This action might not be possible to undo. Are you sure you want to continue?
Contents lists available at SciVerse ScienceDirect
journal homepage: www.elsevier.com/locate/ultson
Characterization and relative sonocatalytic efﬁciencies of a new MWCNT and CdS modiﬁed 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 modiﬁed with MWCNTs and CdS were synthesized by the sol–gel method followed by solvothermal treatment at low temperature. The chemical composition and surface structure of the CdS/ CNT–TiO2 composites were investigated by X-ray diffraction, speciﬁc 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/CNT–TiO2 composites. It was found that RhB was quickly and effectively degraded under different ultrasonic conditions. As expected, the nanosized CdS/CNT–TiO2 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 modiﬁed TiO2 composites under different ultrasonic conditions was also discussed. Ó 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 efﬂuents 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 . 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 . When irradiated with ultraviolet light with a wavelength
⇑ Corresponding author. Tel.: +82 41 660 1337; fax: +82 41 688 3352.
E-mail address: firstname.lastname@example.org (W.-C. Oh). 1350-4177/$ - see front matter Ó 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 ÅOH radicals which oxidize organic compounds in water. The other method relies on high-amplitude ultrasound to irradiate polluted water [3,4]. A powerful acoustic ﬁeld 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 ÅOH which oxidize the substances near them and make them innocuous . On the other hand, research in this ﬁeld 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 . The spectrum of sonoluminescence has a fairly wide range of wavelengths in a liquid and a high intensity of UV emission [6–8]. Accordingly, sonoluminescence can be a practicable method of degrading organic dyes by adding a photocatalyst, because the intense UV ﬂashes 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 [9–13].
This phenomenon is known as ballistic transport [21. In recent years. JSM-5200 JOEL.3. The mixture was transformed into a black green color. CdS has been the subject of intensive research. the Victoria transfer of photogenerated electrons and holes between the valence and conduction bands of semiconductors is important to photocatalysis. CdS/CNT as a doped composite was prepared by the sol–gel process. The functionalized MWCNTs were then used to synthesize the nanosized CdS/CNT composite. Then. so every recombination event involves the loss of holes that might otherwise have promoted degradation. because of its band gap. they are easily transported into the conduction band (CB) of TiO2 which is bound with them. the sample was dried at 393 K and fully milled. [14–18]. 0. were used as cadmium and sulfur precursors. Japan. respectively.3 g of oxidized MWCNTs was added to the solution and stirred further for 45 min in order to sufﬁciently adsorb the Cd2+ ions. solar cells. For comparison... the black green solution was ﬁltered. CNT/TiO2 photocatalyst was synthesized using similar procedures except for heating at 773 K for 1 h and named CT.e. Finally. photoelectric conversion devices. the adsorption mass transfer rate and efﬁciency of photocatalytic degradation are effectively improved [42–45]. The resultant solution was ﬁltered and continuously washed with deionized water and ethanol 5 times. the increased amount of generated photo-electrons can decrease the high rate of electron/hole pair recombination. MWCNTs are 1D carbon-based ideal molecules with a nano cylindrical structure. without any scattering from atoms or defects.. The Rhodamine B used was of analytical grade and was purchased from Samchun Pure Chemical Co. m-chlorperbenzoic acid.20]. Preparation of CdS/CNT and CdS/CNT–TiO2 composite sonocatalyst 2. USA. the preparation and characterization of layered metal oxides could be achieved [38–40] and  some novel physical and chemical properties of CdS were discovered. was also purchased from Acros Organics. Finally. Under these conditions. surface chelating. 2. Benzene (99. followed by magnetic stirring for 5 min. etc. codeposition of metals. the photocatalytic efﬁciency of TiO2 was increased by using multi-walled carbon nanotubes (MWCNTs) to prepare MWCNT/TiO2 composites. CdS constitutes a very desirable window layer for many photovoltaic solar cells. which otherwise reduces the quantum yield of the TiO2 process. 