Received: 4 February 2018 Revised and accepted: 17 May 2018

DOI: 10.1002/jccs.201800029

ARTICLE

Investigation of the kinetics and optimization of photocatalytic

degradation of methylene blue
Rania Farouq

Petrochemical Engineering Department, Pharos

University, Alexandria, Egypt
Correspondence
Rania Farouq, Petrochemical Engineering
Department, Pharos University, Alexandria, Egypt.
Email: rania.farouq@pua.edu.eg
Studying and optimizing the photocatalytic degradation of methylene blue dye in a
tubular reactor using different types of titanium dioxide are the main concerns of
the present research. Subsequent experiments using a heterogeneous process
(UV/H2O2/TiO2) were conducted to investigate the effects of the changing amounts
of catalyst dosing, pH values, time, and the initial dye concentration on the process
performance. Response-surface methodology (RSM) experiment based on a
mixture-analysis experiment was applied. The results show that an initial dye con-
centration of 20 ppm at pH = 2 with the addition of H2O2 (0.2 mL) to the pollutant
stream represents the best conditions of the photocatalytic process with 97.6% of
dye degradation when using 1.5 g TiO2/L of the pollutant solution. All the experi-
mental data showed good agreement with the predicted results obtained from statis-
tical analysis.

KEYWORDS

kinetics, methylene blue (MB), mixture analysis, photocatalytic, RSM

1 | INTRODUCTION capacity and the photogenerated electrons have reduction

Water could be contaminated by various types of discharges
(such as heavy metals, dyes, and pesticides), which can be
toxic, or causing skin irritation, and even posing a serious
hazard to living organisms. Although various treatment
methods have been distinguished, these methods have lim-
ited applications due to their high cost and poor degradation
efficiency.[1–4] However, adsorption has been proven to be
very effective for the removal of dyes. Photocatalysis
appears to be quite promising as a cost-effective alternative
in environmental pollution remediation and solar-energy
conversion. Semiconductor-based photocatalyst materials
include metal oxides, sulfides, nitrides, and their mixed solid
solutions.[5–8] Photocatalysts are described by filled valence
bands and empty conduction ones. At the point when a pho-
ton has energy equivalent to or more noteworthy than the
band gap, an electron is elevated to the conduction band,
abandoning a positive hole in the valence band.[9] In this
way, a photocatalytic response continues, which is attribut-
able to holes and electrons created in materials by engross-
ing light energy. The photogenerated gaps have oxidation
capacity.[10,11]
Titanium dioxide is a prime candidate in photocatalytic
reactions. The main advantages of TiO2 are its high chemical
stability when exposed to acidic and basic compounds, its
nontoxicity, its relatively low cost, and its high oxidizing
power. Several studies have been reported on the application
of TiO2 photocatalysts in reducing the harmful effects of oil
spills as well as in various environmental applications such
as photodegradation of organic and inorganic pollutants,
decolorization of dyes, water purification, and hydrogen pro-
duction from the water-splitting reaction.[12–20]
TiO2 exists in three different crystalline modifications:
anatase, brookite, and rutile. Rutile is a thermodynamically
stable state, while the other two phases are metastable
states.[21] It is known that bare polycrystalline anatase and
rutile TiO2 samples show different photoactivities.[22] How-
ever, anatase exhibits the highest overall photocatalytic
activity.[23] In spite of the extensive investigation of TiO2,
there is no accepted explanation for the distinctions of the
photocatalytic activity of various polymorphs or surface

