Photocatalytic Degradation of

Journal of Environmental Engineering and Journal of Environmental Engineering and Science, 2016, 11(4), 96–107
Science http://dx.doi.org/10.1680/jenes.16.00016
Paper 16.00016
Volume 11 Issue JS4 Received 28/06/2016; accepted 18/10/2016
Published online 15/11/2016
Photocatalytic degradation of red dye:
optimisation using RSM
Ossman, Farouq and Abdelfattah ICE Publishing: All rights reserved
Photocatalytic degradation of
red dye: optimisation using RSM
Mona E. Ossman PhD Marwa Abdelfattah PhD
Professor, Petrochemical Engineering Department, Pharos University, Assistant Professor, Petrochemical Engineering Department, Pharos
Alexandria, Egypt; City for Scientific Research and Technological University, Alexandria, Egypt
Application, Alexandria, Egypt
Rania Farouq PhD
Assistant Professor, Petrochemical Engineering Department, Pharos University,
Alexandria, Egypt (corresponding author: [email protected])
The aim of this research was to apply experimental design methodology to the optimisation of the photocatalytic
degradation of red dye present in waste water. This paper reports the broad range of several photocatalyst composite
efficiencies for photocatalytic degradation of red dye in waste water samples from textile industries. Three composites,
which were graphitic carbon nitride (g-carbon nitride (C3N4))/zinc oxide (ZnO), g-carbon nitride/titanium dioxide (TiO2)
and zinc oxide nanoparticles, were prepared using different precursors (zinc chloride, zinc nitrate etc.). The catalysts were
characterised by Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron
microscopy. The catalytic performance of different photocatalysts was tested using different variables such as dosage,
stirring speed, composite structure and dye concentration. Two methods were used to optimise the operating conditions.
The results indicate that the photocatalytic degradation of the red dye solution at the resulting optimum condition,
which was found to be after 90 min of ultraviolet irradiation, can reach 68, 57 and 53% when using zinc oxide
nanoparticles, titanium dioxide/carbon nitride and zinc oxide/carbon nitride, respectively, as catalysts.
Notation waste water (Fu et al., 2012; Li et al., 2011; Liu et al., 2013; Priac
A stirring speed et al., 2014). Heterogeneous photocatalysis involves photoreactions
B weight of the catalyst (g/ml) that occur at the surface of the catalyst (Priac et al., 2014).
C concentration of the dye after a certain time period t Depending on where the initial excitation occurs, photocatalysis can
(mg/ml) be generally divided into two classes of processes: a catalysed
Co initial concentration of the dye (mg/ml) photoreaction and a sensitised photoreaction (Linsebigler et al., 1995;
Ka adsorption constant Litter, 1999). Semiconductors (titanium dioxide (TiO2), zinc oxide
kr rate constant (ZnO), iron (III) oxide (Fe2O3), cadmium sulfide (CdS), zinc sulfide
Xi uncoded value of the ith test variable (ZnS) etc.) may act as photocatalysts for the redox process due to
X0 uncoded value of the ith test variable at the centre point their electronic structures, characterised by a filled valence band and
xi coded value of the ith variable an empty conduction one (Chen et al., 2013; Fang et al., 2014; Guo
Y predicted response et al., 2011). The semiconductor titanium dioxide is a non-toxic, low-
βi, βj, βij coefficients estimated from the regression cost photocatalyst and is used as an additive in various products, such
η percentage of photocatalytic removal as cosmetics, food and pharmaceuticals. Interest in photocatalysis has
focused on the use of titanium dioxide as a photocatalyst for the
Introduction removal of organic and inorganic pollutants from water because of
Organic dyes contain large groups of organic compound pollutants. the ability of titanium dioxide to oxidise organic and inorganic
Owing to their high chemical stability, dyes can have a toxic or an substrates in air and water (Bonetta et al., 2013; Ibhadon and
inhibitory effect on living organisms when combined with various Fitzpatrick, 2013). However, this compound is widely used as a
heavy metal oxides. Conventional waste water treatment plants self-cleaning material for surface coating in many applications
cannot degrade most of these pollutants, as it is difficult to treat dye (Bonetta et al., 2013; Yu et al., 2010). Zinc oxide has been often
waste water by chemical and physical processes because of its considered a valid alternative to titanium dioxide because of its good
complex molecular structures. optoelectronic, catalytic and photochemical properties along with its
low cost. The photocatalytic activity of zinc oxide is almost similar to
Alternative methods for the decontamination of dye waste waters are that of titanium dioxide, as the band gap energy of zinc oxide is the
the biological methods (Rai et al., 2014; Raj et al., 2012). However, same as that of titanium dioxide. In aqueous solution, zinc oxide
photocatalysis has been considered as a cost-effective alternative to shows a photocorrosion tendency with illumination by ultraviolet
biological treatment processes for the treatment of dye-containing (UV) light. Zinc oxide has been used as a photocatalyst in waste
96
Journal of Environmental Engineering and Photocatalytic degradation of red dye:
Science optimisation using RSM
Volume 11 Issue JS4 Ossman, Farouq and Abdelfattah
Offprint provided courtesy of www.icevirtuallibrary.com