2.2. such as difﬁcult recovery. two beakers containing 40 mL of benzene were prepared separately. because of its optical and electrical properties [31–33]. Materials and reagents The titanium n-butoxide (99%) used as the titanium alkoxide precursor to form TiO2 was purchased from Acros Organics.. Experimental 2. XRD. the doping. the doping of CdS nanostructures has attracted intensive attention.. suggesting that combining CdS particles and TiO2NTs might result in synergetic effects in the photocatalytic reaction. For the oxidization of the surface of the MWCNTs. Synthesis of CNT-supported CdS composites Because the MWCNTs are very stable. Various methods have been reported to improve the photocatalytic efﬁciency by the modiﬁcation of the surface or bulk properties. To improve the catalysis activity of TiO2. high absorption coefﬁcient. It was discovered that. reasonable conversion efﬁciency. used as a solvent.59 mmol of CdCl2ÁH2O was dissolved in 50 mL of deionized water. 2. Korea. 2. Then. Therefore. However. In this experiment.22] by which the electrons are considered to move freely through the structure.. Characterizations of CdS/CNT–TiO2 composite The synthesized powders were characterized using a variety of techniques. i. light-emitting diodes. CdS/TiO2 nanoparticles have some disadvantages. by controlling the particle size and microstructure of CdS or by combining it with some other layer compound or solid porous material. USA. resulting in the deposition of CdS on the surface of the MWCNTs. These photocatalyst composites were named CCTa and CCTb. they need to be treated with strong acids to introduce active functional groups on their surface. Photocatalysis involves the oxidation of a chemical by photo holes from the semiconductor. Scanning electron microscopy (SEM. the S2À ions react with Cd2+. Korea. CdS is one of the most important II–IV group semiconductors.9%) powder with a diameter of 20 nm and length of 5 lm was purchased from Carbon Nanomaterial Technology Co. was purchased from Samchun Pure Chemical Co. The crystal phases of the composite photocatalysts were obtained by X-ray diffraction (XRD. While the electrons formed by UV irradiation migrate to the surface of the MWCNTs. 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. Japan) .. we combined the advantages of introducing MWCNTs and CdS to design an effective catalyst. The prepared catalysts were characterized by BET.1.. the use of TiO2 as a photocatalyst is limited mainly by the recombination of the generated photo-holes and photo-electrons.2. 2. In our previous works [19. easy cohesion and a low utilization rate in practical applications. 4 mL of TNB was then added to the solution. through the accumulation of carriers. These catalysts were irradiated with ultrasonic waves with different irradiation intensities and their catalytic activity was compared with that of CdS/CNT–TiO2 particles. Ltd. Korea. the CdS/CNT composite was obtained.4 g of the as-prepared CdS/CNT composites were added to the solution with constant stirring for 6 h. USA). washed with deionized water and ethanol 5 times and then dried at 373 K. Shimata XD-D1. Zhu et al. SEM and TEM techniques. photocatalysis and environmental sensors [23–30]. and the power mixtures of CdS/CNT that reacted with TNB were dried at 393 K for 12 h. 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. Ltd. Cadmium chlorideÁ1-hydrate (CdCl2ÁH2O) and sodium sulﬁdeÁ5-hydrate (Na2SÁ5H2O) purchased from Junsei Chemical Co. mixing of two semiconductors. stability and low cost .L. which are extensively applied in optical and electronic ﬁelds. New Jersey. Ltd. such as biological labeling. / Ultrasonics Sonochemistry 20 (2013) 478–484 479 However. as alternative powder photocatalysts.. used as an oxidized reagent. Ltd. Three. which can conduct electricity at room temperature with essentially no resistance. EDX. the samples were heated to 773 K for 1 h. Some alternative methods are immobilizing nanoparticles onto an inert and porous supporting matrix. Synthesis of CdS/CNT–TiO2 composite Before being used. In this report. reported  that CdS nanoparticles decorated with titanate nanotubes were effective for the degradation of RhB.2. such as titanate nanotubes  mesoporous silica  and titanosilicate zeolite . 0. Japan) at room temperature using CuKa radiation. 2.. coating of an insulating oxide layer. Japan and Yakuri Pure Chemicals Co.0 g MCPBA was suspended in 80 mL of benzene as a solvent.5%). After completion. Hence. New Jersey. A solution of Na2S (30 mL) was prepared separately and added dropwise to the solution with constant stirring for 8 h at 353 K. Ltd. Crystalline MWCNT (95. Xiao et al.2.1. The Brunauer–Emett– Teller (BET) surface area was determined by N2 adsorption measured at 77 K using a BET speciﬁc surface area analyzer (Monosorb.
