Sonocatalytic degradation of acid red B and rhodamine B catalyzed by nano-sized ZnO powder under ultrasonic irradiation

Nano-sized ZnO powder was introduced to act as the sonocatalyst after the treatment of high-temperature activation, and the ultrasound of low power was used as an irradiation source to induce nano-sized ZnO powder performing sonocatalytic degradation of acid red B and rhodamine B. At the same time, the effects of operational parameters such as solution pH value, initial concentration of dyestuff and addition amount of nano-sized ZnO powder have been examined in this paper. We found that the degradation ratios of acid red B and rhodamine B in the presence of nano-sized ZnO powder were much higher than that with only ultrasonic irradiation. However, the degradation ratio of acid red B was about two times higher than that of rhodamine B for the initial concentration of 10.0 mg/L, addition amount of 1.0 g/L nano-sized ZnO powder, solution acidity of pH 7.0 and 60 min irradiation experimental condition. The difference of the degradation ratios can be illustrated by the difference of chemical forms of acid red B and rhodamine B in aqueous solution and the surface properties of nano-sized ZnO particles. In addition, the researches on the kinetics of sonocatalytic reactions of acid red B and rhodamine B have also been performed and found to the follow pseudo first-order kinetics. All the experiments indicated that the sonocatalytic method in the presence of nano-sized ZnO powder was an advisable choice for the treatments of non- or low-transparent organic wastewaters in future.     

Investigation on the sonocatalytic degradation of acid red B in the presence of nanometer TiO2 catalysts and comparison of catalytic activities of anatase and rutile TiO2 powders

Here, the nanometer anatase and rutile titanium dioxide (TiO(2)) powders were introduced to act as the sonocatalysts during the ultrasonic degradation of azo dye-acid red B which was chosen as model compound. The ultrasound of low power was used as an irradiation source to induce TiO(2) particles performing catalytic activity. It was found that the processes of sonocatalytic degradation were different between nanometer anatase TiO(2) and nanometer rutile TiO(2). For nanometer anatase TiO(2) catalyst, the acid red B was mainly oxidated by the holes on the surface of nanometer anatase TiO(2) particles, so that the decolorization and degradation happened at the same time. For the nanometer rutile TiO(2) catalyst, the acid red B was mainly oxidated by the *OH radicals from the ultrasonic cavitation, so that the decolorization of azo bond takes place primarily, and then the degradation of naphthyl ring does. The intermediates of acid red B in the presence of nanometer anatase and rutile TiO(2) powders have been monitored by UV-vis spectra and high performance liquid chromatography (HPLC), respectively. All experiments indicated that the degradation effect of acid red B in the presence of nanometer anatase TiO(2) powder was obviously better than that in the presence of nanometer rutile TiO(2) powder. Hence, the method of sonocatalytic degradation for organic pollutants in the presence of nanometer anatase TiO(2) powder is expected to be promising as an advisable choice for the treatment of organic wastewaters in future.     

Sonocatalytic degradation of methyl orange in the presence of TiO2 catalysts and catalytic activity comparison of rutile and anatase

Rutile and anatase titanium dioxide (TiO(2)) powders were used as sonocatalysts for the degradation of methyl orange which was used as a model compound. Ultrasound was used as an irradiation source. It was found that the sonocatalytic degradation ratios of methyl orange in the presence of TiO(2) powder were much better than ones without any TiO(2), but the sonocatalytic activity of rutile TiO(2) particles was obviously higher than that of anatase TiO(2) particles. Although there are many factors influencing sonocatalytic degradation of methyl orange, the experimental results show that the best degradation ratio of methyl orange can be obtained when the experimental conditions of the initial methyl orange concentration of 10 mg/l, rutile TiO(2) added amount of 500 mg/l, ultrasonic frequency of 40 kHz, output power of 50 W, pH=3.0 and 40 degrees C within 150 min were adopted. In addition, the catalytic activity of reused rutile TiO(2) catalyst was also studied and found to be better than new rutile TiO(2) catalyst sometimes. All experimental results indicated that the method of the sonocatalytic degradation of organic pollutants in the presence of TiO(2) powder was an advisable choice for treating non- or low-transparent organic wastewaters.     

