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Green synthesis using cherry and orange juice and characterization of TbFeO3 ceramic nanostructures and their application as photocatalysts under UV light for removal of organic dyes in water
Journal Pre-proof Green synthesis using cherry and orange juice and characterization of TbFeO3 ceramic nanostructures and their application as photocatalysts under UV light for removal of organic dyes in water
Pourya Mehdizadeh, Yasin Orooji, Omid Amiri, Masoud Salavati-Niasari, Hossein Moayedi PII:
S0959-6526(19)34635-9
DOI:
https://doi.org/10.1016/j.jclepro.2019.119765
Reference:
JCLP 119765
To appear in:
Journal of Cleaner Production
Received Date:
26 April 2019
Accepted Date:
16 December 2019
Please cite this article as: Pourya Mehdizadeh, Yasin Orooji, Omid Amiri, Masoud Salavati-Niasari, Hossein Moayedi, Green synthesis using cherry and orange juice and characterization of TbFeO3 ceramic nanostructures and their application as photocatalysts under UV light for removal of organic dyes in water, Journal of Cleaner Production (2019), https://doi.org/10.1016/j.jclepro. 2019.119765
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier.
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Green synthesis using cherry and orange juice and characterization of TbFeO3 ceramic nanostructures and their application as photocatalysts under UV light for removal of organic dyes in water Pourya Mehdizadeh1, Yasin Orooji2, Omid Amiri*3, Masoud Salavati-Niasari1*, Hossein Moayedi4,* 1Institute
of Nano Science and Nano Technology, University of Kashan, Kashan, P. O. Box. 87317-51167, I. R. Iran.
2College
of Materials Science and Engineering, Nanjing Forestry University, 159 Longpan Road, Nanjing, 210037 (PR China)
3Department
of Chemistry, College of Science, University of Raparin, Rania, Kurdistan Region, Iraq.
4Institute
of Research and Development, Duy Tan University, Da Nang, 550000, Viet Nam
*Corresponding author, Tel: +0098 31 55912383; Email: [email protected]; [email protected] Abstract Water pollution becomes a serious global concern threatening the entire biosphere and affecting the lives of many millions of people around the world. Water pollution causes a variety of diseases and millions of people die annually because of illness related to the dirty water. TbFeO3 nanostructures were synthesized by green sonication method. Cherry and orange juice were used as natural surfactant and results were compared by those obtained by chemical surfactants (SDS and CTAB). Then as-prepared TbFeO3 nanostructures were applied to treat wastewater containing Methyl orange, Acid Blue 92, Acid Black 1, and Acid Brown 214. In addition, the effect of pH and containment concentration on the photocatalytic activity of TbFeO3 nanostructure was studied. Using orange juice as surfactant leads helped to boost the photocatalytic activity of TbFeO3 nanostructure. As prepared TbFeO3 nanostructure were characterized with XRD, SEM, TEM, EDX, DRS, BET and FT-IR. Keywords: Orange juice; Photocatalysis; Green chemistry; TbFeO3; Nanostructures.