© 2018 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J Chin Chem Soc. 2018;1–7. http://www.jccs.wiley-vch.de 1
2 FAROUQ
orientations. Possible explanations may be categorized as
follows:
Anatase has a larger band gap than rutile TiO2. While
this decreases the light that can be absorbed, it may raise the
valence band to higher energy levels with respect to redox
potentials of the adsorbed particles. This increases the oxida-
tion “power” of electrons and facilitates electron transfer
from the TiO2 to the adsorbed molecules.[24] This explana-
tion was also expanded to explain the surface orientation-
dependent activities by suggesting that different surfaces
exhibit different band gaps.[25]
The surface properties may play a role in the adsorption
of molecules and subsequent charge transfer to the mole-
cules. The surface properties may not just be polymorph
dependent but may differ largely for the same material for
different surface orientations or reconstructions,[26,27] and
consequently may contribute to the observation of pro-
nounced surface effects in photocatalytic activities. The sur-
face properties may again be subdivided into (a) chemical
effects, for example, the coordination structure of surfaces
that controls the adsorption of molecules,[28] (b) the elec-
tronic structure of the clean surface[29] or defects and adsor-
bate (e.g.,hydroxyl)-induced states that may be crucial for
charge trapping and separation at the surface,[30]
(c) interaction of molecules with surface defects,[31] and
(d) surface potential differences (such as work function dif-
ferences measured in a vacuum or flat-band potentials in
aqueous solution)[32,33] may affect charge transfer from the
photocatalyst to molecules.
Anatase exhibits an indirect band gap that is smaller than
its direct band gap. However, rutile has a fundamental band
gap that is either a direct or an indirect band gap, and is fun-
damentally the same as its direct band gap. Semiconductors
with an indirect band gap generally exhibit longer charge-
carrier lifetimes compared to the direct gap materials. A lon-
ger electron–hole pair life in anatase than in rutile would
increase the chance for charge carriers to participate in sur-
face reactions. One evidence for longer charge-carrier life-
times in anatase than in rutile comes from transient
photoconductivity measurements on single-crystalline
samples.[34]
Upon irradiation with UV, the electrons on the surface of
the TiO2 are excited to the conduction band and positive
holes are formed in the valance band. The electrons and
holes can either recombine and produce thermal energy or
react with other molecules. The holes react with the electron
donor (OH¯ or H2O) in the solution to produce OH
, which
oxidizes the organic compounds on the surface. The holes
can oxidize the organic target by direct electron transfer.[11]
This article investigates the degradation of methylene
blue using H2O2 and TiO2 in the presence of UV light. Sub-
sequent experiments were conducted to investigate the
effects of various amounts of catalyst dosing, pH values, and
the initial dye concentration on the process using the
response-surface methodology (RSM).
2 | M AT E RI A L S AN D M E T H O DS
2.1 | Materials and equipment
Methylene blue dyestuff (λmax = 665 nm), a heterocyclic
basic dye, has a molecular weight of 373.9 g/gmol. Its scien-
tific name is basic blue (9) with the molecular formula:
C16H18N3SCl and the structural formula.
TiO2 (Anatase type) is used as a photocatalyst with a
particle size of 0.05 mm and a density of 3.78 g/cm3. Start-
ing materials were of commercial reagent grade TiO2 with
the anatase structure; anatase was annealed at 525
C for
24 hr, the rutile type has a particle size of 0.05 mm and a
density of 4.23 g/cm3, a TiO2 mixture (79% Anatase, 21%
Rutile) and H2O2 (30%) were used. All chemicals were of
analytical grade and were used as purchased without further
purification and were obtained from Sigma Aldrich, Egypt.
2.2 | Experimental set-up and procedure
The photocatalytic studies were carried out in a tubular
photoreactor with a tube of length 35 cm and diameter 8 cm
(Figure 1). The experiments were conducted in the recircu-
lating batch mode. The reactor consists of a stainless steel
UV unit consisting of a UV lamp with light intensity (39 W/
m2), input, and output stream of water. The solution to be
treated is kept in a 2 L reservoir. After the addition of H2O2
to the suspension, and fixing the pH, the polluted water is
fed with a pump, which is connected to the reservoir having
the polluted water, and it is operated at specific discharge
rate of 0.6 L/min so the pollutant solution was circulated
from the tank to the tubular reactor and again to the tank and
the cycle was repeated. The reservoir was covered with alu-
minum foil to avoid the light penetration.
The dark reaction test is performed by adjusting the ini-
tial pH of the solution to the desired pH value and then sub-
jecting it to magnetic stirring for 2–5 min in the dark to
FIGURE 1 Tubular reactor equipped with a UV-A lamp
FAROUQ 3

TABLE 1 Central composite design with predictive values and their Table 1. MATLAB 2013 software was adopted to
experimental results describe the response surface. To check the accuracy of
Initial MB TiO2 the fitted model, an analysis of variance (ANOVA) was
Run conc. loading Experimental Predicted
no. (mg/L) (g) pH Time removal removal
conducted.
1 5 1.5 2 50 77.340 76.3275
2 5 2 4 30 10.804 11.3395
3 | R E S U L T S AN D D IS C US S IO N
3 10 0.5 2 40 80.568 83.6865
4 10 1 2 40 79.317 79.5860
5 10 1.5 2 40 77.682 71.9630
3.1 | The X-ray diffraction (XRD) of the nanoparticles
6 10 1 4 50 44.3002 42.3437 Figure 2a shows the XRD of the powder of TiO2. The deter-
7 10 1.5 4 50 17.7490 23.7315 mined characteristic 2θ values and [hkl] planes are 25.28