(1 1 2). The catalysts (0. which was hereafter considered as the initial concentration (c0). The EDX spectra were also obtained to determine the elemental composition of the synthesized composites. we can easily see that with increasing concentration of TiO2. 1. Sonocatalytic degradation was tested using the CNT–TiO2.8°. / Ultrasonics Sonochemistry 20 (2013) 478–484 900 800 700 A S SS A:Anatase S: CdS Intensity (counts) S 600 500 400 300 200 A S A S AA A S CCTb CCTa Fig. 25. In Fig. Transmission electron microscopy (TEM. Mecasys Co. It consists of four parts: an ultrasonic generator. indicating that the TiO2 in the prepared CNT/TiO2 composite existed in the anatase phase. it is worth noticing that the characteristic peaks of the MWCNTs could hardly be identiﬁed in any of the patterns of the composite catalysts. The light absorption of the samples was recorded using a UV–vis spectrophotometer (Optizen POP. 37. and (2 0 3) planes of the hexagonal structure of CdS. However. 28. Measurement of sonocatalytic activities The sonocatalytic activities of the CdS/CNT–TiO2 composites were determined by the decomposition of RhB in aqueous solution with ultrasonic generators (Ultrasonic Processor VCX 750. The spectra (550–750 nm) for each sample were recorded and the absorbance was determined at the characteristic wavelength of 554 nm  for the degraded RhB solution. Also. (2 1 1). 48. ice water bath.8°. and 30 kHz. it was concluded that the TiO2 also existed in the anatase phase. 3(b) and (c). we can clearly observe that the MWCNTs were homogenously decorated by well-dispersed particles with only a few TiO2 aggregates. Rhodamine B and atmospheric oxygen. Structural properties by XRD patterns The XRD technique was used to determine the crystallographic structure of the inorganic part of the composite. Schematic diagram of the sonocatalytic reactor.01 g) were suspended in 100 mL of RhB solution with a concentration of 1. (0 0 2). Thus improving the rate of light adsorption and enhancing the photocatalytic efﬁciency of the catalyst. Korea) in the range of 200–750 nm. 60. 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. viz. 90. . The EDX spectra of the CNT/TiO2 and CdS/CNT–TiO2 composites are shown in Fig. 1. 2. (0 0 4). The clean transparent solution was analyzed using a UV–vis spectrophotometer. 3. which was further supported by the observation via SEM. height = 6 cm) ﬁlled with ice was used to make a low temperature environment at around 25 °C.. distinctive TiO2 peaks are found at 25. Korea) operated at a minimum frequency of 20 kHz and output power of 750 W through manual adjusting.480 L. 4. The XRD results of the CNT/TiO2 and CdS/CNT–TiO2 composites are compared in Fig. XRD patterns of CNT/TiO2 and CdS/CNT–TiO2 composites prepared with different contents of TiO2.8°. 43. For the process of degradation of RhB.5° corresponding to the (1 0 1). 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. As the catalytic properties of CdS/CNT–TiO2 composition absorption and degradation the red color of the solution faded gradually with time. EDX and TEM elemental microanalysis of the CNT/TiO2 composites. Results and discussion 3. 48. Meanwhile. 54. and 120 min and the removal of the dispersed powders through centrifuge. 51. From the XRD results of the CdS/CNT–TiO2 composites. the porous structure can be observed and the TiO2 particles are uniformly dispersed on the whole surface of the CdS/CNT composite.. respectively. Ltd. corresponding to the work by Ghows et al. CdS/CNT–TiO2 a and CdS/CNT–TiO2 b catalysts with ultrasonic generators operated at frequencies of 20. and Cu. constant temperature controller. and 66. Fig.4. A schematic diagram of the sonocatalytic is shown in Fig. 2. (1 0 2).%) of the CNT/TiO2 and CdS/CNT– TiO2 composites prepared with different contents of TiO2 are shown in Table 1. the additional prominent peaks at angles (2h) of 24. and reactor. (1 0 5).3°.5°. It can be clearly seen that the CNT/TiO2 composite contained three main elements.3°. 26.8° were indexed to the reﬂections from the (1 0 0). and (2 0 4) planes of anatase. respectively. 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. 3(a). and Ti. In the CdS/ CNT–TiO2 composites.1°. Zn. C.8°. 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. For the CNT/TiO2 composite. The reactions were carried out in an open cylindrical stainless glass vessel. 100 0 CT 10 20 30 40 50 0 was used to observe the surface morphology and structure of the CdS/CNT–TiO2 composites treated with TNB. and 62. 3. existed in some of the CCTb samples (which might have . after heat treatment at 773 K.2. such as Cl. there were some signiﬁcant differences in the particle size distribution in these two images. 3(c) shows a great particle size distribution of sample CCTb.0 Â 10À5 M in a glass vessel. The EDX microanalyses (wt.1. (1 1 0). all of the samples showed the peaks of O and Ti. though some impurity elements. Zhu et al.9°. 2. a plastic container (diameter = 20 cm. 36. six 60 70 80 2 theta( ) Fig. (1 0 3). O.0°. In the spectra. The ultrasonic irradiation of the reactor was done for 30. 3. SEM and EDX analysis The SEM images of the CNT/TiO2 and CdS/CNT–TiO2 composites prepared with different concentrations of TiO2 are shown in Fig.7°.6°. 53. (1 0 1). JEOL. JEM-2010. In Fig. (2 0 0).