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1. Introduction Water pollution becomes a serious global concern threatening the entire biosphere and affecting the lives of many millions of people around the world. Water pollution causes a variety of diseases and millions of people die annually because of illness related to the dirty water. The dye contaminant is the common water pollution which should be treated before their drop. The small amounts of dyes (below 1 ppm) change the color and quality of water and considerably influence the water environment. The current conventional methods only convert one type of pollution into another. For example, adsorbing contaminant from water onto a solid adsorbent purified the water, but transfers the pollutant onto the solid form. Now the adsorbent is a new pollutant that should be treated. In addition, conventional water treatments techniques need a complicated design. Therefore researchers are looking for eco-friendly treatment methods for degradation of the pollution instead of converting them from one form to another. Photocatalysis treatment is proper ways that address these issues by Advanced Oxidation Process (AOP). During AOP, the contaminants will be mineralized by converting pollutant to water and carbon dioxide with the help of strong radicals (.OH and O2.−). The photocatalysis is an effective AOP for the removal of organic contaminant. However, some issues such as low quantum efficiency due to inefficient visible light remain as a barrier in the commercial application of photocatalysis. Titanium dioxide has received great attention since Fujishima and Honda discovered its capability to split water in 1972 [1]. Frank and Bard also used TiO2 as a photocatalyst to treat water for the first time. TiO2 has a wide band gap (3.2 eV) that limits its absorption to the UV lights. Therefore it shows the photocatalytic activity in UV lights. On the other hand, approximately 5% of solar-terrestrial radiation is visible UV. Therefore, we tried to introduce a new photocatalyst which show highly photocatalytic activity (our research objective). [1–5] It has been demonstrated that different semiconductors such as TiO2 and ZnO could absorb photons with energy higher than the band gap energy of semiconductor and produce electron and holes. [5-10] These produced electrons and holes could initiate decomposition of organic pollution. [11, 12] Using photocatalysis has some 2
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advantages. For instance, it does not require expensive oxidants and it carried out under ambient conditions. [13, 14]. Perovskite oxides materials are considered as an important class of multifunctional materials which show a variety of interesting properties including optical, electronic transport and, magnetic, and dielectric properties. Recently, the photocatalytic activity of perovskite oxides such as BiFeO3, LaNiO3, YMnO3, LaFeO3, and TbFeO3 has attracted considerable attention due to their relatively small bandgaps. [15–20] Among them, TbFeO3 nanostructure considered as a promising candidate because of extraordinary magnetic and optical behaviors like spin-canted antiferromagnetism and spin-reorientation transitions [21–23]. Up to now, few synthesis routs were applied to prepare TbFeO3 nanostructures. For example, Pei Song Tang and et. al. reported the synthesis of TbFeO3 nanoparticles by microwave method [24]. In another reported Li and et . al. prepared rare earth based Tb nanostructures by hydrothermal method [25]. H. Yang and et. al applied polyacrylamide gel route to prepare TbFeO3 nanostructures [26].
Here we prepared sponge like TbFeO3 nanostructure by using sonochemistry method and using two natural surfactants (cherry and orange juices). Then as-prepared TbFeO3 nanostructures were applied to treat water containing Methyl orange, Acid Blue 92, Acid Black 1, Acid Brown 214 as an organic contaminant. Acid Blue 92 is the double class azo dye, blue powder which is soluble in water and ethanol and widely used dyeing wool, silk, viscose, leather, paper, and soap. Acid Black 1 is a diazo, black powder which is soluble in water and ethanol. It is mainly used for silk, wool, polyamide fiber, and its blended fabric dyeing and printing. It also can be used in the manufacture of ink, for paper, electrical-controlled aluminum, soap, leather, wood, biological, medicine and cosmetics shading. Acid Brown 214 is a brown dye which mainly used for leather color.