8 10 2 4 30 7.5520 8.9102 [101], 37.80
[004], 48.05
[200], 53.91
[105], 55.06

9 20 0.5 4 30 12.0705 11.6329 [211], 63.07
[204], 69.23
[116], 70.89
[220], and 75.38

10 20 1.5 4 30 7.5275 8.1397 [215], respectively. The XRD patterns of the TiO2 sample
11 20 2 4 30 3.3190 1.1092 demonstrate the formation of an anatase phase.[18–22]
12 30 0.5 2 50 49.4220 51.9709 Figure 2b shows the characteristic XRD pattern of the rutile
13 30 1 2 40 33.9560 35.8827
14 30 1.5 2 50 62.5213 58.3219
15 30 2 2 40 40.5893 43.6572
16 30 0.5 4 40 17.2840 9.51930
17 30 1 4 50 22.9279 24.4069
18 30 1.5 4 40 6.5097 10.8290
19 30 2 4 50 12.1213 10.2030
20 5 0.5 9 50 34.9975 33.7218
21 5 1.5 9 30 8.1300 8.2546
22 30 0.5 9 30 27.6467 30.2718
23 30 0.5 9 50 33.3763 33.7283
24 30 1 9 40 23.1527 23.9350
25 30 1.5 9 30 8.8840 6.2757

attain adsorption equilibrium. Samples are centrifuged for

separation of TiO2 powder. The concentration of Methylene
Blue in test samples was determined at λmax = 665 nm using
a Spectrophotometer Pharmacia NOVA SPEC® Rapid.

2.3 | Mixture analysis

In the present study, mixture analysis was used to optimize
the four parameters (initial concentration of the methylene
blue (MB) dye, TiO2 loading, pH, and time) on the
selected Response Function (degradation of MB). These
four parameters were selected as independent variables to
evaluate their influence on dye degradation. The experi-
mental data are suitable for a second-order polynomial
equation

X
k X
k−1 X
k−1 X
k
y = β0 + β i Xi + βii Xi 2 + βij Xi Xj + ε
i=1 i=1 i=1 j=1

where y is the response, β0, βi, and βii are the regression
coefficients of variables for intercept, linear, quadratic, and
interaction terms, respectively. Xi and Xj are the independent
variables and ε is the residual term.
The experimental values of MB dye degradation FIGURE 2 X-ray diffraction patterns of (a) the anatase sample; (b) the
under various experimental conditions are shown in rutile sample; (c) and the anatase–rutile mixture
4 FAROUQ
FIGURE 3 Effect of the catalyst concentration (anatase TiO2) on dye
degradation of 20 ppm dye solution
structure. The strong diffraction peaks at 2θ = 27.4, 36.1,
39.2, 41.2, 44.0, 54.4, and 56.7
can be indexed to the
(110), (101), (200), (111), (210), (211), and (220) crystal
planes of rutile TiO2.
Figure 2c shows the XRD pattern used for the crystal-
phase identification of the anatase–rutile phase. The XRD
pattern of the powder reveals the anatase (1 0 1) and emerg-
ing peak of rutile (1 1 0), indicating that the sample is a mix-
ture of anatase and rutile.
3.2 | Effects of the catalyst concentration (anatase
TiO2) on dye degradation
Figure 3 shows the effect of different concentrations of Ana-
tase TiO2 on the degradation of MB. Results indicate that a
catalyst concentration of 1.5 g/L of dye solution at pH = 2,
using 0.2 mL of H2O2 and 20 ppm dye concentration gives
the highest percentage of dye degradation, among other cata-
lyst concentrations examined; 0.5 g, 1 g and 2 g/L of dye
solution. This is because lower concentrations of the catalyst
will not be enough to complete the photodegradation pro-
cess. On the other hand, higher concentrations will increase
the turbidity of the solution, thus, reducing the light trans-
mission through the solution due to the increase in light
scattering.[35]
3.3 | Effect of dye concentration
The effect of the initial concentration of the dye on the rate
of dye degradation was investigated by varying the initial
FIGURE 4 Effect of the initial dye concentration on its degradation
FIGURE 5 Effect of pH values on dye degradation (for initial dye
concentration 30 ppm)
dye concentration from 5–30 ppm. Figure 4 shows the effect
of dye concentrations on the process of photocatalytic degra-
dation. It is observed that the concentration of 20 ppm
shows better results of photocatalytic degradation at pH = 2,
TiO2 = 1.5 g, and H2O2 = 0.2 mL compared to the case of
10, 5, and 30 ppm dye concentrations. The rate of degrada-
tion is proportional to the formation of •OH [36] that are
formed by the reaction of holes with adsorbed OH− and
H2O. The adsorbed OH− positions are replaced by dye ions,
thus the generation of •OH will be reduced because there
are only fewer active sites available for the generation of
•OH. This proves that the rate of degradation decreases with
increasing initial dye.
3.4 | Effect of pH values
Figure 5 shows the effect of pH values on the photocatalytic
degradation of methylene blue. In this study, a pH value of
2 showed the highest percentage degradation (among other
studied values of pH 4 and pH 9), at TiO2 = 1.5 g, dye con-
centration = 30 ppm and H2O2 = 0.2 mL.
The rate of degradation increases with decreasing pH
values. The TiO2 surface is positively charged in acidic
media; but it is negatively charged under alkaline conditions.
The role of pH in photocatalytic removal of MB can be
explained by considering the properties of the catalyst at dif-
ferent pH values. The point of zero charge TiO2 is 6.25;
thus, the surface of the catalyst will be positively charged at
pH lower than 6.25, and negatively charged at pH higher
than 6.25.[37] At low pH values, electrostatic interactions
between the positive catalyst surface and dye ions lead to
strong adsorption of the latter on the catalyst surface.
3.5 | Photocatalytic degradation using different types
of TiO2
Different TiO2 types have been tested to investigate their
efficiency towards dye degradation under identical experi-
mental conditions, and the results are presented in Figure 6.
The types used are: anatase, rutile and a mixture of both of
them of 79% anatase and 21% rutile. The results clearly indi-
cate that anatase TiO2 is the most active in the degradation
of methylene blue dye.
FAROUQ 5