Treatment of nano-sized rutile phase TiO2 powder under ultrasonic irradiation in hydrogen peroxide solution and investigation of its sonocatalytic activity

The treated mixed-crystal TiO(2) powder with high sonocatalytic activity was obtained through utilizing ultrasonic irradiation in hydrogen peroxide solution. At the same time, some influencing factors (including heat-treated temperature and heat-treated time) on the sonocatalytic activity of treated mixed-crystal TiO(2) powder were also considered through the degradation of methylene blue in aqueous solution. In this work, it was found that the sonocatalytic degradation ratio of methylene blue in the presence of treated mixed-crystal TiO(2) powder was much higher than ones in the presence of nano-sized rutile phase TiO(2) powder and with onefold ultrasonic irradiation. At last, the methylene blue in aqueous solution was completely degraded and became some simple inorganic anions such as NO(3)(-), SO(4)(2-) and Cl(-). All experiments indicated that the sonocatalytic method adopting treated mixed-crystal TiO(2) powder as sonocatalyst was an advisable choice for the treatments of non- or low-transparent wastewaters in future.     

Investigation on transition crystal of ordinary rutile TiO2 powder and its sonocatalytic activity

The transition crystal TiO(2) sonocatalyst was prepared utilizing the method of ultrasonic irradiation in hydrogen peroxide solution. The sonocatalytic activity of the transition crystal TiO(2) powder was validated through the degradation of methyl orange in aqueous solution by ultrasonic irradiation. The results show that the sonocatalytic activity of the transition crystal TiO(2) powder is obviously higher than that of pure rutile and anatase TiO(2) powders as well as mixed rutile and anatase TiO(2) powders according to the proportion of corresponding transition crystal TiO(2) catalyst. The degradation ratio of methyl orange in the presence of the transition crystal TiO(2) catalyst surpasses 75% within 80 min ultrasonic irradiation, while the degradation ratios are 55.93%, 51.68% and 40.88%, respectively, for rutile, mixed and anatase TiO(2) powders.     

The investigation of sonocatalytic activity of Er3+:YAlO3/TiO2-ZnO composite in azo dyes degradation

In this work, the emphasis was mainly placed on investigating the sonocatalytic activity of TiO(2)-ZnO mixed with Er(3+):YAlO(3), namely, Er(3+):YAlO(3)/TiO(2)-ZnO composite. It is able to utilize the sonoluminescence light to improve the sonocatalytic degradation of organic dyes. The Er(3+):YAlO(3) as up-conversion luminescence agent was synthesized by sol-gel and auto-combustion method, and then Er(3+):YAlO(3)/TiO(2)-ZnO composite as sonocatalyst were prepared by ultrasonic dispersion and liquids boil method. The prepared up-conversion luminescence agent and composites were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Acid Red B dye was selected to examine the sonocatalytic activity of Er(3+):YAlO(3)/TiO(2)-ZnO composite. The degradation reaction processes were monitored by UV-vis spectrophotometer and ion chromatogram. The influences on the activity of the Er(3+):YAlO(3)/TiO(2)-ZnO such as Ti/Zn molar ratio, heat-treated temperature and heat-treated time were studied. The results showed that the Er(3+):YAlO(3)/TiO(2)-ZnO composite exhibited a significantly high sonocatalytic activity compared with other catalysts in the degradation of Acid Red B. And the sonocatalyst with 1:1 Ti/Zn molar ratio heat-treated at 550°C for 60min showed the highest sonocatalytic activity. At last, the experiment also indicated that it has a good sonocatalytic activity to degrade other organic dyes.     

Investigation on the transition crystal of ordinary rutile TiO2 powder by microwave irradiation in hydrogen peroxide solution and its sonocatalytic activity

The transition crystal TiO(2) catalyst with high sonocatalytic activity was obtained utilizing the microwave irradiation in hydrogen peroxide solution. At the same time a series of affecting factors (microwave irradiation time, heat-treated time and heat-treated temperature) to prepare the TiO(2) catalyst on the sonocatalytic degradation of parathion were considered in this paper. The ultrasound of low power was used as an irradiation source to induce treated TiO(2) particles to perform catalytic activity. The results show that the sonocatalytic activity of the transition crystal TiO(2) powder is obviously higher than those of pure ordinary rutile and anatase TiO(2) powders. At last, the parathion in aqueous solution was degraded completely and became some simple inorganic ions such as NO(3)(-), PO(4)(3-), SO(4)(2-), etc. The degradation ratio of parathion in the presence of the transition crystal TiO(2) catalyst attains nearly 80% within 60 min ultrasonic irradiation, while corresponding ones are only 65.23% and 53.88%, respectively, for pure ordinary rutile and anatase TiO(2) powders.     