98 Ti 35. the BET surface areas of the CNT/TiO2 composite decreased greatly to 103. Fig. so it can be attested that the CdS/CNT–TiO2 composites were formed. and (c) CCTb. / Ultrasonics Sonochemistry 20 (2013) 478–484 481 Fig.84 29.41 42. 5.21 6. (b) CCTa. (b) CCTa.42 been introduced from the experimental procedure). while samples CCTa and CCTb were 123. which is 211. and (c) CCTb. 3.51 m2/g. respectively. 4. 4(b) and (c). The results of the TEM analysis corresponded Table 1 EDX elemental microanalysis (wt.11 38. decreased the BET surface area. Samples Elements C CT CCTa CCTb 39.06 34. These results indicate that there was large change in the micropore size distribution for the CNT/TiO2 and CdS/CNT–TiO2 composites compared with that of the corresponding MWCNTs. the TiO2 particles ﬁlled the pores of the MWCNTs and. TEM images of CNT/TiO2 and CdS/CNT–TiO2 composites prepared with different contents of TiO2: (a) CT.41 0.53 and 102 m2/g.3.L. Zhu et al.91 12. SEM images of CNT/TiO2 and CdS/CNT–TiO2 composites prepared with different contents of TiO2: (a) CT. 3.05 25.%) of CNT/TiO2 and CdS/CNT–TiO2 composites prepared with different contents of TiO2. thus. BET analysis The BET surface areas of the CNT/TiO2 and CdS/CNT–TiO2 composites prepared with different contents of TiO2 are summarized in Table 2. It can be considered that after being treated with TNB. Cd and S elements with the same peak (wavelengths) existed in Fig. . 3.35 Impurity 0 0 3.68 Cd 0 6.43 m2/g. TEM analysis The TEM images of the CNT/TiO2 and CdS/CNT–TiO2 composites are shown in Fig. In comparison with the BET surface area of the pristine MWCNTs.06 O 25.51 S 0 0.4.
Zhu et al.1%.20 0. Adsorption ability To obtain an accurate degradation data of the CNT/TiO2 and CdS/CNT–TiO2 composites. 7. pure adsorption experiments were 0.B η/100(%) 0. 5(a).30 0.1% and 38. Samples Pristine MWCNT CT CCTa CCTb SBET (m2/g) 211. A few regular black dots were observed. TiO2 and the CNT matrix.30 0. and (c) CCTb. From the ﬁgure.5.1. CCTa and CCTb under an intensity of 20%.55 Sonodegradation rate (%) 0. The difference in the particle size distribution between the images in Fig. EDX elemental microanalysis of the CNT/TiO2 and CdS/CNT–TiO2 composites: (a) CT.5.35 0. CdS/CNT– TiO2 composites. 3. This suggests that the presence of the MWCNTs can efﬁciently inhibit the agglomeration of CdS–TiO2 and improve the dispersion of the nanoparticles. In addition. A generally precipitate-free and smooth interface was observed among the CdS. After irradiation for 120 min. 6. 8 shows an independent diagram Fig.45 0. With increasing intensity from 20% to 25% and 30%. The size of the TiO2 particles was approximately 10–20 nm and they were distributed uniformly on the surface of the CNTs. A comparison of the degradation reduction ratio between the different ultrasonic irradiation intensities is shown in Fig. 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. performed under dark conditions and the results are shown graphically in Fig. there was no apparent agglomeration of the CdS /CNT–TiO2 nanoparticles.25 0.10 0.00 CT CCTa CCTb Fig. with increasing contents of TiO2. all of the samples exhibit good degradation efﬁciency of RhB. Sonocatalytic activities Sonocatalytic degradation as a novel decomposing technology for water treatment has attracted much attention in recent years. The mean size of the CdS nanoparticles was approximately 8–10 nm. From Fig. CT and CCTb show nearly equal adsorption abilities because they have similar BET surface areas. Fig. 5. the level of RhB adsorption by CCTa shows that it has the best adsorption ability among the three samples.428 103. On the other hand.60 0.8% of the RhB solution being degraded for samples CT.15 0. . Sonocatalytic activity of different samples evaluated by the decomposition of RhB solution under different ultrasonic intensities for 120 min.51 123. 28. because it has the biggest BET surface area. 5(b) and (c) was clearly observed. with 17.15 0. as obtained from the image. 7. respectively.53 102 Adsorption capabilities of Rh. which correspond to CdS particles.10 0. It is worth noting that using high-amplitude ultrasound to irradiate polluted water can generate OHÅ radicals for use in the oxidation process of dyes.05 0. (b) CCTa. which excites the TiO2 particles and causes them to act as a photocatalyst during sonication.40 0. the sonocatalytic efﬁciency of RhB was also accordingly increased.482 L. 3. The sonocatalytic efﬁciency of RhB increased with increasing concentration of TiO2. sonoluminescence involves the use of intense UV-light. In other words.05 0.25 0. 6.2. with those of the SEM analysis. / Ultrasonics Sonochemistry 20 (2013) 478–484 Table 2 BET surface areas of pristine MWCNT and CNT/TiO2.00 CT 20% 25% CCTa 30% CCTb 20% 25% 30% Different ultrasonic intensity Fig. the CdS particles with a small size were attached uniformly to the surface of the CNT tubes. Degradation procedure 3.5.50 0.35 0. Meanwhile.20 0. Adsorption capabilities of RhB solution for different samples under magnetic stirring for 30 min.
