiratory problems, skin irritation, and sore
eyes [6]. Acid Blue 1 or Sulfan Blue with the molecular formula
8].
For the treatment of sewage, several techniques such as biological
treatment, incineration, absorption, and electrochemical approaches are
investigated. It should be noted that each of them has its drawbacks,
including time-consuming biological treatments, uncompleted com­
bustion through incineration, and the inability to remove pollutants
efficiently [9]. Moreover, most of these procedures need high capital
costs. Nano-photocatalysis is a type of advanced oxidation process
(AOP) using hydroxyl free radicals (OH.) to destroy organic compounds.
In fact, the energy of photons results in changes in electron layers of
nano-photocatalysts [10]. The outcome is the production of a large
number of active radicals of hydrogen and oxygen. These radicals and
electron cavities provide the best condition to remove a wide range of
pollutants [11]. There are numerous photocatalysts such as TiO2, WO3,
ZnO, CdS, SnIn4S8, among which ZnO has been widely studied for its
stability, consistency in the environment, suitable price, and nontoxicity
[12–17]. The great band gap of ZnO is the reason for its activation in just
ultraviolet light. On the other hand, the couple velocity of holes and

* Corresponding author.
E-mail address: s_ashraf@guilan.ac.ir (S.S. Ashraf Talesh).