TABLE 3 ANOVA for the response-surface quadratic model

Sum of Mean
squares D.O.F. square F value p value
x1 1,336.30 1 1,336.30 58.384 1.7564−05
x2 333.91 1 333.91 14.589 0.003376
x3 1,499.90 1 1,499.90 65.536 1.0612−05
x4 271.63 1 271.63 11.868 0.0062781
x1*x2 443.49 1 443.49 19.377 0.001331
x1*x3 1,054.70 1 1,054.70 46.081 4.8094−05
x1*x4 386.02 1 386.02 16.866 0.0021213
x2*x3 519.02 1 519.02 22.677 0.00076615
x2*x4 145.69 1 145.69 6.365 0.030233
x3*x4 375.36 1 375.36 16.40 0.0023247
FIGURE 6 Photocatalytic degradation efficiency of different TiO2 types
x21 8.8252 1 8.8252 0.38559 0.54852

3.6 | Model fitting and statistical analysis x22 41.251 1 41.251 1.8024 0.20911
x23 926.85 1 926.85 40.496 8.2063−05
To optimize the reaction conditions of MB dye degradation,
x24 82.902 1 82.902 3.6222 0.086166
a central composite design (CCD) with a total number of
Error 228.87 10 22.887
25 experiments was applied for the response-surface model-
ing. In Table 1, the experimental and predicted responses are R2: 0.986, adjusted R2: 0.965.

