Chapter VI Dye Separator

6.1. INTRODUCTION

Increasing attention in the field of water pollution control due to its many

advantages, and TiO2 has especially been widely used owing to chemical stability, non-

toxicity, easy synthesis, high reactivity, and environmental friendliness (1). However,

there are two major bottlenecks for TiO 2 as a photo-catalyst: first, the utilization rate of

visible light is low, TiO2 can only absorb ultraviolet light; second, the photo-electron-hole

in recent years, photo-catalytic treatment of refractory organic pollutants has attracted

pairs in TiO2 particles are easy to compound, resulting in low photo-quantum efficiency

and poor photo-catalytic activity (2,3). At present, the methods of expanding the TiO 2

photo-response and suppressing the carrier recombination are mainly to modify TiO 2 by

various means (4, 5).

Also, TiO2 is loaded on other functional materials to promote the separation of

photo-induced charges and prolong the recombination time of photo-generated charge,

which is also an effective way to improve TiO 2 photo-catalytic performance and improve

the wastewater treatment effect (6). Graphene (GR) is a two-dimensional structure

consisting of a single layer of a hexagonal lattice of carbon atoms, which are covalently

bonded to each other. This structure gives excellent electrical conductivity and thermal

conductivity, and high mechanical strength and large specific surface area of GR (7,8)

makes GR a promising candidate for use in sensors (9,10), energy storage and transfer

(11,12), nano-electronics (13), supercapacitors (14), composite materials (15), and other

areas. Graphene oxide (GO), an oxide of GR, still retains the layered structure of GR

after oxidization. However, many oxygen-containing functional groups are introduced to

the GO monolith of each layer. It is generally considered that hydroxyl and epoxy groups

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are distributed on GO monolith, while carboxyl and carbonyl groups introduced to the

edge of the monolith. The introduction of these oxygen-containing functional groups

increases the complexity of a single GR structure. Therefore, in addition to some

properties of GR, it also has a lot of specific features, such as excellent adsorption

properties (16, 17). If TiO2 is combined with GO, the composite can effectively promote

the separation and migration of photo-generated charges due to excellent electron

conduction of GO and can enrich organic substances within the wastewater to the surface

of the composite photo-catalyst due to excellent adsorption performance of GO, thus

increasing the possibilities of contact with the photo-catalyst and achieving better

degradation and removal of these contaminants (18, 19).

In this study, GO was prepared with a modified Hummers method and ultrasonic

mechanical delamination, while TiO2 nanoparticle was prepared with the sol-gel method.

Accordingly, the GO/TiO2 composite photocatalyst with different proportions of GO was

prepared by the sol-gel method and was characterized by scanning electron microscope

(SEM), x-ray diffraction (XRD), and Raman spectroscopy. The methylene blue (MB)

synthetic dye wastewater was taken as the target pollutant, in an attempt to study the

effect on the treatment of synthetic dye wastewater by photocatalytic treatment process

under UV irradiation, especially in terms of organic molecular degradation. Most studies

in the past on the treatment of MB synthetic wastewater were focused on the probability

to treat this kind of water using the composite photo-catalyst. In this study, the treatment

process of MB synthetic wastewater by the composite photo-catalyst under different

reaction conditions were studied in detail. At the same time, the reaction mechanism of

using the composite photo-catalyst to treat MB synthetic wastewater was preliminarily

discussed.

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6.2. MATERIALS AND METHODS

6.2.1. CHEMICALS AND REAGENTS

Sulfuric acid (H2SO4, >98.0%,), Hydrochloric acid (HCl, >36.0%,), Sodium

hydroxide (NaOH, >98.0%), Hydrogen peroxide (H2O2, >30.0%), Ammonia (NH3,

>98.0%), Acetone (C3H6O), Potassium permanganate (KMnO4), Methyl alcohol (CH3OH,

>99.5%), Ethyl alcohol (C2H5OH, >96.0%), the above reagents are all produced in

Tianjin Komeo Co., Ltd., Tianjin, China. Sodium nitrate (AR), Tetrabutyl titanate (AR),

Graphite Powder (AR), are produced in Sinopharm Chemical Reagent Co., Ltd.,

Shanghai, China.