https://doi.org/10.1016/j.ceramint.2021.06.151
Received 15 April 2021; Received in revised form 17 June 2021; Accepted 19 June 2021
Available online 20 June 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
L. Aeindartehran and S.S. Ashraf Talesh
Fig. 1. Preparation scheme of Ni-decorated ZnO catalyst.
electrons and the wide bandwidth are counted as restrictions of
employing ZnO as a photocatalyst [18]. To address this problem, many
attempts have been made so far. For example, Rathore et al. [19] pro­
duced N-doped ZnO using a precipitation method. An enhancement was
achieved from the N-doped ZnO for degradation of azure B dye
compared to the pure catalyst form. In another work, Yang et al. [20]
used a method of replacing the hydrothermal process to decorate Ni (as
Ni0 and Ni2+ forms) on the ZnO photocatalyst. In this method, the
morphology of the ZnO photocatalyst and its photocatalytic activity was
enhanced. Le et al. [21] studied the photocatalytic activity of ZnO
nanoparticles using KF and thermal shock. According to this study, both
visible light and UVA photocatalytic activity for degradation of methy­
lene blue increased. They attributed the observed enhancement in ZnO
performance to the increment in zinc vacancies of the modified ZnO and
hydroxyl groups of the surface.
In this research, Ni-decorated ZnO nanoparticles were synthesized
using the sol-gel method to accurately control the homogeneity of the
solution and final shape of the nanoparticles. To analyze the structure
and morphology of provided nanoparticles, X-ray Diffraction (XRD),
Field Emission Scanning Electron Microscopy (FESEM), Transmission
Electron Microscope (TEM), Energy-Dispersive X-ray Analysis (EDX),
and Fourier-Transform Infrared Spectroscopy (FT-IR) were exploited.
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Furthermore, a UV–Vis spectrophotometer was used to evaluate the
absorption spectra of the samples. The main aim of this study was to
optimize the combined effects of the four independent variables: Ni
percentage, catalyst dosage, dye concentration, and pH utilizing a cen­
tral composite design (CCD). The experimental design, statistical anal­
ysis, and response surface plots were done by the Design Expert Software
(version 10). It is worth mentioning that, for the first time, the Ni-
decorated ZnO photocatalyst was applied to degrade Acid Blue 1.
2. Materials and methods
2.1. Materials
Zinc acetate dihydrate (Zn (CH3COO)2⋅2H2O) and Acid Blue 1 were
obtained from Merck. Nickel nitrate Hexahydrate (Ni (NO3)2⋅6H2O) and
methanol (CH3OH) were purchased from Loba Chemie. Sodium hy­
droxide pellets (NaOH) were from Carlo Erba. Absolute ethyl alcohol
(C2H5OH, 99.6%) was provided by Zakaria Jahrom. Co. Deionized water
was used for all the experiments conducted. All mentioned materials
were used without further purification.
2.2. Synthesis of photocatalyst
2.2.1. Preparation of ZnO nanoparticles
The sol-gel method was utilized to synthesize ZnO nanoparticles at
different Ni concentrations. The procedures were all performed at room
temperature. After dissolving an appropriate amount of zinc acetate
powder into 100 ml of methanol, the resulting 0.2 M solution was stirred
for 90 min. Next, NaOH (1 M) was added dropwise to the prepared so­
lution until its pH level reached 10. The solution was agitated again for
120 min. Then, it was centrifuged at 2000 rpm for 15 min and subse­
quently dried at 70 ◦ C overnight.
2.2.2. Decoration of Ni on ZnO
25 ml of ethanol was mixed under stirring with the synthesized ZnO
powder from the previous step. After a few minutes, with respect to the
intended concentration of Ni in photocatalyst, a suitable amount of
nickel nitrate was added to the mixture and agitated for 1 h to form the
sol part. Depending on the amount of nickel nitrate, a proper volume of
NaOH (1 M) was added drop by drop to form the gel under stirring for 1
h. The formed gel was dried at 80 ◦ C for 18 h. Finally, the resulting white
powder was ready to use for the experiments. The process of fabricating
the resulting catalyst is provided in Fig. 1.
2.3. Characterization of the photocatalyst
Using X-ray diffraction (XRD, Philips, pw1800, with Cu Kα radia­
tion), the structures of samples were determined. The morphology of the
samples was assessed by FESEM (SIGMA VP), TEM (EM 208 S Philips),
EDX (Oxford instrument), and FT-IR (Spectrum two) techniques.
Furthermore, a UV–Vis spectrophotometer (Jenway, England) was used
to determine the photocatalytic activity and absorption spectrum.
2.4. Photocatalytic activity
The photocatalytic activity of pure ZnO and Ni-decorated ZnO
nanoparticles were examined in the absence of light. Moreover, a UV
light (Hg lamp mercury 6 W, China) was applied as the irradiation
source. 100 ml of Acid Blue 1 solution was prepared with various initial
concentrations as a pollutant. Then, a certain amount of the synthesized
catalyst was added to the Acid Blue 1 solution under stirring. Before the
radiation step, the suspension was placed in the dark for 30 min to reach
the adsorption-desorption equilibrium. When the lamp was switched on,
the photocatalytic procedure began and samples were periodically
collected from the beaker to assess the degree of color degradation. The
samples including the catalyst particles, were instantly centrifuged to
L. Aeindartehran and S.S. Ashraf Talesh Ceramics International 47 (2021) 27294–27304

Table 1 Since four independent variables were opted in this study, the parameter
Independent values quantity planned by CCD. of Alpha is 2. The rotatable design enhances the prediction quality
Variables Units Ranges because the preferred features of constant prediction variance at all
points, which have the same distance from the design center, are sup­
− 2 − 1 0 1 2
plied by the rotatable design [24]. According to the CCD data process,
Ni percentage wt% 0 0.5 1 1.5 2 the ranges of the independent values are shown in Table 1. Applying
Catalyst dosage g/L 0.3 0.6 0.9 1.2 1.5
Dye concentration mg/L 10 15 20 25 30
CCD, these parameters were estimated by a quadratic polynomial
pH value – 7 8 9 10 11 equation for the four parameters expressed as Eq. (3) [25]:

