Ultrasonics Sonochemistry 20 (2013) 478484

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Characterization and relative sonocatalytic efciencies of a new MWCNT and CdS modied TiO2 catalysts and their application in the sonocatalytic degradation of rhodamine B
Lei Zhu, Ze-Da Meng, Chong-Yeon Park, Trisha Ghosh, Won-Chun Oh
Department of Advanced Materials Science & Engineering, Hanseo University, Chungnam 356-706, Republic of Korea

a r t i c l e

i n f o

a b s t r a c t
TiO2 nanoparticles modied with MWCNTs and CdS were synthesized by the solgel method followed by solvothermal treatment at low temperature. The chemical composition and surface structure of the CdS/ CNTTiO2 composites were investigated by X-ray diffraction, specic surface area measurements, energydispersive X-ray spectroscopy, transmission electron microscopy, and scanning electron microscopy. Then a series of sonocatalytic degradation experiments were carried out under ultrasonic irradiation in the presence of CNT/TiO2 and the CdS/CNTTiO2 composites. It was found that RhB was quickly and effectively degraded under different ultrasonic conditions. As expected, the nanosized CdS/CNTTiO2 photocatalyst showed enhanced activity compared with the non CdS treated CNT/TiO2 material in the sonocatalytic degradation of RhB. The sonocatalyst CCTb with 34.68% contents of Ti heat treated at 500 C for 1 h showed the highest sonocatalytic activity. The synergistic effect of the greater surface area and catalytic activities of the composite catalysts was examined in terms of their strong adsorption ability and interphase interaction by comparing the effects of different amounts of MWCNTs and CdS in the catalysts and their roles. The mechanism of sonocatalytic degradation over the CdS/CNT modied TiO2 composites under different ultrasonic conditions was also discussed. 2012 Elsevier B.V. All rights reserved.

Article history: Received 23 December 2010 Received in revised form 4 March 2012 Accepted 1 August 2012 Available online 11 August 2012 Keywords: CdS MWCNT TiO2 Ultrasound irradiation Sonocatalytic activity Rhodamine B

1. Introduction Colored wastewater is released in textile efuents and contains potentially environmentally hazardous components. Within the ecosystem, this colored wastewater is a dramatic source of pollution, eutrophication, and perturbations in aquatic life. Moreover, a variety of organic chemicals are produced during the dyeing process and some have been shown to be carcinogenic [1]. With the growing awareness of the decreasing amount of available water resources, many methods, including physical, chemical, and biological methods, are being used in wastewater treatment and recycling. Among them, there are two well-known methods that have been reported. One is the use of a TiO2 photocatalyst, which is the most widely used because of its good activity, chemical stability, commercial availability, and inexpensiveness. TiO2 has three main crystal structures: anatase, which tends to be more stable at low temperature; brookite, which is usually found in minerals and has an orthorhombic crystal structure; and rutile, which is the stable form at higher temperature. Anatase has higher photocatalytic activity and has been studied more than the other two forms of TiO2 [2]. When irradiated with ultraviolet light with a wavelength
Corresponding author. Tel.: +82 41 660 1337; fax: +82 41 688 3352.
E-mail address: wc_oh@hanseo.ac.kr (W.-C. Oh). 1350-4177/$ - see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.ultsonch.2012.08.005

shorter than 380 nm (the band-gap energy of TiO2 is 3.2 eV), the activated TiO2 generates OH radicals which oxidize organic compounds in water. The other method relies on high-amplitude ultrasound to irradiate polluted water [3,4]. A powerful acoustic eld produces many thousands of bubbles in water, which results in repeated growth and collapse cycles every acoustic cycle. The temperature within the bubbles is so high that the solute substances vaporized inside them are immediately decomposed. The temperature near the bubbles is still high and the resulting thermal dissociation of water results in the formation of hydroxyl radicals OH which oxidize the substances near them and make them innocuous [3]. On the other hand, research in this eld has led to some new properties being discovered. According to the theoretical and experimental investigations, sonochemistry is related to sonoluminescence, because both of them originate from the high temperature condition inside the collapsing bubbles [5]. The spectrum of sonoluminescence has a fairly wide range of wavelengths in a liquid and a high intensity of UV emission [68]. Accordingly, sonoluminescence can be a practicable method of degrading organic dyes by adding a photocatalyst, because the intense UV ashes of light caused by sonoluminescence can activate TiO2 effectively. Moreover, some researchers have begun to use nano-sized TiO2 powder and other sonocatalysts to degrade organic pollutants under ultrasonic irradiation [913].