6.2.2. CHARACTERIZATION OF INSTRUMENTATION

Photochemical reactor (Homemade), Ultraviolet light spectrophotometer

(UV3600, SHIMADZU, Kagoshima, Japan), Precision electronic balance (SARTORIUS,

Göttingen, Germany), pH meter (SARTORIUS, Göttingen, Germany), vacuum drying

oven (DZF-6020, SHUANGXU, Shanghai, China), High-pressure reactor (Beitang

chemical machinery equipment, Shenyang, China), Magnetic stirrer (Shanghai INESA

Scientific Instrument CO., LTD. Shanghai, China), Ultrasonic cleaner (SB-5200,

NingboXinzhi, Ningbo, China), High-speed centrifuge (TG16-WS, Hunan Xiangyi,

Changsha, China), Scanning Electron Microscope (ZeissUltraPlus, Jena, Germany), X-

Ray Diffraction (X Pertpro, PANalytical B.V, Almelo, The Netherlands), XploRA ONE

(BWS465-785S, B&WTek LLC, Ltd., Delaware, USA).

6.2.3. SYNTHESIS OF GRAPHENE OXIDE (GO)

Firstly, graphite oxide was prepared by modified Hummers method, then mixed

with hydrochloric acid and centrifuged at a speed of 7000–10,000 r/min, followed by the
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removal of sulfate ions and neutralization with deionized water. A certain amount of

centrifuged graphite oxide was mixed with a small amount of deionized water and the

mixture received ultrasonic treatment for 1 h at a frequency of 45 Hz. The resultant GO

solution was vacuum dried at 30°C to obtain GO powder.

6.2.4. SYNTHESIS OF TiO2 NANOCOMPOSITE

The mixture of 10 mL butyl titanate and 18 mL anhydrous ethanol was stirred for

10 min, to obtain mixed solution A; another mixture of 18 mL anhydrous ethanol, 3 mL

glacial acetic acid, and 3.3 mL deionized water was stirred for 5 min, to obtain mixed

solution B (A and B were simultaneously prepared). After solution A was stirred well,

solution B was slowly added dropwise to solution A at a rate of 3 mL/min and stirred for

5 min, then 0.7 mL formamide was added to the reaction system and the solution was

stirred for an additional 20–30 min until a white substance generated in a pale yellow

transparent solution and its fluidity gradually deteriorated. After 1 h of stirring, the

solution became an alcohol gel state, namely titanium dioxide alcohol gel. The gel was

sealed and placed ageing for 1–2 days, then calcined in a muffle furnace at 450°C for 4 h

to obtain light yellow particles doped with a few black particles. Subsequently, the

particles were cooled to room temperature and crushed into powder, which was the white

TiO2 nanocomposite.

6.2.5. SYNTHESIS OF GO/TiO2 NANOCOMPOSITE

Different weights of GO were mixed with TiO 2 hydrogel and electromagnetically

stirred for about 10 min until the mixture became alcohol gel, then the mixture was

stirred with a glass rod for 10–20 min and calcined in a muffin furnace at 450°C for 4 h.

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The resulting particles were cooled to room temperature and crushed into powder,

making the composite photo-catalyst.

6.2.6. PHOTO CATALYSIS VALUATION METHYLENE BLUE (MB)

Methylene blue (MB) solution was used as the photo-catalyst substrate in the

valuation. UV–vis Spectrophotometer was used to measure the absorbance under 664 nm.

The photo-catalyst degradation percentage was calculated using the following equation:

A = (C0 − C) × 100%/C0, (1)

where A is degradation, C0 (mg/L) is the initial methyl blue (MB) concentration,

C (mg/L) is the substrate concentration after the photo-catalyst. The initial methyl blue

concentration used in the valuation was 10 mg/mL, and the ultraviolet (UV) light source

was 254 nm for the irradiation of the photo-catalyst.