Author copy for personal use, not for distribution
water for decomposing halogen compounds and azo dye compounds CH2OH
(Benhebal et al., 2013; Muthirulan et al., 2013). Zinc oxide HO
O H
nanoparticles can be synthesised using various techniques such as OH O CH3 O
hydrothermal synthesis, sol–gel synthesis, wet chemical synthesis, HO C OH
precipitation, microemulsion, chemical vapour deposition, solid-state OH
reaction and laser ablation (Benhebal et al., 2013; Yu et al., 2010). HO OH
Carbon nitride (C3N4) has been identified as a new form of organic OH O
polymer-like material with diverse properties and is considered to be
Figure 1. Structure of red dye
the most stable allotrope of various cyanide (CN) structures under
ambient conditions (Sridharan et al., 2013).
Graphitic carbon nitride/titanium dioxide composite
It has been reported that graphitic carbon nitride (g-carbon nitride) Graphitic carbon nitride/titanium dioxide composite was obtained
is the most stable allotrope of carbon nitride at ambient atmosphere, by adding an 0·2 g of g-carbon nitride and 9·8 g of titanium dioxide
and it has rich surface properties which make it an attractive to methanol and stirring at room temperature for 24 h. Afterwards,
alternative for use as a catalyst, due to the presence of basic surface the composite photocatalyst was obtained by evaporating the
sites. The ideal g-carbon nitride consists solely of an assembly of C–N methanol (Miranda et al., 2013).
bonds without electron localisation in the π state (Zhu et al., 2014).
Graphitic carbon nitride/zinc oxide composite
Several composite materials in combination with g-carbon nitride Melamine, 0·074 g, was dispersed in 25 ml of zinc chloride solution
have been also reported, such as g-carbon nitride–bismuth tungstate (0·5 mol/ml) in a 250-ml glass beaker, and the suspension was
(Bi2WO6) (Liu et al., 2012; Miranda et al., 2013; Nishikawa et al., vigorously stirred for 20 min. Then, 25 ml of sodium carbonate
2013; Zhao et al., 2012). (0·5 mol/ml) solution was added dropwise into the suspension and
stirred magnetically for 30 min. Subsequently, the mixture was
The aim of this work was to study the degradation of red dye using filtered, washed with deionised water for several times and dried
g-carbon nitride/zinc oxide, g-carbon nitride/titanium dioxide and at 60°C for 24 h. The precursor of g-carbon nitride/zinc oxide
zinc oxide nanoparticles and characterise these composites by using photocatalyst in a g-carbon nitride ratio of 5·0 weight % (wt.%) was
techniques such as Fourier transform infrared spectroscopy (FTIR), obtained (Liu et al., 2012).
scanning electron microscopy (SEM) and transmission electron
microscopy (TEM). The effect of various parameters such as dye Zinc oxide nanoparticles
concentration, photocatalyst dosage and stirring speed were The zinc oxide nanoparticles were prepared by the precipitation
investigated. method using zinc nitrate and sodium hydroxide as precursors
and soluble starch as a stabilising agent. Starch, 0·3 g, was dissolved
in 100 ml of distilled water at 27°C. Zinc nitrate, 10 ml of 0·1 mol/l
Experimental work solution, was added to the starch solution. The obtained
The photocatalytic activities of different photocatalysts were solution was stirred constantly using a magnetic stirrer for 2 h until
evaluated by degradation of red dye under UV light (λ = 365 nm). complete dissolution occurred. Subsequently, 10 ml of 0·2 mol/l
The UV light was provided by a 12-W UV light lamp. sodium hydroxide solution was added drop by drop to the
solution from the side-walls. The reaction was allowed to
Chemical reagents proceed for 2 h after the complete addition of sodium hydroxide
Melamine, titanium dioxide, zinc chloride (ZnCl2), sodium solution. After the completion of the reaction, the solution was
carbonate (Na2CO3), zinc nitrate, sodium hydroxide and soluble allowed to settle down for 24 h. The supernatant solution was
starch were used as precursors for the synthesis of photocatalyst discarded carefully, and the remaining solution was centrifuged.
composites. All chemicals were of analytical grade and were used In order to remove the by-products and excessive starch bound
as purchased without further purification. The dyestuff used to to the nanoparticles, the precipitate was washed with ethanol
model waste water pollution is red dye with λmax = 487 nm and a repeatedly. Zinc oxide nanoparticle powder was obtained after
molecular weight of 373·9 g/mol. Its scientific name is carminic drying at 100°C (Lanje et al., 2013).
acid; its structure is shown in Figure 1.
Results and discussion
Ionised water was used throughout this study.
Characterisation of the photocatalyst
Synthesis FTIR
Carbone nitride preparation FTIR spectra were collected by means of an infrared (IR)
Graphitic carbon nitride was obtained by simple calcination of spectrometer. The morphology of the prepared samples was
melamine at 580°C for 4 h in a covered alumina crucible in order to analysed using high-resolution SEM, and high-resolution TEM
prevent sublimation of melamine (Miranda et al., 2013). was performed in a transmission electron microscope operating at
97