Y(%) = b0 + b1 A + b2 B + b3 C + b4 D + b12 AB + b13 AC + b14 AD + b23 BC

eliminate catalyst particles. The concentration of Acid Blue 1 solution
was estimated by a UV-VIS spectrophotometer at the maximum ab­
sorption wavelength of the dye (637 nm). The degradation efficiency of
the experiments can be calculated by Eq. (1) [22]:
Degradation rate% = (C0 − C)/C0 × 100
where C0 and C are the initial and final concentrations of the pollutant,
respectively.
2.5. Experimental design
In this research, four factors were considered as significant experi­
mental variables influencing photocatalytic efficiency. To optimize the
independent variables, mainly catalyst dosage, initial concentration of
dye, pH value, and Ni percentage, the central composition design (CCD)
was employed by the design expert software (version 10). The number of
experiments for four parameters was determined in Eq. (2) [23]:
2n + 2n + 6 = 24 (16 tests for factorical points) + 4 × 2 (8 tets for axial points)
+ 6 (central points) = 30, n = 4
It should be mentioned that the parameter of Alpha (α), representing
the design rotatability, was considered as the distance from the center
point in a CCD. This value relies on the number of experiment variables.
+ b24 BD + b34 CD + b11 A2 + b22 B2 + b33 C2 + b44 D2
(3)
where Y represents the variable response. b0 shows the intercept. b1, b2,
b3, b4, are the coefficients of the independent variables. b11, b22, b33, b44,
(1)
are quadratic coefficients. b12, b23, b13, b14, b24, and b34 are the inter­
action coefficients. Furthermore, A, B, C, and D are the independent
variables, including Ni percentage in the fabricated catalyst, the catalyst
dosage, the dye concentration, and the pH value, respectively.
3. Results and discussion
3.1. Characterization of catalysts
3.1.1. Nanoparticles morphology
The surface morphologies of the synthesized ZnO and Ni-decorated
ZnO (Ni/ZnO ratio is 1.117 %w.) nanoparticles were characterized by
FESEM and TEM (Fig. 2). As can be seen, there is a regularity in shape
and size in pure ZnO. The sphere-like and randomized hexagonal
(2) structure and constant size of nanoparticles are also observed (Fig. 2- a).
After the incorporation of Ni, the size of the nanostructures increased.
Additionally, the introduction of Ni altered the sample shape to egg-like
by corners following a fair uniformity in size (Fig. 2- b). Due to such

Fig. 2. FESEM images of samples: (a) pure ZnO, (b) Ni-decorated ZnO, TEM images of samples: (c) pure ZnO, (d) Ni-decorated ZnO.

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Fig. 3. EDX spectrum and elemental mapping of (a) pure ZnO and (b) Ni-decorated ZnO.

Fig. 4. FT-IR spectra of nanoparticles: (a) pure ZnO and (b) Ni-decorated ZnO.

changes, the specific surface area grew. Consequently, the available
adsorption surface area for dye fragments on the surface of the catalyst
expanded. Fig. 2-b shows a dispersed aggregate considered to be the
outcome of adding Ni to the pure ZnO that is beneficial to photo­
catalysis; as it helps the adsorption of dye molecules on the surface of the
catalysts and assists the penetration of light during the degradation
process [26]. Regarding the TEM images, Fig. 2-c shows pure ZnO
nanoparticles with visible randomized hexagonal structure. This is
consistent with the XRD and FESEM results. In Fig. 2-d, the addition of
1.117 wt% Ni (optimal content) leads to an increase in the size of the
nanoparticles. This image also displays that the decorated sample has a
hexagonal structure. This confirms the results obtained through the
FESEM images and the XRD spectrum.
The EDX spectrum of the pure ZnO and the modified sample are
presented in Fig. 3. The elemental composition illustrates in Fig. 3- a
confirmed successful synthesis of the pure ZnO nanoparticles by the
presence of Zinc and Oxygen. Elemental mapping of Ni-decorated ZnO
sample (Fig. 3- b) showed the uniform distribution of Zn, Ni, and O with
relative amounts of 68.44, 1.05, and 29.6 wt%, respectively.
3.1.2. Chemical bonding
Fig. 4 indicates the FT-IR spectrum of the pure ZnO compared with
Ni-decorated ZnO to show different chemical bands and surface chem­
istry in the range of 400–4000 cm− 1. The following information is

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Fig. 5. (a) UV–Vis absorption spectra of ZnO nanoparticles, the (αhν)2 versus (hν) for (b) pure ZnO and (c) Ni-decorated ZnO.