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The novelty of work is using cherry and orange juice as a surfactant to control the size of the final products. Cherry and orange juice lead to increases the degradation efficiency. Photocatalytic activity of TbFeO3 rarely was studied. To best of our knowledge, this is the highest degradation efficiency reported so far. 2. Experimental Synthesis of TbFeO3 nanostructures: First, 0.46 mmol of Tb(NO3)3.6H2O and 0.46 mmol of Fe(NO3)3.9H2O was dissolved in 20 mL DI water in two separate beakers. Then we mixed them in 100 mL beaker. A surfactant was added in this step. 5 mL of Tetraethylenepentamine (TEPA) dropped to the above solution, while sonicated under certain power. Finally, the obtained mixture was centrifuged and washed with distilled water and ethanol and dried at 70 ℃. The dried powder was calcinated at 700 °C for 2 h. It should be noticed that Sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) were added with a molar ratio of 1:1 compares to the Tb, in case of using two natural surfactants (cherry and orange juices) 2 mL was added. More detail could be found in Table 1. Photocatalyitic investigation: In order to study the photocatalytic activity of as-prepared TbFeO3 nanostructures, 0.05 g of TbFeO3 nanostructures was dispersed in 50 mL of different dyes (Methyl orange, Acid Blue 92, Acid Black 1, and Acid Brown 214). We put the above mixture in dark place for 6 h to equilibrium the adsorption of dye on the surface of TbFeO3 nanostructures. Then the mixture was irradiated by UV light for 2 h. We read the absorption at a maximum absorption wavelength for each dye every 30 minutes. 3. Results and discussion Here we report a green synthesis of TbFeO3 nanostructures by using sonochemistry. We used cherry and orange juice as a natural surfactant to control the morphology of final perovskite material (TbFeO3) and compare their morphology with those prepared by using SDS and CTAB. We also studied other parameters such as ultrasonic power and time on the morphology and photocatalytic activity of TbFeO3 nanostructures. 4
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X-Ray Diffraction (XRD) pattern of TbFeO3 nanostructures which calcinated at 600 and 700 °C are presented in Fig. 1 a and b. As seen from the presented XRD patterns, amorphous nanostructures were formed when TbFeO3 calcinated at 600 ℃ for 2 h. By increasing calcination temperature to 700 ℃, we observed highly crystalized TbFeO3 nanostructures with orthorhombic crystal system (JCPDS 73-0519). The average crystal size of 17 nm was calculated from scherer equation [27]. Fig. 1c and d shows the XRD patterns for TbFeO3 nanostructures prepared by using SDS and orange juice as surfactant respectively. Fe3O4 was observed as an impurity (JCPDS 01-089-0951) when SDS was used as a surfactant. Fig. 1d clearly illustrates that when orange juice was used as a surfactant, quite pure and highly crystalized TbFeO3 nanostructures were formed. Energy-dispersive X-ray spectroscopy (EDX) of sample 3-6 approves the presence of Tb, Fe, and O in TbFeO3 nanostructures (Fig. 2a-d). Elemental composition of the surface of the TbFeO3 nanostructure was estimated using EDS. The atomic percentage of three elements terbium, iron, and oxygen is listed in Table 2. The surface composition observed was different from the bulk composition targeted. However, from XRD data the phase formation of TbFeO3 was confirmed. In order to study the effect of surfactant on the morphology of TbFeO3 nanostructures, SDS, CTAB, Gerry, and Orange juice were used to prepare TbFeO3 nanostructures and results were illustrated in Fig. 3a-d. Porous TbFeO3 nanostructures were achieved when SDS was used as a surfactant (Fig. 3a). In this case, small particles stack together to form porous structures. By changing the surfactant to CTAB, uniform TbFeO3 nanoparticles were formed (Fig. 3b). Fig. 3c show that using cherry juice as surfactant leads to form sponge like TbFeO3 nanostructures. As seen in Fig. 3d, dense TbFeO3 nanoparticles with 10-20 nm in diameters were achieved when orange juice was used as a surfactant. These scanning electron microscope (SEM) images show that using orange juice as surfactant leads to produce the smallest particles. Since the smallest particles were formed when orange juice was used as the surfactant, orange juice was used to study the effect of other synthesis parameters such as ultrasonic time and power. 5