RuO2/TiO2复合光催化剂的制备及性能研究

采用溶胶-凝胶-浸渍法制备了RuO2/TiO2复合光催化剂, 以紫外灯为光源, 直接耐晒黑G溶液的光催化降解为模型反应, 研究了RuO2/TiO2的光催化性能. 结果表明 掺杂量ω(RuO2)为0.16%、煅烧温度500 ℃、催化剂投加量为5.00 g·L-1时, RuO2/TiO2复合光催化剂催化活性最高. 直接耐晒黑G降解反应遵从Langmuir-Hinshelwood动力学模型, 测得反应速率常数为4.94×10-3 mmol(L·min)-1和吸附常数14.2 L·mmol-1.     

Reactive dye degradation by combined Fe(III)/TiO2 catalyst and ultrasonic irradiation: Effect of Fe(III) loading and calcination temperature

The development of Fe(III)/TiO(2) catalysts for sonocatalytic degradation of Reactive Blue 4 (RB4) dye in water was carried out using sol-gel method. Their surface morphology, phase transformation and surface characteristics were studied using SEM, XRD and surface analyzer, respectively. Phase transformation from amorphous to anatase occurred at 500°C and transformation of anatase to rutile phase occurred at 700°C. Complete rutile phase was formed at 900°C with corresponding increase in the particle size. Increasing in Fe(III) loading led to a reduction in the anatase phase and with the formation of weaker and broader of diffraction peaks. Surface morphology of the prepared catalyst was clearly observed with increasing calcination temperature. Surface area of the prepared catalyst decreased with increasing calcination temperature or increasing Fe(III) loading. The combination of 0.4 mol% of Fe(III)/TiO(2) with ultrasonic irradiation gave the highest sonocatalytic activity in the removal of RB4 from the aqueous solution. On the other hand, the presence of even small amount of rutile inhibited the catalytic activity of catalyst. 1.5 g/L was the optimum amount of catalyst that led to the highest sonocatalytic degradation of RB4 with an efficiency of 90%. Aeration significantly accelerated the reaction rate. Higher removal at 96% could be achieved with the combination of 0.4Fe(III)/TiO(2) and aeration under ultrasonic irradiation.     

Sonocatalytic performance of Tb7O12/TiO2 composite under ultrasonic irradiation

A Tb(7)O(12)/TiO(2) composite was successfully synthesized through a hydrolysis-calcination process. The Tb(7)O(12)/TiO(2) composite catalyst was characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy, UV-Vis absorption/reflection spectroscopy, and X-ray diffraction (XRD). The heterogeneous sonocatalytic oxidation of amaranth in water, containing dispersed pure TiO(2) and Tb(7)O(12)/TiO(2) composite, was investigated under ultrasonic irradiation. The activity of the Tb(7)O(12)/TiO(2) catalyst is higher than that of pure TiO(2) during the sonodegradation of amaranth. The enhanced sonocatalytic activity of the composite may be attributed to the increase in charge separation efficiency and the presence of surface acidity.     

Sonocatalytic degradation of organic dyes and comparison of catalytic activities of CeO2/TiO2, SnO2/TiO2 and ZrO2/TiO2 composites under ultrasonic irradiation

The CeO₂/TiO₂, SnO₂/TiO₂ and ZrO₂/TiO₂ composites were prepared by dispersing various nano-sized oxides (CeO₂, SnO₂, ZrO₂ and TiO₂) with ultrasound and mixing TiO₂ with CeO₂, SnO₂ and ZrO₂, respectively, in boiling water in a molar ratio of 4:1, followed by calcining temperature 500 °C for 60 min. Then a series of sonocatalytic degradation experiments were carried out under ultrasonic irradiation in the presence of CeO₂/TiO₂, SnO₂/TiO₂ and ZrO₂/TiO₂ composites and nano-sized TiO₂ powder. Also, the influences of heat-treatment temperature and heat-treatment time on the sonocatalytic activities of CeO₂/TiO₂, SnO₂/TiO₂ and ZrO₂/TiO₂ composites, and of irradiation time and solution acidity on the sonocatalytic degradation of Acid Red B were investigated by UV–vis spectra. It was found that the sonocatalytic degradation of Acid Red B shows significant variation in rate and ratio that decreases in order: CeO₂/TiO₂ > SnO₂/TiO₂ > TiO₂ > ZrO₂/TiO₂ > SnO₂ > CeO₂ > ZrO₂, and the corresponding ratios of Acid Red B in aqueous solution are 91.32%, 67.41%, 65.26%, 41.67%, 28.34%, 26.75% and 23.33%, respectively. And that the degradation ratio is only 16.67% under onefold ultrasonic irradiation. Because of the good degradation efficiency, this method may be an advisable choice for the treatment of non- or low-transparent wastewaters in the future.     