Fig. 6. Photoluminescence spectra of ZnO and Ni-decorated ZnO nanoparticles at excitation wavelength of 325 nm.

Fig. 7. The X-ray diffraction patterns of (a) Pure ZnO and (b) Ni-decorated ZnO nanoparticles.

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Table 2
Central composite design Table of planned values along with experimental and predicted results for Acid Blue 1 degradation.
Runs A B C D Dye degradation (%) Residuals

Ni percentage (wt%) Catalyst dosage (g/L) Dye concentration (mg/L) pH value Experimental Anticipated

1 2 0.9 20 9 64.39 61.30 3.09

2 1 0.9 10 9 83.98 85.57 − 1.59
3 0.5 0.6 15 8 61.88 60.46 1.42
4 1.5 0.6 25 8 58.58 59.60 − 1.02
5 1 0.9 20 9 76.32 77.30 − 0.98
6 0.5 0.6 25 10 48.75 49.18 − 0.43
7 1 1.5 20 9 65.41 64.88 0.53
8 1 0.9 20 11 67.4 66.41 0.99
9 0.5 1.2 25 8 68.36 67.95 0.41
10 1 0.3 20 9 35.74 35.61 0.13
11 1.5 1.2 25 10 65.98 67.43 − 1.45
12 1 0.9 20 9 75.28 77.30 − 2.02
13 0.5 0.6 25 8 54.08 53.76 0.32
14 0 0.9 20 9 49.88 52.30 − 2.42
15 1 0.9 20 9 78.21 77.30 0.91
16 1.5 1.2 25 8 70.59 72.22 − 1.63
17 1.5 0.6 25 10 52.62 53.87 − 1.25
18 1 0.9 30 9 74.31 72.06 2.25
19 1.5 0.6 15 10 58.73 59.17 − 0.44
20 1 0.9 20 9 78.27 77.30 0.97
21 0.5 1.2 25 10 64.19 64.32 − 0.13
22 1.5 1.2 15 10 73.29 74.24 − 0.95
23 0.5 0.6 15 10 55.42 54.43 0.99
24 0.5 1.2 15 10 72.08 71.08 1.00
25 1.5 0.6 15 8 65.84 66.35 − 0.51
26 1 0.9 20 9 78.42 77.30 1.12
27 1 0.9 20 9 77.32 77.30 0.017
28 1.5 1.2 15 8 80.88 80.48 0.40
29 1 0.9 20 7 76.9 77.23 − 0.33
30 0.5 1.2 15 8 76.78 76.17 0.61