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TbFeO3 nanostructures were prepared under different sonication time (30, 40, and 50 min) to study the effect of sonication time on the morphology of TbFeO3 nanostructures (Fig. 4a, Fig. 3d and Fig. 4b, respectively). As seen from the results, TbFeO3 nanostructures size decreased from 20- 40 nm (Fig. 4a) to 10- 20 nm (Fig. 3d) by increasing sonication time from 30 to 40 min. More increasing in sonication time to 50 min leads to aggregation of particles and increasing size to 40- 60 nm (Fig. 4 b). Three different ultrasonic powers including 40, 60, and 80 W were used to figure out the effect of power on the morphology of as-synthesized TbFeO3 nanostructures (Fig. 4c, Fig. 3d and Fig. 4d, respectively). TbFeO3 nanorods 100-150 nm in diameters were formed when ultrasonic power was 40 W (Fig. 4c). TbFeO3 nanoparticles with diameters of 40- 60 nm were formed by setting ultrasonic power on 60 W (Fig. 3d). When ultrasonic power was 80 W, aggregated TbFeO3 nanorods were assembled (Fig. 4d). Transmission electron microscopy (TEM) images of sample 6 are presented in Fig. 5a- d. TEM results show that uniform TbFeO3 nanoparticles with 5- 10 nm in size were formed under following condition: surfactant= orange juice, power = 60 W, sonication time = 40 min, and calcination temperature= 700 ℃. Diffuse Reflectance Spectroscopy (DRS) was applied to carry out the optical properties of TbFeO3 nanostructures. Fig. 6a-d shows the DRS of as-prepared TbFeO3 nanostructures by using different surfactants. Fig. 6a shows the DRS spectrum of TbFeO3 nanostructures prepared by using SDS. Calculated band gap was 1.6 eV. By changing surfactant to CTAB, band gap increased to 1.8 eV (Fig. 6b). However, using cherry juice leads to decrease in the band gap to 1.7 eV (Fig. 6c). As seen from. Fig. 6d, when orange juice was used band gap increased to 1.9 eV. These results show good agreement with SEM and XRD results, which using orange juice leads to produce the smallest particles. Fourier-transform infrared spectroscopy (FTIR) spectrum of as-prepared TbFeO3 nanostructure prepared by using orange juice is shown in Fig. 7. The peaks at 3442 cm-1 and 1621 cm-1 could be assigned to the O-H 6
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stretching vibrational mode. The peak at 540 and 557 cm-1 is due to the Fe-O stretching vibrations [26]. The weak band, noise type vibrations, seen at 2800 cm−1 presented in the spectra belong to the atmospheric carbon dioxide appearing in many spectra. Since TbFeO3 nanostructure was calcinated at 700 ℃. Adsorption-desorption curve, BET, and BJT of sample 6 were illustrated in Fig. 8a-c. As seen from the figure, Adsorption-desorption curve shows that TbFeO3 nanostructure prepared by using orange juice exhibit a narrow range of uniform mesopores. A narrow loop is a clear sign of delayed condensation on the adsorption branch. BET result shows that specific area for TbFeO3 nanostructure was 20 m2.g-1 (Fig. 8b). From the BJH result which illustrated in Fig. 8 c, pore size is about 20 nm. We evaluated the photocatalytic activity of TbFeO3 nanostructure by study the degradation of Methyl orange (as mono Azo dye), Acid Blue 92 (mono Azo), Acid Black 1 (as Double azo class dye), and Acid Brown 214 (as Triazo dye) under UV light for 2 h. Structure of as used dyes are presented in Fig. 9. Fig. 10 shows the degradation efficiency of these four dyes by using sample 3, 4, 5, and 6 as a catalyst under UV light for 2 h. Photocatalyst test was carried out in 10 ppm dye concentration and neutral pH. Degradation efficiency for sample 3-6 and MO dye was 40 ± 0.5, 75 ± 0.3, 78 ±4, and 98 ± 0.4%, respectively (Fig. 10a). Using SDS as the surfactant leads to the lowest photocatalytic activity while using orange juice as surfactant shows the maximum degradation efficiency during 2 h of irradiation. The same recipe was used to study the degradation of Acid Blue 92 (Fig. 10 b). Sample 3 degrades 29 ± 0.7 % of Acid Blue 92 under UV light for 2 h. By changing the photocatalyst to sample 4, degradation efficiency increased to 61 ± 0.6%. When cherry juice was used as a surfactant in synthesis process of catalyst (sample 5), degradation efficiency of 48 % was achieved. The highest removal efficiency for removal of Acid Blue 92 was achieved by changing surfactant to orange juice (sample 6). Fig. 10 c illustrates the degradation yield for Acid Black 1. Samples 3-6 degrade 19 ± 0.3, 48 ± 0.8, 39 ± 0.5, and 51 ± 0.9 %, of Acid Black 1 in 2 h irradiation, respectively. Finally, Acid Brown 214 was used as organic pollution with 10 ppm in concentration (Fig 10d). Sample 6 shows the highest photocatalytic activity and 7