20 kV. The samples for TEM were prepared by dissolving them in SEM
ethanol. Figure 5 shows the SEM photographs of zinc oxide nanoparticles;
it is clearly seen that the zinc oxide nanoparticles display mainly
The crystal structure of g-carbon nitride can be confirmed by FTIR, sphere-like agglomerates with a diameter in the range between 34
as shown in Figure 2. Thus, pristine carbon nitride exhibits the and 61 nm, which is smaller than 100 nm, the average particle size
typical band at c. 717·1 cm−1. A wide band could also be observed of nanocrystalline powder.
between 2918·92 and 3360 cm−1, which corresponds to the N–H
stretching vibration of the residual NH2 group attached to the sp2- SEM was used to investigate the morphologies of the composite
hybridised carbon (C). The occurrence of such a band clearly samples. Figure 6 shows the SEM images of the titanium dioxide/g-
indicates that the presence of this NH2 group may increase the carbon nitride samples. It is shown that the composite is assembled
nitrogen (N)/carbon ratio. For composite materials, this band would in the form of microspheres. From SEM images, it can be inferred
also correspond to the O–H stretching of the free OH groups on the that the titanium dioxide aggregates cover the large g-carbon nitride
surface of the sample. particles.
The crystal structure of g-carbon nitride (5·0 wt.% zinc oxide) Figure 7 shows the high-magnification SEM photographs of
can be confirmed by FTIR. As shown in Figure 3, the absorption g-carbon nitride/zinc oxide (5·0 wt.%). From Figure 7, it is clearly
band near 1508·08 cm−1 is attributed to C–N stretching. The band seen that the g-carbon nitride/zinc oxide composite displays
near 834·8 cm−1 is attributed to out-of-plane bending modes of C–N mainly sphere-like agglomerates with a diameter of 0·5 µm, which
heterocycles. A broad band near 3401·51 cm−1 corresponds to the are composed of several small spherical nanoparticles, probably
stretching modes of NH2 or NH groups. because melamine plays a conglomeration role in the chemical
precipitation process. In addition, the small spherical nanoparticles
The crystal structure of zinc oxide nanoparticles can be confirmed have a mean size of about 57·47 nm. It can be concluded that zinc
by FTIR. As shown in Figure 4, prominent peaks at 523·51, oxide is evenly distributed on the surface of the sphere-like
1082·1, 1647·29 and 3409 cm−1 are clearly observed. The peak at composite, which favours the formation of a heterojunction and
523 cm−1 corresponds to Zn–O, and the remaining peaks at 1082·1, results in an enhanced photocatalytic activity.
1647·29 and 3409 cm−1 are due to the absorption of water during
the preparation of IR pellets or O–H present in the starch molecules. TEM
The peaks at 931·25, 1021·9 and 2929·6 cm−1 are due to the As shown in Figure 8, the diameter of the zinc oxide particles was
presence of C–O and C–H vibration modes of starch, which act as a found to be smaller than 90 nm. Moderately aggregated particles
capping agent. seem to be present.
51∙8
50
48
46
44
42
1337∙83 261∙93
40 1289∙18
Transmittance: %
1272∙00
38 1150∙00
36
34
32
30
28
1676∙75
26 3266∙96
3360∙11 2818∙92
24 3200∙83 2860∙42 2360∙89
3117∙58 2337∙70
22 665∙90
717∙00
2260∙11 2918∙92 547∙99
20
717∙1
19
4400 4000 3000 2000 1500 1000 500 350
cm–1
Figure 2. FTIR analysis of titanium dioxide and carbon nitride
98