Table 3 Table 4
A summary of the tested statistical method for Acid Blue 1 degradation. Corresponding F-values and P-values and Coefficient estimate for Acid Blue 1
degradation.
Sequential Model Sum of Squares
Factor F-value P-value Coefficient estimate Standard error
Statistical F- P-value Sum of df Mean
methods value Squares Square A 39.47 <0.0001 2.25 0.36
B 417.48 <0.0001 7.32 0.36
Linear vs 6.12 0.0014 1855.76 4 463.94
C 89.04 <0.0001 − 3.38 0.36
Mean
D 57.09 <0.0001 − 2.71 0.36
Quadratic vs 149.37 < 0.0001 1838.60 4 459.65
AB 0.81 0.3827 − 0.39 0.44
2FI
AC 7.332E-004 0.9788 − 0.012 0.44
Cubic vs 3.26 0.0683 36.40 8 4.55
AD 0.43 0.5211 − 0.29 0.44
Quadratic
BC 0.75 0.4006 − 0.38 0.44
2FI vs Linear 0.015 1.0000 9.11 6 1.52
BD 0.29 0.5970 0.24 0.44
Lack of fit tests
CD 0.68 0.4222 0.36 0.44
Statistical F- P-value Sum of df Mean
A2 243.13 <0.0001 − 5.13 0.33
methods value Squares Square
B2 407.94 <0.0001 − 6.77 0.33
Linear 58.46 0.0001 1885.81 20 94.29 C2 1.27 0.2776 0.38 0.33
Quadratic 2.36 0.1776 38.09 10 3.81 D2 16.76 0.0010 − 1.37 0.33
Cubic 0.52 0.6211 1.69 2 0.85
2FI 83.11 <0.0001 1876.69 14 134.05
Summary statistics of model
2
1024 cm− 1 shows the C–O–C bond in both samples [29]. The peak at
Statistical R Adjusted Predicted Deviations. Press
667 cm− 1 is due to the O–
– C–
– O bending vibration. An asymmetric and
methods R2 R2 Std
symmetric C–H stretching bond was detected at peaks from 2850 to
Linear 0.4949 0.4141 0.2956 8.70 2641.36 3000 cm− 1 [30–32]. The observed peak in the range of 400–650 cm− 1
Quadratic 0.9877 0.9762 0.9384 1.75 231.03
Cubic 0.9974 0.9892 0.9319 1.18 255.32
corresponds to the metal-oxygen (M/ZnO and ZnO) stretching modes.
2FI 0.4973 0.2328 0.1578 9.96 3158.05 Accordingly, the peak at 509 cm− 1 is due to ZnO formation. In addition,
the peak around 483 cm− 1 is the sign of Ni–O stretching vibrations [33,
34].
collected according to the spectrum of both samples (Fig. 4- a and b). A
broad peak at about 3400 cm− 1 is ascribed to the bending vibrations of 3.1.3. Optical properties
the adsorbed molecular water, and the O–H stretching bond appeared in The absorption spectra were employed to investigate the excitation
both samples [27]. The peaks observed at around 2330 cm− 1 are due to processes of the Ni-decorated ZnO catalyst. The band gap of the nano­
the adsorbed CO2 on the surface of the samples. The peak at 931 cm− 1 is particles was measured by UV–Vis spectrum and Tauc Eq. (4) [35]:
attributed to the Zn–C bonds [28]. The absorption peaks at around 1300, ( )
1400, and 1600 cm− 1 correspond to the C–O stretching, C–H vibrations (αhν)2 = A hν − Eg (4)
(wagging, twisting), and COO-metal bond, respectively. A sharp peak at

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Fig. 8. Pareto chart analysis to determine the effectiveness of each variable.

Fig. 9. The normal probability plot (a), the graphical plot of predicted versus experimental data (b), the graphs of residual versus predicted values (c).

where hν is photon energy, α is the absorption coefficient, Eg and A are
the band gap energy and constant of the equation, respectively. Fig. 5
demonstrates the VU-Vis absorption spectrum of the pure ZnO and Ni-
decorated ZnO nanoparticles at room temperature. By scheming
(αhν)2 as a function of (hν) and the calculation of linear extrapolation,
the band gap was estimated (Fig. 5). Pure ZnO has the absorption band
edge (λmax) at 350 nm, illustrating the transition of electrons from the
valence band to the conduction band [36]. Ni-decorated ZnO sample
had reposition toward the visible area and a maximum absorption
spectrum in wavelength of 368 nm compared to the pure ZnO (Fig. 5- a).
The absorption shift of the decorated nanoparticles to the visible area
might be associated with the reaction between ZnO and the metal. This
might be due to the generation of impurity state between the valence
and conduction band of ZnO, and also further interaction between
valence electron bands [37,38]. As shown in Fig. 5- b, c, by adding Ni to
ZnO, the band gap quantity decreased from 3.13 to 2.97 eV. Therefore,
the Ni-decorated ZnO composite had a significant red shift in compari­
son with the pure sample. This phenomenon could be attributed to the
sp–d exchange interactivity between the electrons located in the con­
duction band and the localized d electrons of the transition metal-ions
substituting the Zn2+ [20].
Fig. 6 shows the room temperature PL spectrum of the pure and Ni-
decorated ZnO nanoparticles. In the pure sample, the peak at 383 nm
attributes to the UV near-band-edge (NBE) emission. This peak is due to
the recombination of photogenerated electron-hole pairs [39]. A negli­
gible green band (500–575 nm) centered around 558 nm originates from
relatively common defect emission in ZnO nanoparticles, such as oxygen
vacancies or impurities [40,41]. The Ni-decorated ZnO sample