9 483 CT CCTa CCTb 0. it can enhance the adsorption ability. Simple mechanism of RhB degradation by CdS/CNT–TiO2 composite.6 0. it is well known that ultrasonic irradiation can result in the formation of light with a comparatively wide wavelength range below 375 nm.1 1. 9. in this study.L. in order to eliminate the impact of this high When introduced with MWCNTs.7 0. 6. eÀ Þ=TiO2 ! CdSðh Þ=TiO2 ðeÀ Þ þ þ þ ð1Þ ð2Þ ð3Þ ð4Þ of the sonocatalytic degradation of the synthesized samples under ultrasonic irradiation with 30% intensity. the presence of MWCNTs can enhance the rate of migration of photogenerated electrons to the surfaces and decrease the recombination probability of photo-electron–hole pairs . On the other hand. 9. eÀ Þ=TiO2 CdSðh . producing ÅOH radicals on the surface of the semiconductor catalyst. and this high temperature generates many holes. Fig. with the substitution of the oxygen atoms by the CNTs and CdS in the anatase crystal structure of TiO2. there has been no ready-made mechanism and satisfying explanation for the sonocatalytic degradation of organic pollutants in the presence of various semiconductor materials. When the CdS/TiO2 composite was irradiated under ultrasonic radiation.5 0. the experiment was carried out under low temperature conditions. Zhu et al. This whole process is clearly described in Fig. 7 and 8. Overall.8 0. as is well known. due to the special optical properties of CdS. These very intense ﬂashed lights can excite the semiconductor catalyst acting as a photocatalyst and cause a great deal of ÅOH radicals with high oxidative activity to form on the surface of the semiconductor particles. Secondly. The electrons can react with O2 to generate ÅO2À. from the results shown in Figs. CdS=TiO2 þ ultrasonic radiation ! CdS ðh . Firstly. which can increase the quantity of electrons. . it can also absorb light to create photo-induced electrons (eÀ) which are transferred into the conduction band (CB) of the TiO2 and CdS particles.2 -20 0 20 Sonocatalytic effect Adsorption effect 40 60 80 100 120 temperature. the CCTb catalyst showed the best ability not only in terms of its adsorption. thus increasing the amount of electrons. but also its sonocatalytic degradation.4 0. the temperature of the ‘‘hot spot’’ produced by ultrasonic cavitation in water medium can reach 105 or 106 °C. the CdS/CNT–TiO2 composites have a narrower band gap and can increase the level of sonodegradation under different ultrasonic intensities.6. eÀ þ O2 ! Å O2À h h þ þ OHÀ ! Å OH þ H2 O ! Å OH þ h þ þ ð5Þ 3. Therefore. Therefore. 8. This narrow band-gap allows CdS/TiO2 to adsorb more photons and this will enhance the catalytic efﬁciency of TiO2 under light irradiation. 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. / Ultrasonics Sonochemistry 20 (2013) 478–484 1. and the holes theoretically migrate to the surface and react with OH– or H2O to generate ÅOH. Sonodegradation mechanism Up till now.3 0. The reactions can be expressed as follows: Removal of Rh.B Ultrasonic irradiation time (min) Fig. Relative concentration of the RhB solution degraded by the different samples under ultrasonic irradiation with 30% intensity for 120 min. 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. new levels are introduced between the conduction and valence bands of TiO2. 9. It is well known that the band-gap of CdS/TiO2 nanocomposites is smaller than that of pure TiO2. A schematic illustration of the formation of hydroxyl radicals on CNT/TiO2 and CdS/CNT–TiO2 under ultrasonic irradiation is shown in Fig. Two mechanisms referred to as sonoluminescence and ‘‘hot spot’’ have been suggested to explain the process of sonocatalytic degradation .0 0. These radicals can then react with the adsorbed pollutants. In addition.