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However, the use of TiO2 as a photocatalyst is limited mainly by the recombination of the generated photo-holes and photo-electrons. Photocatalysis involves the oxidation of a chemical by photo holes from the semiconductor, so every recombination event involves the loss of holes that might otherwise have promoted degradation. Therefore, the Victoria transfer of photogenerated electrons and holes between the valence and conduction bands of semiconductors is important to photocatalysis. Various methods have been reported to improve the photocatalytic efciency by the modication of the surface or bulk properties, i.e. the doping, codeposition of metals, surface chelating, mixing of two semiconductors, coating of an insulating oxide layer, etc. [1418]. In our previous works [19,20], the photocatalytic efciency of TiO2 was increased by using multi-walled carbon nanotubes (MWCNTs) to prepare MWCNT/TiO2 composites. MWCNTs are 1D carbon-based ideal molecules with a nano cylindrical structure, which can conduct electricity at room temperature with essentially no resistance. This phenomenon is known as ballistic transport [21,22] by which the electrons are considered to move freely through the structure, without any scattering from atoms or defects. While the electrons formed by UV irradiation migrate to the surface of the MWCNTs, they are easily transported into the conduction band (CB) of TiO2 which is bound with them. Hence, the increased amount of generated photo-electrons can decrease the high rate of electron/hole pair recombination, which otherwise reduces the quantum yield of the TiO2 process. CdS is one of the most important IIIV group semiconductors, which are extensively applied in optical and electronic elds, such as biological labeling, light-emitting diodes, photoelectric conversion devices, solar cells, photocatalysis and environmental sensors [2330]. CdS constitutes a very desirable window layer for many photovoltaic solar cells, because of its optical and electrical properties [3133]. CdS has been the subject of intensive research, because of its band gap, high absorption coefcient, reasonable conversion efciency, stability and low cost [34]. In recent years, the doping of CdS nanostructures has attracted intensive attention. It was discovered that, by controlling the particle size and microstructure of CdS or by combining it with some other layer compound or solid porous material, such as titanate nanotubes [35] mesoporous silica [36] and titanosilicate zeolite [37], the preparation and characterization of layered metal oxides could be achieved [3840] and [41] some novel physical and chemical properties of CdS were discovered. The transportation of photogenerated carriers between the energy band of CdS and TiO2NTs could prevent the recombination of the charges and improve the photocatalysis activity. Xiao et al. reported [35] that CdS nanoparticles decorated with titanate nanotubes were effective for the degradation of RhB, suggesting that combining CdS particles and TiO2NTs might result in synergetic effects in the photocatalytic reaction. However, as alternative powder photocatalysts, CdS/TiO2 nanoparticles have some disadvantages, such as difcult recovery, easy cohesion and a low utilization rate in practical applications. Some alternative methods are immobilizing nanoparticles onto an inert and porous supporting matrix; through the accumulation of carriers, the adsorption mass transfer rate and efciency of photocatalytic degradation are effectively improved [4245]. In this report, we combined the advantages of introducing MWCNTs and CdS to design an effective catalyst. To improve the catalysis activity of TiO2, CdS/CNT as a doped composite was prepared by the solgel process. The prepared catalysts were characterized by BET, XRD, EDX, SEM and TEM techniques. These catalysts were irradiated with ultrasonic waves with different irradiation intensities and their catalytic activity was compared with that of CdS/CNTTiO2 particles.