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Fig. 10. Box-Cox plot of the model.
Fig. 11. Perturbation plot, Ni percentage (A), catalyst dosage (B), dye con­
centration (C) and pH value (D).
illustrates intensity reduction by the absence of significant shifting of the
peak’s position. This decrement proves the decrease in electron-hole
recombination [26]. The green emission is also quenched in the deco­
rated sample. This observation displays charge carrier separation within
the structure of the Ni-decorated ZnO nanoparticles [42]. It reveals the
presence of deposited Nickel nanoparticles in the ZnO structure which
hinders the recombination of the electron-hole pairs by capturing elec­
trons [43].
3.1.4. X-ray diffraction
The phase analysis of catalysts was carried out by XRD measure­
ments in the range of 4◦ –60◦ . In Fig. 7, the XRD patterns of the pure
sample and the modified ZnO nanoparticles are shown. The peaks
clearly distinguished in both pure and Ni-decorated ZnO samples are
consistent with the hexagonal ZnO, documented in the Joint Committee
on Powder Diffraction Standards (JCPDS) [44]. In the pure sample,
several crystalline peaks composed of the ZnO are observed. There is no
additional diffraction peak, indicating that the pure sample of ZnO is
crystalline and pure [29]. Unquestionably, there is no detectable trace of
Ni in the decorated ZnO. This absence in the XRD figure is because Ni2+
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ions are extremely dispersed into the lattice of ZnO and substituted Zn2+
ions [45]. From the Debye-Scherer Eq. (5) [46], the average crystal size
of the fabricated nanoparticles was calculated:
180 K ​ λ
D= (5)
π ​ β ​ cosθ
where D, K, λ, θ, and β are the crystallite size of the nanoparticle, the
shape factor (0.89), the wavelength of used radiation, the diffraction
angle and full width at half of the maximum peak in radians (FWHM),
respectively. The average size of nanoparticles increased from 19.19 to
24.79 nm due to the decoration of Ni on the ZnO samples.
3.2. Central-composite design model
The obtained experimental results and predicted values by the model
are provided in Table 2. This shows the effect of the variable amounts on
dye degradation. According to the model analysis, a quadratic response
surface was specified to explain how the experimental results and in­
dependent values were related by following Eq. (6):
Dye ​ degradation ​ (%) = 77.30 + 2.25 ​ A + 7.32 ​ B − 3.38 ​ C − 2.71 ​ D
− 0.39 ​ AB − 0.012 ​ AC − 0.29 ​ AD − 0.38 ​ BC + 0.24 ​ BD + 0.36 ​ CD
− 5.13 ​ A2 − 6.77 ​ B2 + 0.38 ​ C2 − 1.37 ​ D2
(6)
The model was manipulated to assess the response of different sta­
tistical methods. The results are presented in Table 3. F-value should
have a greater amount than the F-distribution value for a limited degree
of freedom at a level of significance α (tabulated F = 2.36 at 95% sig­
nificance) [47]. Accordingly, F-value was reported to be 149.37, which
was significant. There was only a 0.01% chance that this large F-value
could occur due to the noise. A useful factor in distinguishing the
interaction pattern between the variables is P-value [48]. Both the sig­
nificant P-value of the model (<0.0001) and the insignificant P-value for
lack of fit (0.1776 > 0.05) showed that the quadratic model was reliable
for this research. The obtained coefficient of determination (R2) was
0.9877 meaning the model can deviate 0.9877% of the data. Adjusted
and predicted R2 are in agreement with each other. This means that the
predicted quadratic model can be efficiently exploited to navigate the
design space [49]. Additionally, the high value of adjusted R2 (0.9762)
confirms the acceptable consistency between the experimental and
predicted results, which is a sign of the appropriate predictability of the
model [50]. The small value of PRESS (predicted residual error sum of
square = 231.03) reveals that the model can fit the data. Table 4 shows
the effect of each coefficient on the degradation, suggesting that the
second-order polynomial equation is suitable to describe the relation­
ship between the dye degradation and selected variables. Consequently,
this model is trustable to predict Acid Blue 1 degradation by the syn­
thesized Ni-decorated ZnO nanoparticles.
Another analysis measuring the percentage of each parameter’s ef­
fect on the result is called the Pareto analysis provided in Eq. (7) [51]:
( 2 )
bi
Pi = ∑ 2 × 100(i ∕ = 0) (7)
bi
where bi is the operational parameter influencing the process of dye
degradation.
The results are shown in Fig. 8. The parameters that had an insig­
nificant effect on the process (less than 1%) were removed from this
figure. According to the results, catalyst dosage has the main effect on
dye degradation (35.21%). In fact, by increasing the catalyst amount,
more active sites are available to participate in the radical formation
[52].
The normal probability plot (Fig. 9- a) depicts that the residuals are
close to the diagonal line. This reveals that since the plot shows the
independence of the residuals, the model could sufficiently explain the
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Fig. 12. 3D response surface plots, (a) Ni percentage and catalyst dosage, (b) dye concentration and Ni percentage, (c) pH value and Ni percentage, (d) dye con­
centration and catalyst dosage, (e) pH value and catalyst dosage, (f) pH value and dye concentration.