6.2.7. TREATMENT OF SYNTHETIC DYE WASTEWATER

Photo-catalytic treatment of MB dye wastewater was carried out in a home-made

photo-catalytic reactor. The effect of GO incorporation amount on improving the

photocatalytic activity of composite photocatalyst was investigated. The composite

photo-catalysts prepared with different GO loads were used to treat MB dye wastewater

under ultraviolet light, and the optimal composite photo-catalyst was screened out.

Before the photocatalytic reaction, the petri dish containing 50 mL MB synthetic dye

wastewater and nano photo-catalyst was placed in a black box for 30 min. after the

adsorption equilibrium was reached, the ultraviolet light was turned on for 150 min and

stirred continuously during the light so that the nano photo-catalyst could be in full

contact with synthetic dye wastewater. Accordingly, the effects of the amount of

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composite photo-catalyst, the initial pH value of synthetic wastewater, and the initial

concentration of synthetic wastewater on the treatment effect were investigated, and the

optimal parameters were obtained under different conditions.

6.2.8. EFFECT OF PHOTO-CATALYTIC PROCESS ON METHYLENE BLUE

(MB) DYE STRUCTURE

The effect of the photo-catalytic process on dye molecular structure was analyzed

by UV-visible full-wave scanning of MB synthetic dye wastewater before and after

treatment with composite photo-catalyst.

6.3. RESULTS AND DISCUSSION

6.3.1. SCANNING ELECTRON MICROSCOPE (SEM)

Analysis Figure 15a, b shows the SEM images of TiO2 nanoparticle and Figure

15c, d shows the composite photo-catalyst with GO. Appl. Sci. 2019, 9, x FOR PEER

REVIEW 4 of 12 3. Results and Discussion 3.1. Scanning Electron Microscope (SEM)

Analysis Figure 15a, b shows the SEM images of TiO 2 nanoparticle and Figure 15c, d

shows the composite photo-catalyst with GO.

(a) (b)

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(c) (d)

Figure 15. Scanning electron microscope (SEM) images of TiO2 nanoparticle and
composite photo-catalyst with graphene oxide (GO): (a,b) SEM images of TiO2
nanoparticle at different resolutions; (c) SEM images of composite photo-catalyst at 3%
GO content; (d) SEM images of composite photo-catalyst at 23% GO content.

The above SEM scanning results showed that, in the absence of GO doping, TiO 2

powder was spherical and some particles agglomerated together to clusters. When the GO

doping amount was 3%, the size of the GO monolith was slightly larger than that of TiO 2

nanoparticles, so TiO2 nanoparticles dispersed and adhered to the GO monolith. The

agglomeration of spherical particles in different parts was slightly different and relatively

dispersed between GO monolith structures with few connections, and the surface of the

composite material was mainly composed of TiO 2. When the GO doping amount was

23%, GO accounted for a large proportion of the formed structure, and TiO 2 particles

adhered to GO monolith of different structures, respectively, and the formed clusters

contributed to the GO monolith-like structure.

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6.3.2. X-RAY DIFFRACTION (XRD) ANALYSIS OF COMPOSITE PHOTO-

CATALYST

Figure 16. X-ray diffraction (XRD) patterns of (1) TiO2 and (2) TiO2-GO.

Figure 16 is an XRD pattern of TiO2 and TiO2-GO composite photo-catalyst.

As shown in Figure 2, diffraction peaks at 2θ = 25.3°, 37.8°, 48.0°, 53.9°, 62.7°, 70.3°,

and 75° belonged to diffraction peaks of the (101), (004), (200), (105), (211), and (204)

crystal planes of the anatase. XRD pattern revealed that the prepared TiO 2 is at anatase

phase, with strong and sharp diffraction peak, indicating good crystallinity. The

comparison of the two images demonstrated that TiO2 was still present as an anatase

phase in composite photo-catalyst, but there was no characteristic diffraction peak of GO

in the composite photo-catalyst, which indicated that the presence of GO does not affect

the crystal form and structure of TiO 2. This phenomenon may be explained by low GO

content (15%) in the composite photo-catalyst and covered by the diffraction peak of

TiO2 at 25.4° [20].