Preparation of cube micrometer potassium niobate (KNbO3) by hydrothermal method and sonocatalytic degradation of organic dye

Cube micrometer potassium niobate (KNbO₃) powder, as a high effective sonocatalyst, was prepared using hydrothermal method, and then, was characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). In order to evaluate the sonocatalytic activity of prepared KNbO₃ powder, the sonocatalytic degradation of some organic dyes was studied. In addition, some influencing factors such as heat-treatment temperature and heat-treatment time on the sonocatalytic activity of prepared KNbO₃ powder and catalyst added amount and ultrasonic irradiation time on the sonocatalytic degradation efficiency were examined by using UV–visible spectrophotometer and Total Organic Carbon (TOC) determination. The experimental results showed that the best sonocatalytic degradation ratio (69.23%) of organic dyes could be obtained when the conditions of 5.00 mg/L initial concentration, 1.00 g/L prepared KNbO₃ powder (heat-treated at 400 °C for 60 min) added amount, 5.00 h ultrasonic irradiation (40 kHz frequency and 300 W output power), 100 mL total volume and 25–28 °C temperature were adopted. Therefore, the micrometer KNbO₃ powder could be considered as an effective sonocatalyst for treating non- or low-transparent organic wastewaters.     

Comparative study on the process behavior and reaction kinetics in sonocatalytic degradation of organic dyes by powder and nanotubes TiO2

Sonocatalytic degradation of various organic dyes (Congo Red, Reactive Blue 4, Methyl Orange, Rhodamine B and Methylene Blue) catalyzed by powder and nanotubes TiO₂ was studied. Both catalysts were characterized using transmission electron microscope (TEM), surface analyzer, Raman spectroscope and thermal gravimetric analyzer (TGA). Sonocatalytic activity of powder and nanotubes TiO₂ was elucidated based on the degradation of various organic dyes. The former catalyst was favorable for treatment of anionic dyes, while the latter was more beneficial for cationic dyes. Sonocatalytic activity of TiO₂ nanotubes could be up to four times as compared to TiO₂ powder under an ultrasonic power of 100 W and a frequency of 42 kHz. This was associated with the higher surface area and the electrostatic attraction between dye molecules and TiO₂ nanotubes. Fourier transform-infrared spectrometer (FT-IR) was used to identify changes that occurred on the functional group in Rhodamine B molecules and TiO₂ nanotubes after the reaction. Sonocatalytic degradation of Rhodamine B by TiO₂ nanotubes apparently followed the Langmuir-Hinshelwood adsorption kinetic model with surface reaction rate of 1.75 mg/L min. TiO₂ nanotubes were proven for their high potential to be applied in sonocatalytic degradation of organic dyes.     

Sonocatalytic degradation of methyl parathion in the presence of nanometer and ordinary anatase titanium dioxide catalysts and comparison of their sonocatalytic abilities

The degradation of methyl parathion (O,O-dimethyl-O-(4-nitrophenyl)-phosphorothioate) using anatase titanium dioxide (TiO₂) powder as heterogeneous sonocatalysts is reported. The influences of reaction parameters such as the species of TiO₂ sonocatalysts, methyl parathion concentrations, TiO₂ adding amount, pH, ultrasonic intensity, ultrasonic frequency and temperature have been investigated and the optimal conditions for eliminating methyl parathion have been identified. The efficiencies of sonocatalytic degradation in both nanometer and ordinary anatase systems are compared and the results indicate that the sonocatalytic activity of nanometer anatase TiO₂ powder is better than that of ordinary anatase TiO₂ powder. The primary degradation and the total mineralization of methyl parathion have been monitored by high performance liquid chromatography (HPLC) and UV–vis spectra, respectively. Methyl parathion got destroyed to some extent in both nanometer and ordinary anatase systems under ultrasonic irradiation. The kinetics for the degradation process of methyl parathion follows the first-order reaction. The degradation ratio of methyl parathion surpassed 90% within 50 min in the optimal experiment conditions.     

Sonophotocatalytic degradation of methyl orange by nano-sized Ag/TiO2 particles in aqueous solutions

Sonophotocatalytic behaviour of methyl orange (MeO) in aqueous solution illuminated by light generated by a xenon lamp was investigated. For all three kinds of photocatalysts: Degussa P25 (75% anatase, 25% rutile, with a surface area of 55.07 m(2)/g), Yili TiO(2) (mainly anatase, with a surface area of 10.45 m(2)/g) and Ag/TiO(2) (silver loaded on Yili TiO(2)), the degradation followed pseudo-first order kinetics. The results showed a synergistic effect between sonolysis and photocatalysis. Some parameters affecting the sonophotocatalytic degradation of MeO with nanoparticles Ag/TiO(2) were determined. The results indicated that the degradation ratio of MeO increased with the increase of ultrasonic power. An optimum 60 mg/L of Ag/TiO(2) added to relatively low concentrations of MeO was proved to have the most effective degradation efficiency. The study on the effects of hydroxyl radical (*OH) scavengers (i.e. mannitol and dimethyl sulfoxide) on the MeO degradation indicated that *OH radicals played an important role during MeO degradation, which enhanced MeO to be completely decomposed.     