shown as well. The software suggested a quadratic model as

residuals fall on a straight line, which recommended that the
shown in Table 2.
errors are dispersed typically.[25] In addition, structure-less
Table 3 shows the ANOVA for the response surface of the
patterns in the plot of residuals versus the predicted response
quadratic model. The ANOVA implies that the model is signif-
show that the model is accurate.
icant with p values less than .05 (.00053677), which indi-
cates that the model terms are highly significant.[38]
An “R2” value of 0.986 is in reasonable agreement with
3.7 | Reaction kinetics
the “Adj. R2” of 0.965 (within 0.2%), which additionally
infers a great predictability of the model.[25] The photocatalytic reaction can be described using the
An empirical second-order polynomial equation was Langmuir–Hinshelwood model:
established and was written as follows (Table 4):
Ka kr C
r= ð1Þ
y = −37:995−6:1259 x1 + 36:479 x2 −9:2077 x3
* * * 1 + Ka C
+ 7:4603* x4 + 1:3272* x1 * x2 + 0:29252* x1 * x3 where r is the reaction rate (mg/L min), kr is the specific
+ 0:070329x1 * x4 −6:7549* x2 * x3 −0:84686* x2 * x4 reaction rate constant (mg/L min), and Ka is the equilibrium
−0:42767* x3 * x4 −0:019616* x21
constant of the reactant (L/mg). By integrating the equation
−7:0451* x22 + 2:0534* x23 + −0:06406* x24
Co
where y is the percentage degradation of the MB dye, x1, x2, ln + kr ðCo −C Þ = kr Ka t ð2Þ
C
x3, and x4 are the terms to those coded values of the initial
concentration of the MB dye, TiO2 loading, pH, and time, The equation can be simplified to a first-order equation
respectively. In Figure 7, it is observed that the high correla- in the form:
tion between the experimental data and predicted values  
Co
(R2 = 0.986) demonstrates that data fit great with the model. ln = Ka kr t = ko t ð3Þ
C
A residuals analysis was carried out to confirm the accuracy
of the model, using the normal probability plot of the resid-
uals (Figure 8) and the plot of the residuals versus the pre-
dicted response (Figure 9). Figure 8 indicates that the

TABLE 2 Sequential model fitting for the MB dye

Sum of Degree of Mean

Source squares freedom square F value p value Remark
Linear 8,331.4 4 2082.80 5.5559 .0035607
Interaction 5,099.2 6 849.86 4.9605 .0064157
Quadratic 7,268.8 10 726.88 31.7590 3.013e−06 Suggested
Cubic 7,497.7 20 374.88 — —
FIGURE 7 Predicted vs. actual values of photodegradation percentage
6 FAROUQ

Normal probability plot of residuals

0.99

0.95
0.9

0.75
Probability

0.5

0.25

0.1
0.05
FIGURE 10 First-order kinetic plot for the methylene blue dye
0.01
-6 -4 -2 0 2 4 6 8
Residuals TABLE 5 First-order rate constant of decomposition of the methylene blue
dye on different types of TiO2
FIGURE 8 Normal probability plots of the residuals
Catalyst type Rate constant (k, min−1)
Anatase TiO2 0.006474548
Rutile TiO2 0.002253679
Plot of residuals vs. fitted values 79% Anatase- 21% rutile 0.001556131
8

6 Co and C are the reactant concentrations (ppm) at time zero

and time t, respectively.
4
Figure 10 shows the pseudo-first order kinetic data for
2
the Methylene Blue dye. The ko value of anatase TiO2 was
Residuals

found to be much higher than for other types. This result

0 confirms that anatase TiO2 is a much more effective catalyst
material than any other type. Using the obtained data, the
-2
rate constant k values of the MB dyes were calculated and
-4 listed in Table 5.

-6
0 10 20 30 40 50 60 70 80 90
Fitted values 4 | C O NC L U S IO N S
FIGURE 9 Plot of the residuals against the predicted response
Photocatalytic degradation of methylene blue was investi-
gated using different types of TiO2. A multivariate experi-
mental design was employed to develop a quadratic model
TABLE 4 Coefficient of the regression model and its significance as the functional relationship between the studied factors,
Coefficient Standard such as photocatalyst dosage, the initial concentration of
(estimated) error F value p value
methylene blue dye, time, and pH of the solution to deter-
(Intercept) −37.995 85.103 −0.44646 0.66478
mine the optimum degradation percentage of methylene
x1 −6.1259 1.724 −3.5533 0.0052396
blue. Under optimal conditions (1.5 g TiO2 loading, 20 ppm
x2 36.479 19.781 1.8442 0.094951
methylene blue, and at pH 2), the removal of 97.6% of meth-
x3 −9.2077 8.0481 −1.1441 0.27924
ylene blue was achieved.
x4 7.4603 3.2218 2.3155 0.0431
x1*x2 1.3272 0.30149 4.4019 0.001331
x1*x3 0.29252 0.043092 6.7883 4.8094−05 OR CID

x1*x4 0.070329 0.017125 4.1068 0.0021213 Rania Farouq http://orcid.org/0000-0002-1616-7169

x2*x3 −6.7549 1.4185 −4.7621 0.00076615
x2*x4 −0.84686 0.33566 −2.523 0.030233
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How to cite this article: Farouq R. Investigation of
the kinetics and optimization of photocatalytic degra-
dation of methylene blue. J Chin Chem Soc. 2018;
1–7. https://doi.org/10.1002/jccs.201800029