Fig. 13. Optimized values for a final response via CCD.

relationship between the tested variables and the results [53]. The
graphical plot of the predicted data versus experimental data (Fig. 9- b)
illustrates good consistency between these two parameters. The graphs
of residual versus predicted values (Fig. 9- c) exhibit unsystematic
dispersion of the residues and distribution between − 4 and +4. Addi­
tionally, the Box-Cox plot (Fig. 10) verifies the good predictability of the
model and that there is no need for transformation of the model
response.
To probe the simultaneous effect of four variables on dye removal,
the perturbation plot was drawn which is shown in Fig. 11. Generally,
this plot compares among all factors’ influences at a particular point in
the design space [54]. Ni percentage (A), catalyst dosage (B), dye con­
centration (C), and pH value (D) were the controlling parameters in Acid
Blue 1 degradation. Hence, the existence of the curvature for catalyst
dosage is proof that this factor is more influential than the others. This is
in agreement with the responses provided in Fig. 8.
3D surface plots represented in Fig. 12 show the type of interaction
between the independent variables and helps to understand the opti­
mum condition. This figure shows a second-order polynomial equation
by setting two out of four parameters fixed. As can be seen, catalyst
dosage changed from 0.3 to 1.5 g/L, and Ni percentage varied from 0 to
2 %w. Dye concentration and pH values were 20 mg/L and 9, respec­
tively. According to Fig. 12- a, the changes in both Ni percentage and
catalyst dosage parameters had a certain effect on the efficiency of the
photocatalyst.
Adding metal to the structure of the catalyst increases the dye