L. Soc.F. Nishimura. M. B 39 (2002) 75–90. R. 255 (2008) 740–742. Conductivity studies on spray-pyrolysed CdS ﬁlms in ambient conditions. photochemical and photocatalytic aspects of metal nanoparticles. L. H.C.Y. Ind. K. Mater. 14 (2007) 184–190. 44–45 (2001) 419–425. W. 3 (1996) 205–208. Fast and easy synthesis of core-shell nanocrystal (CdS/TiO2) at low temperature by micro-emulsion under ultrasound.A. Am. Chem.  Y.B. Bell. References  H. Hoffmann. Xu.  F. Lush. Nagaveni. M.  W. B: Environ. R. 68 (8) (1995) 2439–2445. T. Wu. J.  A. Hegde. G.  P. Today 98 (2004) 431–439. Ge.V. Okitsu. P.Z. Growth Des.P. Phys. O. Sonoluminescence. S. Sonochem. C.  Z. Li.D.  J. C. Li. Enhanced photocatalytic activity of supported TiO2: dispersing Effect of SiO2 J. Inﬂuence of preparation technique on the structural. 9 (1990) 1025–1027.  X. G.  N. Huang. 169 (2009) 486–491. Adv. Phys. Eiichi. Y. G. Y. Liu. Chen. Zhang.K. Direct splitting of water under visible light irradiation with an oxide semiconductor photocatalyst. S. Y. Zhang.  N. Visible light induced hydrogen evolution on CdS K4Nb6O17 photocatalyst. S. Chen. Characterizing the structure and properties of individual wire-like nanoentities. A. Park. Ultrason.L. Photochem. Photocatalytic activity of WOx–TiO2 under visible light irradiation. Photocatalytic activity of CdS nanoparticles incorporated in titanium silicate molecular sieves of ETS-4 and ETS-10. Mendoza. K.W. M. Ye. Degradation of the cationic dye rhodamine B in aqueous anionic surfactant/TiO2 dispersions under visible light irradiation: evidence for the need of substrate adsorption on TiO2 particles.  R. Phys. K. M. Under ultrasonic irradiation.T. Yang.J. J.S. B. Schulz-Ekloff. 32 (1998) 2394–2400. Hazard. J. 29 (2001) 167–176. Mater. EDX analysis showed that the elemental contents of CdS/CNT–TiO2 were mainly C. Cao.F. Crocein Orange G. Y. 27 (2006) 1423–1428. Compared with the pristine MWCNTs. K.H. Catal. K.K. Langmuir 20 (2004) 2900–2907. Lachheb. Phys. Zhang. Cheng. Ghows.L. Oh.  W. J.  H. Chem. Lua. J.G. Congo Red. A. Yoshida.  M. Kunio.R. Phys. K. Photocatalytic hydrogen evolution from water on nanocomposites incorporating cadmium sulﬁde into the interlayer. Chavez. Apikyan. Investigation on transition crystal of ordinary rutile TiO2 powder and its sonocatalytic activity. Purushothaman. Sonochem. Muñoz-Aguirre. A.C. Zhao. Sonochem. M. Barber.: Electr. Cells 69 (2001) 189–194. 122 (1999) 57–60. Formation of CdS nanoparticles within functionalized siliceous MCM-41. Balkan Phys. Okitsu.K. 12 (2000) 1295–1298. Ìzci. Kose. Sci. Yang. Gonzalez.  H. 57 (2005) 23–30.  W. 35 (2002) 1063– 1069. Investigation of energy band gap and optical properties of cubic CdS epilayers. Rodríguez. Mater. Kinetics of photocatalytic degradation of aniline in water over TiO2 supported on porous nickel. T. H.W. Sonochem. Guo. J. P.P. Synthesis of CdS and ZnS nanowires using single-source molecular precursors. G. Chem. A: Chem. Huang. Phys.  P.H.S. 3.-Chim. A: Chem. Shimizu.  Y.V. Technol. Preparation and characterization of netted sphere-like CdS nanostructures. Rathousky. P.L. Energy Mater. K. P. Lieber. B 108 (2004) 4086–4093. Y. Mater.  H. C. 15 (2009) 190–195. Tetsuya. Dadjour.C. Weninger. Lett. E. K. Putterman. Yamamoto. Valyomana. J. W.  