2. Experimental 2.1. Materials and reagents The titanium n-butoxide (99%) used as the titanium alkoxide precursor to form TiO2 was purchased from Acros Organics, New Jersey, USA. Crystalline MWCNT (95.9%) powder with a diameter of 20 nm and length of 5 lm was purchased from Carbon Nanomaterial Technology Co., Ltd., Korea. For the oxidization of the surface of the MWCNTs, m-chlorperbenzoic acid, used as an oxidized reagent, was also purchased from Acros Organics, New Jersey, USA. Benzene (99.5%), used as a solvent, was purchased from Samchun Pure Chemical Co., Ltd., Korea. Cadmium chloride1-hydrate (CdCl2H2O) and sodium sulde5-hydrate (Na2S5H2O) purchased from Junsei Chemical Co., Ltd., Japan and Yakuri Pure Chemicals Co., Ltd., Japan, respectively, were used as cadmium and sulfur precursors. The Rhodamine B used was of analytical grade and was purchased from Samchun Pure Chemical Co., Ltd., Korea. 2.2. Preparation of CdS/CNT and CdS/CNTTiO2 composite sonocatalyst 2.2.1. Synthesis of CNT-supported CdS composites Because the MWCNTs are very stable, they need to be treated with strong acids to introduce active functional groups on their surface. In this experiment, 2.0 g MCPBA was suspended in 80 mL of benzene as a solvent. Then 1 g of MWCNTs powder was put into the solution and the mixture was treated by magnetic stirring for 6 h at 353 K. The resultant solution was ltered and continuously washed with deionized water and ethanol 5 times. Then, the sample was dried at 393 K and fully milled. The functionalized MWCNTs were then used to synthesize the nanosized CdS/CNT composite. 2.59 mmol of CdCl2H2O was dissolved in 50 mL of deionized water. Then, 0.3 g of oxidized MWCNTs was added to the solution and stirred further for 45 min in order to sufciently adsorb the Cd2+ ions. A solution of Na2S (30 mL) was prepared separately and added dropwise to the solution with constant stirring for 8 h at 353 K. Under these conditions, the S2 ions react with Cd2+, resulting in the deposition of CdS on the surface of the MWCNTs. The mixture was transformed into a black green color. After completion, the black green solution was ltered, washed with deionized water and ethanol 5 times and then dried at 373 K. Finally, the CdS/CNT composite was obtained. 2.2.2. Synthesis of CdS/CNTTiO2 composite Before being used, two beakers containing 40 mL of benzene were prepared separately. Three, 4 mL of TNB was then added to the solution, followed by magnetic stirring for 5 min. 0.4 g of the as-prepared CdS/CNT composites were added to the solution with constant stirring for 6 h, and the power mixtures of CdS/CNT that reacted with TNB were dried at 393 K for 12 h. Finally, the samples were heated to 773 K for 1 h. These photocatalyst composites were named CCTa and CCTb. For comparison, CNT/TiO2 photocatalyst was synthesized using similar procedures except for heating at 773 K for 1 h and named CT. 2.3. Characterizations of CdS/CNTTiO2 composite The synthesized powders were characterized using a variety of techniques. The crystal phases of the composite photocatalysts were obtained by X-ray diffraction (XRD, Shimata XD-D1, Japan) at room temperature using CuKa radiation. The BrunauerEmett Teller (BET) surface area was determined by N2 adsorption measured at 77 K using a BET specic surface area analyzer (Monosorb, USA). Scanning electron microscopy (SEM, JSM-5200 JOEL, Japan)

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900 800 700

A
S SS

A:Anatase S: CdS

Intensity (counts)

S
600 500 400 300 200

AA

CCTb

CCTa

Fig. 1. Schematic diagram of the sonocatalytic reactor.

100 0

CT
10 20 30 40 50
0

was used to observe the surface morphology and structure of the CdS/CNTTiO2 composites treated with TNB. The EDX spectra were also obtained to determine the elemental composition of the synthesized composites. Transmission electron microscopy (TEM, JEOL, JEM-2010, Japan) at an acceleration voltage of 200 kV was used to examine the size and distribution of the CdS deposited on the MWCNT surface and TiO2 attached to the surface of the CdS/CNT composite. The light absorption of the samples was recorded using a UVvis spectrophotometer (Optizen POP, Mecasys Co., Ltd., Korea) in the range of 200750 nm. 2.4. Measurement of sonocatalytic activities The sonocatalytic activities of the CdS/CNTTiO2 composites were determined by the decomposition of RhB in aqueous solution with ultrasonic generators (Ultrasonic Processor VCX 750, Korea) operated at a minimum frequency of 20 kHz and output power of 750 W through manual adjusting. The catalysts (0.01 g) were suspended in 100 mL of RhB solution with a concentration of 1.0 105 M in a glass vessel. Prior to irradiation, the suspensions were magnetically stirred in the dark for 30 min to ensure the establishment of an adsorption/desorption equilibrium among the sonocatalyst, Rhodamine B and atmospheric oxygen, which was hereafter considered as the initial concentration (c0). For the process of degradation of RhB, a plastic container (diameter = 20 cm, height = 6 cm) lled with ice was used to make a low temperature environment at around 25 C. A schematic diagram of the sonocatalytic is shown in Fig. 1. It consists of four parts: an ultrasonic generator, constant temperature controller, ice water bath, and reactor. Sonocatalytic degradation was tested using the CNTTiO2, CdS/CNTTiO2 a and CdS/CNTTiO2 b catalysts with ultrasonic generators operated at frequencies of 20, 25, and 30 kHz, respectively. The reactions were carried out in an open cylindrical stainless glass vessel. The ultrasonic irradiation of the reactor was done for 30, 60, 90, and 120 min and the removal of the dispersed powders through centrifuge. The clean transparent solution was analyzed using a UVvis spectrophotometer. The spectra (550750 nm) for each sample were recorded and the absorbance was determined at the characteristic wavelength of 554 nm [46] for the degraded RhB solution. As the catalytic properties of CdS/CNTTiO2 composition absorption and degradation the red color of the solution faded gradually with time. 3. Results and discussion 3.1. Structural properties by XRD patterns The XRD technique was used to determine the crystallographic structure of the inorganic part of the composite. The XRD results of the CNT/TiO2 and CdS/CNTTiO2 composites are compared in Fig. 2. For the CNT/TiO2 composite, after heat treatment at 773 K, six