Ultrasonic-assisted degradation of phenazopyridine with a combination of Sm-doped ZnO nanoparticles and inorganic oxidants

Pure and samarium doped ZnO nanoparticles were synthesized by a sonochemical method and characterized by TEM, SEM, EDX, XRD, Pl, and DRS techniques. The average crystallite size of pure and Sm-doped ZnO nanoparticles was about 20 nm. The sonocatalytic activity of pure and Sm-doped ZnO nanoparticles was considered toward degradation of phenazopyridine as a model organic contaminant. The Sm-doped ZnO nanoparticles with Sm concentration of 0.4 mol% indicated a higher sonocatalytic activity (59%) than the pure ZnO (51%) and other Sm-doped ZnO nanoparticles. It was believed that Sm³⁺ ion with optimal concentration (0.4 mol%) can act as superficial trapping for electrons in the conduction band of ZnO and delayed the recombination of charge carriers. The influence of the nature and concentration of various oxidants, including periodate, hydrogen peroxide, peroxymonosulfate, and peroxydisulfate on the sonocatalytic activity of Sm-doped ZnO nanoparticles was studied. The influence of the oxidants concentration (0.2–1.4 g L⁻¹) on the degradation rate was established by the 3D response surface and the 2D contour plots. The results demonstrated that the utilizing of oxidants in combination with Sm-doped ZnO resulting in rapid removal of contaminant, which can be referable to a dual role of oxidants; (i) scavenging the generated electrons in the conduction band of ZnO and (ii) creating highly reactive radical species under ultrasonic irradiation. It was found that the Sm-doped ZnO and periodate combination is the most efficient catalytic system under ultrasonic irradiation.     

TiO2/SnO2复合光催化剂的制备及性能

采用特殊液相沉淀法制备纳米级的TiO2/SnO2复合粒子,对制备的纳米TiO2/SnO2采用XRD、TEM等手段进行了表征。用它做催化剂在日光下对甲基橙溶液进行了光催化实验。结果表明,纳米级TiO2/SnO2复合催化剂比纯TiO2的催化活性好,当SnO2摩尔百分数为20%时效果最佳,在60min内对10mg/L的甲基橙水溶液的降解率高达90.2%,具有较好的光催化活性。     

Characterization and relative sonocatalytic efficiencies of a new MWCNT and CdS modified TiO2 catalysts and their application in the sonocatalytic degradation of rhodamine B

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, energy-dispersive 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.     

氧化锌纳米粉体的制备及其光催化性能研究

采用溶胶-凝胶法制备了氧化锌光催化剂,分别利用XRD、TG、FT-IR对所制粉体进行了表征。结果表明ZnO为六方晶系纤锌矿型,粒子大小约为27nm。粉体的IR光谱表明,热处理后NH基团和单乙酸锌的吸收峰消失,在470cm-1附近出现Zn-O伸缩振动。纳米粉体的光催化降解水杨酸实验结果显示出,焙烧后所得的纤锌矿型ZnO粉体具有较高的光催化活性,以310nm波长光照射16小时可降解水杨酸95.1%。     

Sonocatalytic removal of naproxen by synthesized zinc oxide nanoparticles on montmorillonite

ZnO/MMT nanocomposite as sonocatalyst was prepared by immobilizing synthesized ZnO on the montmorillonite surface. The characteristics of as-prepared nanocomposite were studied by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) techniques. The synthesized samples were used as a catalyst for sonocatalytic degradation of naproxen. ZnO/MMT catalyst in the presence of ultrasound irradiation was more effective compared to pure ZnO nanoparticles and MMT particles in the sonocatalysis of naproxen. The effect of different operational parameters on the sonocatalytic degradation of naproxen including initial drug concentration, sonocatalyst dosage, solution pH, ultrasonic power and the presence of organic and inorganic scavengers were evaluated. It was found that the presence of the scavengers suppressed the sonocatalytic degradation efficiency. The reusability of the nanocomposite was examined in several consecutive runs, and the degradation efficiency decreased only 2% after 5 repeated runs. The main intermediates of naproxen degradation were determined by gas chromatography–mass spectrometry (GC–Mass).