F.Q. Vijayakumar. Cho. Vacuum 51 (1998) 349– 355. Science 266 (1994) 248–250.K. A 295 (1) (2005) 71–78. G. 8 (2008) 629–634. Zelaya. X. Ling. Acta Phys. Sonochem. Choi. Greenﬁeld.  M. Hidaka. J.  K. Zhu et al. Nagata. Appl. Al Kuhaimi. J. Ray. Yu. Zhao. Puzenat. Y.F. 254 (2008) 7522– 7526.D. Formation of CdS nanoparticles using starch as capping agent. Eng. they showed good adsorption effects. Korean Chem. Nakui. Sci. Phys.B. 4. sonochemistry (H2O2 yield) and bubble dynamics: frequency and power effects. Z. H.  A. Preparation and characterization of CdS nanoparticles decorated into titanate nanotubes and their photocatalytic properties. Entezari. J. Y. Hiller. Lee. solution growth and spray pyrolysis. Kondo. Hazard. F. G. Zhang. Photocatalytic degradation of orange II by TiO2 catalysts supported on adsorbents. W. Photochem. Microporous Mesoporous Mater. Hu. Barakat. and Ti with a small quantity of S and Cd. Phys. J. which is a typical textile dyestuff.J. S. Jiang. J. 5 (1997) 1115–1119. . Valyomana. M. C 112 (2008) 1001–1007. Y. Houas. Ultrason.  W. Lett.J. Guan. Weninger. N. W. McClure. Environ. Elaloui.S.  S. Meanwhile. J. Zukal.M. Wang. Wang.  C. G. Sci. Multibubble sonoluminescence spectra of water which resemble single-bubble sonoluminescence. Heat treatment effects on the characteristics and sonocatalytic performance of TiO2 in the degradation of organic dyes in aqueous solution. 14 (2007) 246–252.  P. 146 (2007) 636–639. Liu. Appl.: B 106 (2002) 1227–1230. G. Ultrason. Decomposition of chloroﬂuorocarbons and hydroﬂuorocarbons in water by ultrasonic irradiation. B: Environ. Bull. J.  R. Xiao. Ultrasound as a catalyser of aqueous reaction systems: the state of the art and environmental applications. K. Surf. Grieser. Catal. Characterization and catalytic activity of core–shell structured gold/palladium bimetallic nanoparticles synthesized by the sonochemical method. Kanthale. Bae.N.M.  M. Y. Sci. Catal. Ma. Cryst. Jiang.  P.  H.  D. Wellmann. J. M. H. Nanotechnology 19 (2008) 015706–015713. T.Q. C. Tanaka. J. R. Chem. Belen.484 L. Sin.P. F.Y. San-Martin Martínez. Chen. Growth Des. Wang. Photocatalytic degradation of 2-chlorophenol by Co-doped TiO2 nanoparticles. Purushothaman. Nature 414 (2001) 625–627. V. S. Mater. Cui. Rev. Subbanna. E. Soc. Surf. Characterization of AC/TiO2 composite prepare with pitch binder and their photocatalytic activity. Hayes.M. Appl.L. A. Appl. Synthesis and photocatalytic properties of CdSintercalated metal oxides. Singh. Murata.C. Charlier. C. Z. Guo. Zhang. Chem. 141 (2001) 209– 217.  A. K. Sonocatalytic degradation of methylene blue with TiO2 pellets in water. 11 (1992) 616–618. J. The CdS and TiO2 particles were uniformly loaded on the wall of the MWCNTs in the form of small spots.G. P. E. Ultrason. Jpn. Tezcanli. Putterman. Effect of annealing temperatures on the electrical transport properties of spray-pyrolysed CdS ﬁlms. Ultrason.J. Methyl Red.G. Sayama.  K.C. C. Chem. C 111 (49) (2007) 18195–18203. Wark. W.A. 125 (2003) 11498–11499. Kim. Catal. Y. Li. F. 84 (2000) 5640–5643. G. Abdullah. Sol.  