60

70

80

2 theta( )
Fig. 2. XRD patterns of CNT/TiO2 and CdS/CNTTiO2 composites prepared with different contents of TiO2.

distinctive TiO2 peaks are found at 25.3, 37.8, 48.0, 53.8, 54.9, and 62.5 corresponding to the (1 0 1), (0 0 4), (2 0 0), (1 0 5), (2 1 1), and (2 0 4) planes of anatase, respectively, indicating that the TiO2 in the prepared CNT/TiO2 composite existed in the anatase phase. However, it is worth noticing that the characteristic peaks of the MWCNTs could hardly be identied in any of the patterns of the composite catalysts, which was further supported by the observation via SEM, EDX and TEM elemental microanalysis of the CNT/TiO2 composites. From the XRD results of the CdS/CNTTiO2 composites, it was concluded that the TiO2 also existed in the anatase phase. Meanwhile, the additional prominent peaks at angles (2h) of 24.7, 26.5, 28.3, 36.6, 43.8, 48.1, 51.8, and 66.8 were indexed to the reections from the (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (1 1 2), and (2 0 3) planes of the hexagonal structure of CdS, corresponding to the work by Ghows et al. [47]. 3.2. SEM and EDX analysis The SEM images of the CNT/TiO2 and CdS/CNTTiO2 composites prepared with different concentrations of TiO2 are shown in Fig. 3. In Fig. 3(a), we can clearly observe that the MWCNTs were homogenously decorated by well-dispersed particles with only a few TiO2 aggregates. In Fig. 3(b) and (c), the porous structure can be observed and the TiO2 particles are uniformly dispersed on the whole surface of the CdS/CNT composite. Also, we can easily see that with increasing concentration of TiO2, there were some signicant differences in the particle size distribution in these two images. Fig. 3(c) shows a great particle size distribution of sample CCTb. Very large amounts of CdS grains and TiO2 grains were regularly adsorbed and coated on the surface of the MWCNTs and this special structure greatly prevented the CdS grains and TiO2 grains from agglomerating. Thus improving the rate of light adsorption and enhancing the photocatalytic efciency of the catalyst. The EDX microanalyses (wt.%) of the CNT/TiO2 and CdS/CNT TiO2 composites prepared with different contents of TiO2 are shown in Table 1. It can be clearly seen that the CNT/TiO2 composite contained three main elements, viz. C, O, and Ti. In the CdS/ CNTTiO2 composites, the amount of C element decreased and the amount of Ti element increased with increasing volume ratio of TNB in the benzene used for the formation of the TiO2 grains. The EDX spectra of the CNT/TiO2 and CdS/CNTTiO2 composites are shown in Fig. 4. In the spectra, all of the samples showed the peaks of O and Ti, though some impurity elements, such as Cl, Zn, and Cu, existed in some of the CCTb samples (which might have

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Fig. 3. SEM images of CNT/TiO2 and CdS/CNTTiO2 composites prepared with different contents of TiO2: (a) CT, (b) CCTa, and (c) CCTb.

Fig. 4. TEM images of CNT/TiO2 and CdS/CNTTiO2 composites prepared with different contents of TiO2: (a) CT, (b) CCTa, and (c) CCTb.