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degrades 60 ± 0.4 % of Acid Brown 214 in 2 h. These indicate that using oranges juice as surfactant lead to improving photocatalytic activity. This could happen because smaller and uniform TbFeO3 nanoparticles were formed when orange juice was used as the surfactant. To best of our knowledge, this is the highest degradation efficiency reported so far. For example, H.Yang et. al. report that TbFeO3 degrades 30 % of methyl orange under 40 W visible light irradiation for 6 h, while our prepared TbFeO3 degraded 90 % of methyl orange [28]. Peisong Tang et al. report 40 % of MO was decomposed after 120 min by using TbFeO3 under visible light [29]. In order to study the effect of pollution concentration on degradation efficiency, sample 6 was used as the most efficient photocatalyst. We studied the degradation of three concentration of Acid Blue 92 (5, 10, and 15 ppm). 91 % of Acid Blue 92 was degraded in 2 h of irradiation when the concentration was 5 ppm (Fig. 11a). By increasing the concentration of organic pollution to 10 ppm, degradation efficiency decreased to 64 ± 0.6 % under the same irradiation time (Fig. 11b). Fig. 11c illustrates that sample 6 degrades 42 ± 0.4 % of Acid Blue 92 when the concentration was 15 ppm. We figure out the effect of pH on the degradation yield by using Acid Blue 92 as organic pollution. Results for degradation of Acid Blue 92 by sample 6 in acidic (pH= 3), neutral (pH=6.8) , and basic condition are summarized in Fig. 12. 100 ± 0.7 % of Acid Blue 92 was degraded when pH adjust to 3 by using HNO3 (Fig. 12a). In neutral pH (pH=6.8) degradation percentage was 64 (Fig. 12 b), while about 92 ± 0.5 % of Acid Blue 92 was degraded in basic pH (pH=10) (Fig. 12c). It is a very tough task to explain the effect of pH on the efficiency of dye photodegradation because of its multiple roles. Highest degradation efficiency was achieved at acidic pH. This could happen because of strong adsorption of the Acid Blue 92 on the TbFeO3 particles as a result of the electrostatic attraction of the positively charged TbFeO3 with the negatively charged dye (Acid blue 92) [30, 31]. In addition higher degradation efficiency achieved at basic pH compare to the neutral pH. This
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could be happen because of easer formation of hydroxyl radicals at basic pH levels [30, 32]. Hydroxyl radicals can be formed by the reaction between hydroxide ions and positive holes. As seen from XRD results, sample 3 has impurity (Fe3O4) that why it shows the lowest photocatalytic activity. In the other hand, sample 6 shows the highest photocatalytic activity probably due to the highly crystallinity, purity and smaller particle size. Degradation happens according to the following mechanism: TbFeO3 absorbed photons and generates electron and holes. It results in the promotion of an electron in the conductive band (eCB−) and formation of a positive hole in the valence band (hVB+) [33]. The hVB+ and eCB− are powerful oxidizing and reducing agents, respectively. The hVB+ reacts with organic compounds and oxidize them. The hVB+ can also oxidize organic compounds by reacting with water to generate Hydroxyl radical (•OH). •OH produced by has the second highest oxidation potential (2.80 V) could oxidize most of organic compounds [34]. Electron in conductive band can react with O2 forming an anion radical (O2.-). Further reaction can lead to the formation of hydrogen peroxide which lead to the formation of •OH [35]. All these generated radicals oxidize organic compounds. 4. Conclusion In conclusion, TbFeO3 nanostructures were prepared by the green and simple method. Base on the results, using orange juice as surfactant leads to produce very pure and highly crystalized TbFeO3 nanostructure with uniform shape and size. In the other hand, Fe3O4 was observed as an impurity when chemical surfactant such as SDS was used in the synthesis of TbFeO3 nanostructure. It seems SDS reduces Fe+3 ion to Fe2+ in the presence of ultrasonic waves. The effect of different parameters such as calcination temperature, type of surfactant, ultrasonic power and time on the morphology of TbFeO3 nanostructure were studied. TbFeO3 nanostructures prepared under the following condition show the highest photocatalytic activity: calcination temperature= 700 ℃, surfactant= orange juice, ultrasonic power= 60 W, and ultrasonic time= 40 min. As prepared TbFeO3 9
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nanostructures were used to treat water contain Methyl orange, Acid Blue 92, Acid Black 1, and Acid Brown 214. In addition, the effect of the concentration of contaminant and its pH on the degradation efficiency were studied. TbFeO3 nanostructures show higher photocatalytic activity in an acidic environment and lower contaminant concentration. Acknowledgements Authors are grateful to the council of Iran National Science Foundation; INSF (97017837) and University of Kashan for supporting this work by Grant No (159271/122).