46·5
44
42 4376·25
4336·02 3904·41 2419·46 1947·96
40 3949·93
4303·71 3857·93 2309·48
38 4166·89 3803·05 2340·68
4026·48 2105·00 354·86
36 3749·49
34 372·52
32
30
Transmittance: %
28
739·83
26
707·45
24 893·40 472·21
22 1047·78
20 953·89
18
16 834·80
14
12
10
8
1584·66
6 3401·51
1508·68
4
2·5
4400 4000 3000 2000 1500 1000 500 350
cm–1
Figure 3. FTIR analysis of g-carbon nitride (5·0 wt.% zinc oxide)
28·5
26
2168·44
24 2148·79
22
20
Transmittance: %
18
16 860·52
14
763·36
1647·29 931·25
12 1240·30
706·54
10
1417·65
8 2929·60 1377·77
568·77
6 3409·88 1021·90 523·51
1155·64 476·82
4 432·81
1082·10
2·4
4400·0 4000 3000 2000 1500 1000 500 350
cm–1
Figure 4. FTIR analysis of zinc oxide nanoparticles
99

86·21 nm
50·56 nm
51·72 nm
57·47 nm
40·23 nm
61·80 nm
33·71nm
20 kV ×35 000 0∙5 μm 023313 20 kV ×35 000 0·5 µm 023317
Figure 5. SEM photographs of zinc oxide nanoparticles Figure 6. SEM photographs of titanium dioxide/carbon nitride
Figure 9 shows a TEM image of the composite photocatalyst Photocatalytic activity of the different types
g-carbon nitride/zinc oxide. It clearly shows that the mean size of of photocatalysts
the composite particles is approximately 67 nm. To study dye degradation, some parameters which affect removal
efficiency, such as the amount of catalyst and the initial
The morphology of g-carbon nitride/titanium dioxide was observed concentration, were studied.
by TEM. As shown in Figure 10 from the TEM image of the
g-carbon nitride/titanium dioxide hybrid, it can be seen that The degradation of red dye was estimated by applying the following
the titanium dioxide particles disperse on the surface of g-carbon equation
nitride. Graphitic carbon nitride/titanium dioxide displayed a firm
connection between titanium dioxide and g-carbon nitride, indicating
that the formation of a heterojunction was possible. Figure 10
shows that the mean size of the composite particles is in the range
of 50–72 nm.
Zn-1.tif 100 nm
20 kV ×35 000 0·5 µm 023315 Print Mag: 138 000× @7∙0 in HV = 80∙0kV
9:22:02 a 02/07/15 Direct Mag: 10 000×
AMT camera system
Figure 7. SEM photographs of g-carbon nitride/zinc oxide Figure 8. TEM analysis of zinc oxide nanoparticles
100

probability of the red dye molecules reacting with hydroxyl radicals

decreases.
Effect of dye initial concentration

The effect of increasing the initial concentration of the dye from 5
to 25 parts per million (ppm) at a catalyst dosage of 0·1 g at 200
revolutions per minute (rpm) was investigated. The results are
illustrated in Figure 12. As can be seen, when the dye concentration
74·3 nm
57·9 nm
increases from 5 to 10 ppm, the percentage of removal increases;
however, it decreases with increasing initial concentrations. This
66·2 nm induces an inner filter effect, and the path length of the photons
70·4 nm
entering the solution decreases and the quantity of intermediates
increases as well, competing through side reactions with the parent
dye decomposition. Molecules will be adsorbed on the surface of
the photocatalyst, and the active sites of the catalyst will be reduced;
thereby, the generation of hydroxyl radicals decreases. Another
reason may be that at higher dye concentration, UV light might
be absorbed by the dye rather than by the g-carbon nitride/zinc
oxide composite particles, and this reduces the photodegradation
efficiency.
Zn C3N4-2.jpg
Print Mag: 138 000× @7·0 in 100 nm
9:30:24 a 02/07/15 HV = 80·0 kV Effect of stirring speed
Direct Mag: 10 000×
AMT camera system
The stirring speed in the experiment ranged from 200 to 800 rpm.
The results illustrated in Figure 13 show that by increasing stirring
Figure 9. TEM analysis of g-carbon nitride/zinc oxide speed, photocatalyst degradation is increased slightly from around
54% at 200 rpm to 63% at 800 rpm, which means that the effect of
the stirring speed is insignificant.
1:
ηð%Þ ¼ ð C C C Þ100
o
o
50·4 nm
where η is the percentage of photocatalytic removal, Co is the initial
concentration of the dye (mg/ml) and C is the concentration of the
dye after a certain time period t (mg/ml).
Effect of photocatalyst dosage

33·9 nm
In photocatalysis, one of the main parameters of the discoloration
59·3 nm
of the dye solution is photocatalyst dosage. Different dosages of
g-carbon nitride/zinc oxide composite were used to degrade red
dye. The results obtained for a radiation time of 120 min are shown
in Figure 11. As the loading of the photocatalyst increases from 0·2
to 0·3 g/ml, the photodegradation rate increases from 44 to 60%
after 90 min. In this case, the number of photons and the adsorbed
68·8 nm
molecules increase and the density of the molecule in the area 72·1 nm
of illumination also increases, which causes an increase in the
degradation rate (Senthilkumaar et al., 2005). Whereas in the case
of catalyst loading above 0·3 g/ml, the degradation rate falls,
which may be due to the fact that the added catalyst blocks light
TiO2 C3N4-2.jpg
transmission through the solution and increases light scattering. Print Mag: 138 000× @7·0 in 100 nm
9:36:31 a 02/07/15 HV = 80·0 kV
Further increase in the catalyst amount may result in the Direct Mag: 10 000×
AMT camera system
deactivation of the activated molecules due to collision with
the ground-state molecules (Fotiadis et al., 2007). Therefore,
Figure 10. TEM analysis of g-carbon nitride/titanium dioxide
the generation of hydroxyl radicals will be decreased and the
101