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6.3.3. RAMAN SPECTROSCOPY ANALYSIS OF COMPOSITE PHOTO-

CATALYST

Figure 17 shows the Raman spectra of TiO2 and TiO2-GO composite photo-

catalysts. There were three peaks of 396 cm−1 (B1g), 513 cm−1 (A2g), and 639 cm−1 (Eg)

in the Raman spectrum of TiO2, as the vibration mode of anatase phase TiO 2 [21], two

peaks appeared at 1330 and 1600 cm−1 in the Raman spectrum of TiO 2-GO composite

photo- catalysts, with ID/IG = 1.03, which was slightly lower than that of GO (ID/IG =

1.6) [22]. This is probably due to the GO reduction during the reaction. Also, three peaks

appearing in the low-frequency region were identical to those of pure TiO2 vibration

peak, indicating that TiO2 in the composite photo-catalyst is still at the anatase phase.

Appl. Sci. 2019, 9, x FOR PEER REVIEW 5 of 12 Figure 16. X-ray diffraction (XRD)

patterns

of TiO2 (1) and TiO2-GO (2).

Figure 17. Raman Spectra of (1) TiO2 – GO (2) TiO2

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Figure 17 shows the Raman spectra of TiO2 and TiO2-GO composite photo-

catalysts. There were three peaks of 396 cm−1 (B1g), 513 cm−1 (A2g), and 639 cm−1 (Eg)

in the Raman spectrum of TiO2, as the vibration mode of anatase phase TiO 2 [21], two

peaks appeared at 1330 and 1600 cm−1 in the Raman spectrum of TiO 2-GO composite

photo- catalysts, with ID/IG = 1.03, which was slightly lower than that of GO (ID/IG =

1.6) [22]. This is probably due to the GO reduction during the reaction. Besides, three

peaks appearing in the low-frequency region were identical to those of pure TiO2

vibration peak, indicating that TiO2 in the composite photo-catalyst is still at the anatase

phase.

6.4. RESULTS OF PHOTO-CATALYTIC DEGRADATION UNDER DIFFERENT

CONDITIONS

6.4.1. THE AMOUNT OF GO ON THE PHOTO-CATALYTIC ACTIVITY

Figure 18 revealed the treatment effect of 50 mL MB dye wastewater at a

concentration of 20 mg/L by 50 mg composite photo-catalyst doped with 0, 3, 5, 8, 10,

15,

18, 20, 23, 25, and 28 wt% GO under light irradiation, absorbance value was measured

every 0.5 h, a total of 2.5 h. Results showed that the photocatalytic activity when GO was

added was better than that of pure TiO 2, and the peak was observed when the amount of

GO was 15 wt%. After 2.5 h of treatment, the degradation rate reached 91%. When the

doping amount was about 15 wt%, the GO monolith structure and TiO 2 nanoparticles

formed a relatively uniform and reasonable structure. GO can reduce the probability of

photo-generated electrons compounded with holes, and improve the photocatalytic

activity of TiO2 due to its good conductivity.

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At the same time, GO can adsorb MB molecules onto the surface of the composite

catalyst, increase the number of active sites, and improve the catalytic reaction effect due

to its good adsorption properties. A small amount of GO doping was associated with the

limitation of the catalytic reaction effect. When the amount of GO doping is relatively

high, a considerable part of spherical TiO 2 nanoparticles entered the structure mainly

formed by GO, while GO was not subject to reduction, exerted poor light transmittance,

and adsorbed more dye molecules onto the surface of the catalyst, leading to scarce

exposure of internal TiO2 particles to ultraviolet light and a reduced probability of photo-

generated charges separating from the catalyst surface. With excellent conductivity, a

high GR content may promote the recombination of photo-generated electrons and holes,

cause the deactivation of the photo-catalyst, and therefore, the treatment effect of the

synthetic dye wastewater tends to decrease.