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Figure Caption Fig. 1. XRD pattern of As-prepared TbFeO3 Nanostructures: a) sample 1 (blue pattern), b) sample 2 (red pattern), c) sample 3 (black pattern), and d) sample 6 (purple pattern). When orange juice was used as a surfactant (sample 6), quite pure and highly crystalized TbFeO3 nanostructures (JCPDS 73-0519) were formed. The asterisks show the peaks for Fe3O4 (JCPDS 01-089-0951). Fig. 2. EDX results of a) sample 3, b) sample 4, d) sample 5, and d) sample 6. These results approve the presence of Tb, Fe, and O elements. Fig. 3. SEM images of TbFeO3 Nanostructures prepared by using a) Sodium dodecyl sulfate (sample 3), b) cetyltrimethylammonium bromide (sample 4), c) Cherry juice (sample 5), and d) Orange juice (sample 6) as surfactant. More uniform particles were formed when cetyltrimethylammonium bromide and orange juice were used as surfactant, respectively. Fig. 4. a and b show the effect of sonication time on the morphology of TbFeO3 Nanostructures: a) sample 7 and b) sample 8. c and d show the effect of ultrasonic power on the morphology of as synthesized TbFeO3 Nanostructures: c) sample 9 and d) sample 10. Fig. 5. TEM images of some different area of sample 6 (Fig 5 a-d). Fig 5 a-d show that size distribution for sample 6 is narrow and show uniform particles size. Fig. 6. DRS of a) sample 3, b) sample 4, c) sample 5, and d) sample 6. When orange juice was used as surfactant, we observed broad absorption peak. These results indicate type of surfactant dramatically change the optical properties of TbFeO3 Nanostructures.
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Fig. 7. FT-IR spectrum of TbFeO3 Nanostructures prepared by orange juice (sample 6). The peaks at 3442 cm-1 and 1621 cm-1 could be assigned to the O-H stretching vibrational mode. The peak at 557 cm-1 is due to the Fe-O stretching vibrations. Fig. 8. a) Adsorption-desorption curve, b) BET, and c) BJT of sample 6. A narrow loop is a clear sign of delayed condensation on the adsorption branch. BET result shows that specific area for TbFeO3 nanostructure was 20 m2.g-1. From the BJH result which illustrated in Fig. 8 c, pore size is about 20 nm. Fig. 9. Chemical structure of Methyl orange, Acid Blue 92, Acid Black 1, and Acid Brown 214. Fig. 10. Photocatalysis results for the degradation of Methyl orange, Acid Blue 92, Acid Black 1, and Acid Brown 214 by using sample 3, 4, 5, and 6 as catalyst under UV light for 2 h. a) Methyl orange, b) Acid Blue 92, c) Acid Black 1, and d) Acid Brown 214 Fig. 11. The effect of concentration of organic pollution (Acid Blue 92) on the degradation efficiency. a) 5 ppm, b) 10 ppm, c) 15 ppm. Fi g. 12. The effect of pH on the degradation yield by using Acid Blue 92 as organic pollution and sample 6 as catalyst. a) Acidic, b) neutral and c), basic.
Table Caption Table 1. Detail for the synthesis of TbFeO3 nanostructures.