70 70
Dye degradation: %
60 60
Dye degradation: %
50 50
0·1 g
40 25 ppm
0·2 g 40
20 ppm
30 0·3 g 30
15 ppm
20 0·4 g
20 10 ppm
0·5 g
10 5 ppm
10
0
0 20 40 60 80 100 0
Time: min 0 20 40 60 80 100
Time: min
Figure 11. Comparison diagram of photocatalytic degradation of
red dye with different dosages of g-carbon nitride/zinc oxide Figure 12. Comparison diagram of photocatalytic degradation of
composite dye with different dye concentrations
Reaction kinetics
Comparison of photocatalytic activities of different
The photocatalytic reaction follows the Langmuir–Hinshelwood
composites
model
To investigate the efficiency of the different composites, experiments
were carried out at constant conditions of initial concentration,
KakrC
catalyst dosage and stirring speed. The values of efficiency of r¼
titanium dioxide/carbon nitride, zinc oxide/carbon nitride and 2: 1 þ KaC
zinc oxide nanoparticles in the photocatalytic degradation of red
dye were examined; the results are presented in Figure 14. where kr and Ka represent the rate constant and adsorption constant,
The results clearly indicate that zinc oxide is found to be the most respectively. The equation can be simplified to an apparent first-
active in the degradation of red dye. The order of photocatalytic order equation
activity of various photocatalysts for red dye is zinc oxide
nanoparticles > titanium dioxide/carbon nitride > zinc oxide/carbon
nitride.
3:
ln ð CC Þ ¼ K k
o
a r t ¼ kot
As shown in Figure 14, the results indicate that the photocatalytic

degradation of the red dye solution, after 90 min of UV irradiation, A plot of ln(Co/C) against time is represented in Figure 15.
can reach percentages of 68, 57 and 53% when using the catalysts
zinc oxide nanoparticles, titanium dioxide/carbon nitride and zinc The values of ko and the linear regression coefficients of the
oxide/carbon nitride, respectively, which means that the zinc oxide photodegradation of red dye which correspond to the different
nanoparticles have a higher degradation efficiency. composites are listed in Table 1.
100 80
Photocatalytic degradation: %
90 70
80
Dye degradation: %
60
70
50
60 TiO2/C3N4
50 40
40 30 ZnO/C3N4
30
20
20 ZnO nanoparticles
10 10
0 0
0 200 400 600 800 1000 1200 0 15 30 45 60 75 90
Speed: rpm Time: min
Figure 13. Effect of stirring speed on photocatalyst degradation of Figure 14. Comparison of efficiencies of different composites on
red dye the degradation of red dye
102