3.3. BET analysis The BET surface areas of the CNT/TiO2 and CdS/CNTTiO2 composites prepared with different contents of TiO2 are summarized in Table 2. In comparison with the BET surface area of the pristine MWCNTs, which is 211.43 m2/g, the BET surface areas of the CNT/TiO2 composite decreased greatly to 103.51 m2/g, while samples CCTa and CCTb were 123.53 and 102 m2/g, respectively. These results indicate that there was large change in the micropore size distribution for the CNT/TiO2 and CdS/CNTTiO2 composites compared with that of the corresponding MWCNTs. It can be considered that after being treated with TNB, the TiO2 particles lled the pores of the MWCNTs and, thus, decreased the BET surface area. 3.4. TEM analysis The TEM images of the CNT/TiO2 and CdS/CNTTiO2 composites are shown in Fig. 5. The results of the TEM analysis corresponded

Table 1 EDX elemental microanalysis (wt.%) of CNT/TiO2 and CdS/CNTTiO2 composites prepared with different contents of TiO2. Samples Elements C CT CCTa CCTb 39.84 29.91 12.06 O 25.11 38.41 42.98 Ti 35.05 25.06 34.68 Cd 0 6.21 6.51 S 0 0.41 0.35 Impurity 0 0 3.42

been introduced from the experimental procedure). Cd and S elements with the same peak (wavelengths) existed in Fig. 4(b) and (c), so it can be attested that the CdS/CNTTiO2 composites were formed.

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L. Zhu et al. / Ultrasonics Sonochemistry 20 (2013) 478484 Table 2 BET surface areas of pristine MWCNT and CNT/TiO2, CdS/CNT TiO2 composites. Samples Pristine MWCNT CT CCTa CCTb SBET (m2/g) 211.428 103.51 123.53 102

Adsorption capabilities of Rh.B /100(%)

0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00

CT

CCTa

CCTb

Fig. 6. Adsorption capabilities of RhB solution for different samples under magnetic stirring for 30 min.

performed under dark conditions and the results are shown graphically in Fig. 6. From the gure, the level of RhB adsorption by CCTa shows that it has the best adsorption ability among the three samples, because it has the biggest BET surface area. Meanwhile, CT and CCTb show nearly equal adsorption abilities because they have similar BET surface areas. 3.5.2. Sonocatalytic activities Sonocatalytic degradation as a novel decomposing technology for water treatment has attracted much attention in recent years. It is worth noting that using high-amplitude ultrasound to irradiate polluted water can generate OH radicals for use in the oxidation process of dyes. On the other hand, sonoluminescence involves the use of intense UV-light, which excites the TiO2 particles and causes them to act as a photocatalyst during sonication. After irradiation for 120 min, all of the samples exhibit good degradation efciency of RhB. The sonocatalytic efciency of RhB increased with increasing concentration of TiO2, with 17.1%, 28.1% and 38.8% of the RhB solution being degraded for samples CT, CCTa and CCTb under an intensity of 20%, respectively. With increasing intensity from 20% to 25% and 30%, the sonocatalytic efciency of RhB was also accordingly increased. A comparison of the degradation reduction ratio between the different ultrasonic irradiation intensities is shown in Fig. 7. Fig. 8 shows an independent diagram

Fig. 5. EDX elemental microanalysis of the CNT/TiO2 and CdS/CNTTiO2 composites: (a) CT, (b) CCTa, and (c) CCTb.

with those of the SEM analysis. From Fig. 5(a), it could be observed that the TiO2 particles were well dispersed on the wall of the MWCNTs with a few TiO2 particles agglomerated together due to the formation of big grains. The difference in the particle size distribution between the images in Fig. 5(b) and (c) was clearly observed. A few regular black dots were observed, which correspond to CdS particles. The mean size of the CdS nanoparticles was approximately 810 nm, as obtained from the image. In other words, the CdS particles with a small size were attached uniformly to the surface of the CNT tubes. The size of the TiO2 particles was approximately 1020 nm and they were distributed uniformly on the surface of the CNTs. A generally precipitate-free and smooth interface was observed among the CdS, TiO2 and the CNT matrix. In addition, with increasing contents of TiO2, there was no apparent agglomeration of the CdS /CNTTiO2 nanoparticles. This suggests that the presence of the MWCNTs can efciently inhibit the agglomeration of CdSTiO2 and improve the dispersion of the nanoparticles. 3.5. Degradation procedure 3.5.1. Adsorption ability To obtain an accurate degradation data of the CNT/TiO2 and CdS/CNTTiO2 composites, pure adsorption experiments were

0.60 0.55

Sonodegradation rate (%)

0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00

CT 20% 25% CCTa 30% CCTb

20%

25%

30%

Different ultrasonic intensity

Fig. 7. Sonocatalytic activity of different samples evaluated by the decomposition of RhB solution under different ultrasonic intensities for 120 min.