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Fig. 1
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Fig. 2
19
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Fig. 3
20
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Fig. 4
21
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Fig. 5 22
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Fig. 6
23
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Fig. 7
24
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Fig. 8
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Fig. 9 26
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Fig 10
27
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Fig. 11
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Fig. 12
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Table 1 Sample No
Calcination
Surfactant
Neutral surfactant
Ultra time
Ultra power
1
600
-
-
40
60
2
700
-
-
40
60
3
700
SDS
-
40
60
4
700
CTAB
-
40
60
5
700
-
cherry
40
60
6
700
-
orange
40
60
7
700
-
orange
30
60
8
700
-
orange
50
60
9
700
-
orange
40
40
10
700
-
orange
40
80
30
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Table 2 Sample No
Atomic %
Atomic %
Atomic %
Tb
Fe
O
3
6.94
4.82
88.24
4
13.31
8.76
77.92
5
20.13
4.89
74.98
6
8.80
12.45
78.75
31
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TbFeO3 nanostructures were prepared by a green and simple sonochemistry method.
Using orange juice in synthesis of TbFeO3 nanostructures leads to produce a very pure.
As-prepared TbFeO3 nanostructures were used to remove dyes in water.
We studied the effect of the concentration of contaminant and pH on the degradation efficiency.
Pourya Mehdizadeh, Yasin Orooji, Omid Amiri, Masoud Salavati-Niasari, Hossein Moayedi PII:
S0959-6526(19)34635-9
DOI:
https://doi.org/10.1016/j.jclepro.2019.119765
Reference:
JCLP 119765
To appear in:
Journal of Cleaner Production
Received Date:
26 April 2019
Accepted Date:
16 December 2019
Please cite this article as: Pourya Mehdizadeh, Yasin Orooji, Omid Amiri, Masoud Salavati-Niasari, Hossein Moayedi, Green synthesis using cherry and orange juice and characterization of TbFeO3 ceramic nanostructures and their application as photocatalysts under UV light for removal of organic dyes in water, Journal of Cleaner Production (2019), https://doi.org/10.1016/j.jclepro. 2019.119765
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier.
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Green synthesis using cherry and orange juice and characterization of TbFeO3 ceramic nanostructures and their application as photocatalysts under UV light for removal of organic dyes in water Pourya Mehdizadeh1, Yasin Orooji2, Omid Amiri*3, Masoud Salavati-Niasari1*, Hossein Moayedi4,* 1Institute
of Nano Science and Nano Technology, University of Kashan, Kashan, P. O. Box. 87317-51167, I. R. Iran.
2College
of Materials Science and Engineering, Nanjing Forestry University, 159 Longpan Road, Nanjing, 210037 (PR China)
3Department
of Chemistry, College of Science, University of Raparin, Rania, Kurdistan Region, Iraq.
4Institute
of Research and Development, Duy Tan University, Da Nang, 550000, Viet Nam
*Corresponding author, Tel: +0098 31 55912383; Email: [email protected]; [email protected] Abstract Water pollution becomes a serious global concern threatening the entire biosphere and affecting the lives of many millions of people around the world. Water pollution causes a variety of diseases and millions of people die annually because of illness related to the dirty water. TbFeO3 nanostructures were synthesized by green sonication method. Cherry and orange juice were used as natural surfactant and results were compared by those obtained by chemical surfactants (SDS and CTAB). Then as-prepared TbFeO3 nanostructures were applied to treat wastewater containing Methyl orange, Acid Blue 92, Acid Black 1, and Acid Brown 214. In addition, the effect of pH and containment concentration on the photocatalytic activity of TbFeO3 nanostructure was studied. Using orange juice as surfactant leads helped to boost the photocatalytic activity of TbFeO3 nanostructure. As prepared TbFeO3 nanostructure were characterized with XRD, SEM, TEM, EDX, DRS, BET and FT-IR. Keywords: Orange juice; Photocatalysis; Green chemistry; TbFeO3; Nanostructures.