1·4
y = 0·0093x + 0·2494
1·2 R2 = 0·9517
1·0
TiO2/C3N4
0·8 ZnO/C3N4
ln(C0/C)
ZnO nanoparticles
0·6 Linear TiO2/C3N4
Linear ZnO/C3N4
0·4
y = 0·007x + 0·2597 Linear ZnO nanoparticles
y = 0·0076x – 0·0153
0·2
R2 = 0·9495 R² = 0·8867
0
0 20 40 60 80 100
Time: min
Figure 15. ln(Co/C) against time for different composites
According to Table 1, zinc oxide nanoparticles provide better variables, while the removal percentage of red dye was the
agreement with the first-order reaction. dependent response variable in the central composite design. In
order to describe the effects of stirring speed, catalyst dosage and
Statistical methods initial red dye ccentration on percentage removal of red dye, batch
Multiple linear regression modelling experiments were conducted. The coded values of the process
Multiple linear regression (MLR) analysis is commonly used in parameters were determined by the following equation
environmental studies in order to correlate the independent variables
on the examined dependent response. The concentration, catalyst Xi Xo
xi ¼
dosage and stirring speed of the solution were considered in the 5: ΔX
development of mathematical models for the red dye removal rate.
The correlation between the factors (concentration, catalyst dosage
and stirring speed) and the red dye removal rate was obtained by where xi is the coded value of the ith variable, Xi is the uncoded
MLRs. In the study, the Minitab program was used to derive the value of the ith test variable and X0 is the uncoded value of the ith
models of the form test variable at the centre point. The experimental range and levels
of independent variables are given in Table 2. The regression
4: % degradation ¼ 692 161A 231B þ 000111C analysis was performed to estimate the response function as a
second-order polynomial
k k1 k1 k
% removal ¼ β0 þ ∑ X i þ ∑ βii X i 2 þ ∑ ∑ βi j X i X j
where A is the stirring speed, B is the weight of the catalyst (g/ml)
and C is the red dye concentration (mg/ml). 6: i¼1 i¼1 i¼1 j¼1
Experimental design by response surface methodology

The response surface methodology (RSM) was used to optimise where Y is the predicted response. βi, βj and βij are coefficients
the three parameters (stirring speed, catalyst dosage and initial dye estimated from the regression; they represent the linear, quadratic
concentration). The three parameters were selected as independent and cross-products of X1, X2 and X3 on response. Minitab 14 was
Composite ko: min−1 R2

Factor Low (−1) Central (0) High (+1)
Titanium dioxide/carbon nitride 0·007 0·949
Zinc oxide/carbon nitride 0·0076 0·886 Initial concentration: ppm 5 15 25
Zinc oxide nanoparticles 0·0093 0·951 Dosage: gm 0·1 0·3 0·5
Stirring speed: rpm 200 600 1000
Table 1. Pseudo-first-order apparent constant values for the