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L. Aeindartehran and S.S. Ashraf Talesh
degradation via three possible mechanisms: Firstly, the transition metals
(Ni2+ in this case) penetrating the ZnO crystal enhance the electrical
transport of photo-generated charges by being catalytically active and
leave a synergetic effect on the photocatalysis process [55]. Secondly,
metal particles prevent the recombination of electron-hole pairs by
acting as an electron sink. This is feasible through the establishment of
metal-semiconductor heterojunctions [56]. Finally, adsorbed oxygen
acting as an electron scavenger improves the electron-hole separation
produced during photocatalysis [57]. Considering these steps, the
Ni-decorated catalyst outperformed the pure ZnO. Furthermore, its
positive effect increased until the optimum Ni percentage in the catalyst
(1.117%). After the optimum point, the dye removal decrement was due
to the high concentration of decorated metals on the catalyst surface and
the lack of enough hydroxyl production due to the less light penetration
(Fig. 12- a, b, c) [58]. The catalyst dosage effect had the same trend as
the metal percentage. Before 1 g/L of catalyst, its rise was effective in
dye removal because more active sites were available and more dye
molecules were adsorbed that eventually improved the photocatalytic
activity [59]. When the amount of catalyst increased to 1 g/L, more
active surface was provided, leading to a decrease in UV light penetra­
tion. The reason is that a lot of catalyst particles existed in the solution
(Fig. 12- a, d, e) [60]. The effect of the initial dye concentration and the
Ni percentage was studied as well (Fig. 12- b). Acid Blue 1 concentration
varied from 10 to 30 mg/L while catalyst dosage and pH values were 0.9
g/L and 9, respectively. It appears that the degradation percentage of
dye declined by increasing the initial dye. The rate of dye degradation
depended on the possibility of the (OH.) formation on the catalyst sur­
face and the probability of reaction of these (OH.) produced by dye
molecules. Therefore, in the constant quantity of catalyst dosage, the
production of (OH.) remained unchanged; thus, by enhancing the dye
concentration, the possibility of reaction between dye molecules and
hydroxyl radicals decreased [26]. Furthermore, the high concentration
of dye molecules did not let the UV light penetrate the catalyst to pro­
duce charged species. In other words, limited reactive species led to
photocatalytic activity decrement (Fig. 12- b, d, f) [61].
The pH was considered in the range of 7–11, while other parameters
were constant. It should be noted that the pH was adjusted before the
irradiation and it was not maintained during the experiment. The pH is
an important part of photocatalytic efficiency since it has a relationship
with the ionization state of the photocatalyst and the pollutant surface
[62]. Additionally, it can be effective in dye molecule adsorption on the
catalyst surface and can be considered an imperative step for photo­
catalytic oxidation [63]. It is obvious that the dye degradation increased
up to pH 8 and diminished dramatically at higher pH values than 9. The
synthesized ZnO had a zero-point charge at about pH = 9 and a positive
charge at pH values between 5 and 7. Since Acid Blue 1 is an anionic dye
by negative charge, positive ZnO had appropriate conditions for
adsorption of this dye because of its electrostatic attraction [64]. This
phenomenon could suggest that the photocatalytic reaction occurred on
the surface of the catalyst and also, through the reaction of the dye in the
bulk solution including photo-generated holes and hydroxyl free radi­
cals in the catalyst surface vicinity (Fig, 12- c, e, f).
3.2.1. Optimization
An optimization test was performed to distinguish the optimum
operational condition to reach the highest efficiency. Accordingly, the
maximum degradation of Acid Blue 1 (90.23%) was obtained by the
proposed model with Ni percentage = 1.117%, catalyst dosage = 1.07 g/
L, pH = 7.77, and dye concentration = 10 mg/L values. In Fig. 13, the
results are depicted. Since the experimental Acid Blue 1 degradation was
89.13%, the model reliability to anticipate the process efficiency by the
synthesized catalyst at various operational factors was confirmed.
4. Conclusion
In this research, Ni-decorated ZnO nanoparticles were synthesized
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Ceramics International 47 (2021) 27294–27304
successfully by the sol-gel approach. Due to Ni decoration, the spherical
structure almost changed to uniform hexagonal morphology. The cata­
lyst was utilized for Acid Blue 1 dye degradation. Four parameters were
investigated which are as follows, dye concentration, catalyst dosage,
pH value, and Ni percentage in the Ni-decorated ZnO structure. All
factors, except for dye concentration, had an appropriate range impact
the dye degradation process positively. Regarding dye concentration,
the experiments revealed that a decrement in this factor was desirable
for better efficiency. Response methodology was successful to optimize
main operational variables according to central composite design. The
results proved that the model was reliable to predict the process effi­
ciency at various operational parameters according to R2 = 0.9877 and
adjusted R2 = 0.9762. As a result, the optimum condition for the best
degradation equal to 90.23% was gained at the Ni percentage of 1.117%,
catalyst dosage of 1.07 g/L, pH value of 7.77, and dye concentration of
10 mg/L.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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