Figure 18. Degradation of methylene blue (MB) dye wastewater treated by photo-
catalyst containing different GO contents.

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6.4.2. EFFECT OF THE AMOUNT OF PHOTO-CATALYST ON THE TREATMENT

EFFECT

Figure 19 shows the degradation results of 200 mL MB dye wastewater at an

initial concentration of 20 mg/L after 2.5 h of photocatalytic treatment of 50, 100, 150,

200, and 250 mg composite photo-catalyst. The initial pH value was about 7.78. As

shown in Figure 19, with the increasing amount of composite photo-catalyst, the

degradation rate also increased, but when the amount of composite photo-catalyst ranged

from 250 to 300 mg, the degradation rate began to decline, so the optimal removal effect

is achieved at 250 mg photo-catalyst, and the degradation rate reaches 95%. When the

amount of catalyst added achieved 250 mg, the degradation began to decline, because too

much catalyst caused too many suspended solids in the wastewater, and the light

translucency was very low.

Figure 19. Degradation results of MB synthetic wastewater treated with different amounts of
composite photo-catalyst added

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6.4.3. EFFECT OF WASTEWATER pH VALUE ON THE PHOTO-CATALYTIC

EFFECT

Figure 20 shows the treatment of 250 mL MB dye wastewater at an initial

concentration of 20 mg /L and different pH values (1.90, 3.98, 5.94, 7.98, and 10.02)

after

2.5 h of treatment by 250 mg composite photo-catalyst under ultraviolet light irradiation.

The results show that the degradation rate was relatively high at pH = 5.94 and 7.98,

while relatively low at pH = 1.90. When the pH value of the synthetic wastewater was

7.98, the degradation rate reached a peak, up to 94.1%. When the pH reached 10, the

degradation rate began to decline significantly, which was still higher than the

degradation rate at pH = 1.90. The pH value had a great influence on the stability of dye

molecules, and the negative charges on the surface of GO. The GO surface was highly

negatively charged in the pH range from 5.0 to 12.0, which might be ascribed to the

deprotonation of anionic oxygenous functional groups on GO [23]. Highly negatively

charged GO sheets in suspension could not only disperse homogeneously via

electrostatic repulsion but also enhance the electrostatic attraction between them and

cationic MB molecules, obviously improving the adsorption efficiency [24–27].

However, when too many dye molecules are adsorbed on the surface of GO, the active

sites on the surface of the catalyst will be over- occupied, which will affect the

degradation process of dye molecules. At the same time, the pH value affected the

formation of free radicals, and the dispersion, activity, and surface charge of photo-

catalysts during the photocatalytic process [28], and was related to the “isoelectric point”

of Ti. According to previous data [29], the isoelectric point of GO/TiO2 composite was

pH = 6.7. In the solution of pH > 6.7, the surface of the GO/TiO 2 composite was

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negatively charged, and the surface of the catalyst was positively charged.

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MB molecules are organic cations, which are negatively charged in an alkaline medium.

In contrast, the GO/TiO2 composite has a stronger adsorptive capacity for MB molecules.

Therefore, the degradation effect is better under mild alkaline conditions.

Figure 20. Degradation results of MB synthetic dye wastewater at different initial pH values.

6.4.4. EFFECT OF MB DYE WASTEWATER CONCENTRATION ON THE

TREATMENT EFFECT

Figure 21 shows the treatment effect of 200 mL MB dye wastewater at initial

concentrations of 10, 20, 30, 40, 50, 60, 70, and 80 mg/L, after 2.5 h of 200 mg

composite photo-catalyst treatment. The degradation effect of MB dye wastewater peaked

at the concentration of 10 mg/L. If the concentration of synthetic wastewater is too high,

the transparency of wastewater will be reduced, the light will difficult to enter the

wastewater and react with the photo-catalyst, and the dye molecules will accumulate on

the surface of the photo-catalyst, which exceeds the degradation ability of the active site

on the surface of the catalyst. Therefore, the degradation rate of wastewater will be

reduced. It is concluded that such an amount of composite photo-catalyst is suitable to

treat lower concentrations of synthetic wastewater.