different composites Table 2. Design matrix for the central composite designs
103

Run Initial concentration: Dosage: Stirring speed: Removal Removal SE Residual

ppm g rpm (observed): % (predicted): %
1 5 0·1 200 60·44 59·758 7·214 0·682

2 10 0·1 200 66·12 51·497 5·112 14·623
3 15 0·1 200 33·493333 42·098 6.071 −8·604
4 20 0·1 200 28·41 31·561 5·157 −3·151
5 25 0·1 200 20·78 19·885 7·737 0·895
6 5 0·2 200 44·26 55·015 5·112 −10·755
7 5 0·3 200 60·02 51·023 6·071 8·997
8 5 0·4 200 46·54 47·782 5·157 −1·242
9 5 0·5 200 42·3 45·293 7·737 −2·993
10 5 0·1 400 57·32 58·837 5·112 −1·517
11 5 0·1 600 61·54 60·39 6·071 1·15
12 5 0·1 800 64·4 64·417 5·157 −0·017
13 5 0·1 1000 68·62 70·918 7·737 −2·298
14 25 0·1 1000 23·5923 82 21·478 8·078 2·115
15 25 0·5 1000 16·5115 45 18·626 8·078 −2·115
16 25 0·5 200 29·6913 28 27·577 8·078 2·115
17 5 0·5 1000 48·0249 17 45·91 8·078 2·115
SE, standard error
Table 3. The experimental design with variable responses
used for regression analysis of the data obtained and for estimating By analysing the experimental results through RSM, an empirical
the coefficient of the regression equation. correlation for the best photodegradation efficiency was found to be
Statistical combinations of the independent variables with the dye degradation ¼ 345049 167892A 43291B
measured and predicted yield are shown in Table 3. It was observed þ 05523C 22759A2 þ 15033B2 þ 49484C 2
that, for most experiments, the predicted responses express well the
variation in the observed responses. þ 55391AB 23918AC 26357BC
7:
The quadratic response surface model was validated by the analysis
of variance (Anova). Anova is required to test the significance For estimating the effects of the factors, a t-test was performed. The
and adequacy of the model, which can be used to estimate the significance of each factor was determined and is listed in Table 5.
goodness of fit in each case by using the coefficient of determination
(R2). The coefficient of determination was calculated to be 0·883.
Term Coefficient SE coefficient t P
Table 4 shows the results of the Anova analysis of the model.
Constant 34·5049 18·017 1·915 0·097
A −16·7892 2·984 −5·626 0·001
B −4·3291 2·984 −1·451 0·190
Source DF Seq. SS Adj. SS Adj. MS F P C 0·5523 2·984 0·185 0·858
A2 −2·2759 9·023 −0·252 0·808
Regression 9 4251·59 4251·59 472·399 6·20 0·013 B2 1·5033 9·023 0·167 0·872
Linear 3 3856·28 2576·46 858·820 11·28 0·005 C2 4·9484 9·023 0·548 0·600
Square 3 25·75 37·23 12·411 0·16 0·918 AB 5·5391 2·918 1·898 0·099
Interaction 3 369·56 369·56 123·186 1·62 0·270 AC −2·3918 2·918 −0·820 0·439
Residual error 7 532·97 532·97 76·139 BC −2·6357 2·918 −0·903 0·396
Total 16 4784·56
SE, standard error
DF, degree of freedom S = 8·726; R2 = 88·9%; R2(adjusted) = 74·5%
Table 4. Anova for percentage removal Table 5. Factor effect and associated P values
104