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1.1 1.0 0.9

483

CT CCTa CCTb

0.8 0.7 0.6 0.5 0.4 0.3 0.2 -20 0 20

Sonocatalytic effect

Adsorption effect

40

60

80

100

120

temperature, the experiment was carried out under low temperature conditions. A schematic illustration of the formation of hydroxyl radicals on CNT/TiO2 and CdS/CNTTiO2 under ultrasonic irradiation is shown in Fig. 9. It is well known that the band-gap of CdS/TiO2 nanocomposites is smaller than that of pure TiO2, due to the special optical properties of CdS. This narrow band-gap allows CdS/TiO2 to adsorb more photons and this will enhance the catalytic efciency of TiO2 under light irradiation. When the CdS/TiO2 composite was irradiated under ultrasonic radiation, the photogenerated electrons can be excited from the VB of CdS to the CB of TiO2 through the MWCNTs, whereas the photogenerated holes would be left in the valence band of CdS. The electrons can react with O2 to generate O2, and the holes theoretically migrate to the surface and react with OH or H2O to generate OH. These radicals can then react with the adsorbed pollutants. The reactions can be expressed as follows:

Removal of Rh.B

Ultrasonic irradiation time (min)

Fig. 8. Relative concentration of the RhB solution degraded by the different samples under ultrasonic irradiation with 30% intensity for 120 min.

CdS=TiO2 ultrasonic radiation ! CdS h ; e =TiO2 CdSh ; e =TiO2 ! CdSh =TiO2 e

1 2 3 4

of the sonocatalytic degradation of the synthesized samples under ultrasonic irradiation with 30% intensity. Overall, from the results shown in Figs. 6, 7 and 8, the CCTb catalyst showed the best ability not only in terms of its adsorption, but also its sonocatalytic degradation.

e O2 ! O2 h h

OH ! OH H2 O ! OH h

3.6. Sonodegradation mechanism Up till now, there has been no ready-made mechanism and satisfying explanation for the sonocatalytic degradation of organic pollutants in the presence of various semiconductor materials. Two mechanisms referred to as sonoluminescence and hot spot have been suggested to explain the process of sonocatalytic degradation [11]. Firstly, it is well known that ultrasonic irradiation can result in the formation of light with a comparatively wide wavelength range below 375 nm. These very intense ashed lights can excite the semiconductor catalyst acting as a photocatalyst and cause a great deal of OH radicals with high oxidative activity to form on the surface of the semiconductor particles. Secondly, as is well known, the temperature of the hot spot produced by ultrasonic cavitation in water medium can reach 105 or 106 C, and this high temperature generates many holes, producing OH radicals on the surface of the semiconductor catalyst. Therefore, in this study, in order to eliminate the impact of this high

When introduced with MWCNTs, it can enhance the adsorption ability, it can also absorb light to create photo-induced electrons (e) which are transferred into the conduction band (CB) of the TiO2 and CdS particles, thus increasing the amount of electrons. On the other hand, the presence of MWCNTs can enhance the rate of migration of photogenerated electrons to the surfaces and decrease the recombination probability of photo-electronhole pairs [48]. In addition, with the substitution of the oxygen atoms by the CNTs and CdS in the anatase crystal structure of TiO2, new levels are introduced between the conduction and valence bands of TiO2, the electrons generated by TiO2 can be promoted from the valence band to the CNT level introduced by CdS or from lower to the higher CNT levels, which can increase the quantity of electrons. Therefore, the CdS/CNTTiO2 composites have a narrower band gap and can increase the level of sonodegradation under different ultrasonic intensities. This whole process is clearly described in Fig. 9.

Fig. 9. Simple mechanism of RhB degradation by CdS/CNTTiO2 composite.

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4. Conclusions Novel CdS/CNTTiO2 composites for synergetic degradation with different concentrations of titanium (IV) n-butoxide (TNB) were prepared via a simple solgel method. EDX analysis showed that the elemental contents of CdS/CNTTiO2 were mainly C, O, and Ti with a small quantity of S and Cd. The CdS and TiO2 particles were uniformly loaded on the wall of the MWCNTs in the form of small spots. Compared with the pristine MWCNTs, though the surface areas of CNTTiO2 and CdS/CNTTiO2 were greatly decreased, they showed good adsorption effects. Under ultrasonic irradiation, RhB, which is a typical textile dyestuff, was easily and efciently degraded by the CdS/CNTTiO2 composites. Meanwhile, the sonodegradation rate increased with increasing ultrasonic irradiation intensity. Sample CCTb showed higher sonocatalytic activity than the other catalysts.

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