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Figure 21. Degradation result on different concentrations of MB dye wastewater treated

by composite photo-catalyst under UV irradiation.

6.4.5. REPEATED EXPERIMENTAL RESULTS UNDER THE OPTIMUM

CONDITIONS

From the above conditional experiments, the optimum conditions for the

treatment of MB simulated wastewater with composite photo-catalyst are obtained, the

best GO composite ratio is 15 wt.%, the most reasonable amount of composite

catalyst is 200 mg/200 mL, the most suitable initial pH is better under mild alkaline

conditions, and the composite photo-catalyst is suitable to treat lower concentrations of

synthetic wastewater. To study the reproducibility of the resultant composite photo-

catalyst, the cycling number of the photo-catalysis was recorded which is shown in Figure

22.

When each run of the photo-catalysis test was fixed at 150 min for the composite

photocatalyst, it can be seen from the results that composite photo-catalyst can keep the
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degradation rates more than 85% at less for 15 cycles. There was a slight decrease in the

degradation rates during the cycles, which we think might due to the loss of the smaller

nanoparticles which could not be collected from the centrifugation. Besides, in the

process of photo-catalytic wastewater treatment, it is possible to have some reactants or

intermediate products remaining on the surface of the catalyst to cover the active site,

resulting in a gradual decrease in photocatalytic activity. However, even after the 15th

run, the degradation rate could also be more than 85%. These results indicate that the

composite photo-catalyst is a stable photo-catalyst with good cycling life and could be

used for the degradation of the organic pollutants.

Figure 22. Cycling runs of the composite photo-catalyst.

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6.5. PHOTO-CATALYTIC MECHANISM ANALYSIS

The illustration of the Graphene Oxide (GO) supported TiO2 as the photo-catalyst

is shown in Figure 23.

Figure 23. Illustration of the GO supported TiO2 for the photo-catalyst.

As can be seen from Figure 24, with the extension of processing time, the

characteristic absorption peak intensity of MB was getting lower, indicating that the

degradation effect of composite photo-catalyst increased with the processing time. Also,

only the initial characteristic peak intensity of MB gradually decreased throughout the

treatment process, and no new characteristic peak appeared at the other sites. This shows

that when using GO/TiO2 composite photo-catalyst to treat the MB synthetic dye

wastewater, the photo-generated charge directly destroys the luminescent group in MB

molecules, there are no other new luminescent groups produced during the process.

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Figure 24. UV-visible light full-wave scanning results of MB synthetic wastewater

treated by composite photo-catalyst for different periods.

6.6. CONCLUSION

The GO-TiO2 composite photo-catalyst doped with different proportions of GO

was prepared by the sol-gel method and was characterized by SEM, XRD, and Raman

spectroscopy. MB synthetic dye wastewater was taken as the target pollutant to

investigate the composite photo-catalytic activity. Study results showed that TiO 2 in the

composite photo-catalyst is still mainly anatase phase, the catalytic activity is better than

pure TiO2, and the photocatalytic activity reaches the peak when the content of GO is 15

wt%. The composite photocatalyst is more effective for low concentrations of synthetic

wastewater. When 200 mg composite photo-catalyst is used to treat 200 mL of

synthetic wastewater at a concentration of 10 mg/L and an initial pH of about 8 for 2.5 h,

the degradation rate can reach 95.8%. When the GO/TiO2 composite photo-catalyst treats

MB wastewater, photo-generated charge directly destroys the light-emitting groups in

MB molecules, there are no other new light-emitting groups produced in this process.

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