Contour plot Surface plot

0·5
%
Removal
<20
20–30
0·4 30–40
40–50
50–60
>60 60
Dosage: g
Hold values
0·3 Stirring speed: 600 rpm Removal: % 40
20 0·55
0·2 0·40
6 12 0·25 Dosage: g
18 24 0·10
Initial concentration: ppm
0·1
5 10 15 20 25
(a)
1000
%
Removal
900 <20
20–30
800 30–40
40–50
Stirring speed: rpm
>50
700
Hold values
Dosage: 0·3 g 50
600
40
Removal: %
500 30
20 900
400
600
6 12 18 300
300 24 Stirring speed: rpm
200
5 10 15 20 25
Initial concentration: ppm (b)
1000
%
Removal
900 <32
32–36
36–40
800
40–44
Stirring speed: rpm
44–48
700 >48
45
Hold values
600 Initial concentration: 15 ppm 40
Removal: % 35
500
900
30
0·10 0·25 600
400 0·40 0·55 300
Dosage: g Stirring speed: rpm
300
200
0·1 0·2 0·3 0·4 0·5
Dosage: g
(c)
Figure 16. Graphs of surfaces and contours for the percentage dye
degradation: (a) initial concentration and dosage, (b) initial
concentration and stirring speed and (c) dosage and stirring speed
105

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Journal of Environmental Engineering and Journal of Environmental Engineering and Science, 2016, 11(4), 96–107

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Figure 2. FTIR analysis of titanium dioxide and carbon nitride

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Figure 3. FTIR analysis of g-carbon nitride (5·0 wt.% zinc oxide)

Figure 4. FTIR analysis of zinc oxide nanoparticles

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20 kV ×35 000 0∙5 μm 023313 20 kV ×35 000 0·5 µm 023317

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probability of the red dye molecules reacting with hydroxyl radicals

Effect of dye initial concentration

Effect of photocatalyst dosage

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As shown in Figure 14, the results indicate that the photocatalytic

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Figure 15. ln(Co/C) against time for different composites

Experimental design by response surface methodology

Composite ko: min−1 R2

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Run Initial concentration: Dosage: Stirring speed: Removal Removal SE Residual

1 5 0·1 200 60·44 59·758 7·214 0·682

Table 3. The experimental design with variable responses

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Contour plot Surface plot

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