Y. B 106 (2002) 7729–7744. J. Kamat. Hydrazine degradation by ultrasonic irradiation. Catal.N. J. W. Leng. Zhao. Res. Guillard. C. Zhang. Domen. M. Wu. Sample CCTb showed higher sonocatalytic activity than the other catalysts. G. Bhattacharyya. Today 68 (2001) 173–182. Photocatalytic degradation of various types of dyes (Alizarin S.X. W. Herrmann. Appl. J. Synthesis and structure of nanocrystalline TiO2 with lower band gap showing high photocatalytic activity. optical and electrical properties of polycrystalline CdS ﬁlms. Synthesis of anatase TiO2 supported on porous solids by chemical vapor deposition. I. 18 (2011) 629–634. T. Time-resolved spectra of sonoluminescence. Hazard.C. T.  G.  J. Methylene Blue) in water by UVirradiated titania. Ince.A. A. was easily and efﬁciently degraded by the CdS/CNT–TiO2 composites. 80 (1998) 1090–1093. N. K.S. RhB. Yoshida. O. Maeda.  N. Controlled synthesis of hyperbranched cadmium sulﬁde micro nanocrystals. Arakawa.O. K. though the surface areas of CNT–TiO2 and CdS/CNT–TiO2 were greatly decreased. Gordeychuk. Mater. Ismat-Shah. Hirai. J. Maeda. S.  W. M.H. Kawi. Mizukoshi. the sonodegradation rate increased with increasing ultrasonic irradiation intensity.A. Kl ckaya.Z. N. X. D. Characterization and relative photonic efﬁciencies of a new Fe-ACF/TiO2 composite photocatalysts designed for organic dye decomposition. Ding. Barrelet. Balcerski. Jordan. Acc.D.N.G. Electrical. Large-scale and shapecontrolled syntheses of three-dimensional CdS nanocrystals with ﬂowerlike structure. J.Q. Lee. N.Q. Yue.L. Hiller. Didenko. Oshima. Choi. 8 (1997) 151–154. H. B 101 (1997) 7033–7037.G. Vijayakumar. Sol. Zhao. Yoshida. 15 (2008) 143–150.D.H. Zou. Zhang. Conclusions Novel CdS/CNT–TiO2 composites for synergetic degradation with different concentrations of titanium (IV) n-butoxide (TNB) were prepared via a simple sol–gel method. Maeda.T. Photophysical. / Ultrasonics Sonochemistry 20 (2013) 478–484  M. Serpone. Chem. A. Photobiol. K.A. Lett. Liu. Dang. Kim.M. X. Sci. Katsuki.J. Catal. Mater. Lee. M. Cryst. 24 (11) (2008) 1975–1980. Chen. Ashokkumar. J. J. Ravishankar.Y. H. Chem. Wang. M.  S.J.J. S. 173 (2010) 159–167. Ksibi. Yoshimura. W.R. C. Wang. Appl. Lett. K. A: Chem.L. Effects of TiO2 surface ﬂuorination on photocatalytic reactions and photoelectrochemical behaviors. Oh. Photocatalytic production of hydrogen from water with visible light using hybrid catalysts of CdS attached to microporous and mesoporous silicas. optical and structural properties of Cd1ÀxInxS ﬁlms grown by spray pyrolysis method. Photobiol. M. Nagata.  Z. Wang. Degradation of rhodamine B in aqueous solution by using swirling jet-induced cavitation combined with H2O2. A. Madrad.H. Soc. Chen. Lett.Z. Ogino. Ryu. Wu. 131 (2000) 125–132. Bull. Defects in carbon nanotubes.N. Wang. X. Mater.J.  X. Physical and electrical characterization of CdS ﬁlms deposited by vacuum evaporation. Zheng. Rev. Wu.P. Effect of composite modes on photoelectrochemical properties of MWCNTs/TiO2 nanocomposite ﬁlms. Photochem. J. Y. Shangguan. Chem. L. Oikawa. C. T. Photoassisted degradation of dye pollutants. Chem.  J.  Z. Z. Schaeffer. Y. Zhou.B.M. J.P. Shangguan. Photobiol.  A. R. 8 (2008) 717–722. Sci.  J. Ko. Effect of noble gas doping in single-bubble sonoluminescence.
This action might not be possible to undo. Are you sure you want to continue?