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1. Introduction Water pollution becomes a serious global concern threatening the entire biosphere and affecting the lives of many millions of people around the world. Water pollution causes a variety of diseases and millions of people die annually because of illness related to the dirty water. The dye contaminant is the common water pollution which should be treated before their drop. The small amounts of dyes (below 1 ppm) change the color and quality of water and considerably influence the water environment. The current conventional methods only convert one type of pollution into another. For example, adsorbing contaminant from water onto a solid adsorbent purified the water, but transfers the pollutant onto the solid form. Now the adsorbent is a new pollutant that should be treated. In addition, conventional water treatments techniques need a complicated design. Therefore researchers are looking for eco-friendly treatment methods for degradation of the pollution instead of converting them from one form to another. Photocatalysis treatment is proper ways that address these issues by Advanced Oxidation Process (AOP). During AOP, the contaminants will be mineralized by converting pollutant to water and carbon dioxide with the help of strong radicals (.OH and O2.−). The photocatalysis is an effective AOP for the removal of organic contaminant. However, some issues such as low quantum efficiency due to inefficient visible light remain as a barrier in the commercial application of photocatalysis. Titanium dioxide has received great attention since Fujishima and Honda discovered its capability to split water in 1972 [1]. Frank and Bard also used TiO2 as a photocatalyst to treat water for the first time. TiO2 has a wide band gap (3.2 eV) that limits its absorption to the UV lights. Therefore it shows the photocatalytic activity in UV lights. On the other hand, approximately 5% of solar-terrestrial radiation is visible UV. Therefore, we tried to introduce a new photocatalyst which show highly photocatalytic activity (our research objective). [1–5] It has been demonstrated that different semiconductors such as TiO2 and ZnO could absorb photons with energy higher than the band gap energy of semiconductor and produce electron and holes. [5-10] These produced electrons and holes could initiate decomposition of organic pollution. [11, 12] Using photocatalysis has some 2
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advantages. For instance, it does not require expensive oxidants and it carried out under ambient conditions. [13, 14]. Perovskite oxides materials are considered as an important class of multifunctional materials which show a variety of interesting properties including optical, electronic transport and, magnetic, and dielectric properties. Recently, the photocatalytic activity of perovskite oxides such as BiFeO3, LaNiO3, YMnO3, LaFeO3, and TbFeO3 has attracted considerable attention due to their relatively small bandgaps. [15–20] Among them, TbFeO3 nanostructure considered as a promising candidate because of extraordinary magnetic and optical behaviors like spin-canted antiferromagnetism and spin-reorientation transitions [21–23]. Up to now, few synthesis routs were applied to prepare TbFeO3 nanostructures. For example, Pei Song Tang and et. al. reported the synthesis of TbFeO3 nanoparticles by microwave method [24]. In another reported Li and et . al. prepared rare earth based Tb nanostructures by hydrothermal method [25]. H. Yang and et. al applied polyacrylamide gel route to prepare TbFeO3 nanostructures [26].
Here we prepared sponge like TbFeO3 nanostructure by using sonochemistry method and using two natural surfactants (cherry and orange juices). Then as-prepared TbFeO3 nanostructures were applied to treat water containing Methyl orange, Acid Blue 92, Acid Black 1, Acid Brown 214 as an organic contaminant. Acid Blue 92 is the double class azo dye, blue powder which is soluble in water and ethanol and widely used dyeing wool, silk, viscose, leather, paper, and soap. Acid Black 1 is a diazo, black powder which is soluble in water and ethanol. It is mainly used for silk, wool, polyamide fiber, and its blended fabric dyeing and printing. It also can be used in the manufacture of ink, for paper, electrical-controlled aluminum, soap, leather, wood, biological, medicine and cosmetics shading. Acid Brown 214 is a brown dye which mainly used for leather color.
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The novelty of work is using cherry and orange juice as a surfactant to control the size of the final products. Cherry and orange juice lead to increases the degradation efficiency. Photocatalytic activity of TbFeO3 rarely was studied. To best of our knowledge, this is the highest degradation efficiency reported so far. 2. Experimental Synthesis of TbFeO3 nanostructures: First, 0.46 mmol of Tb(NO3)3.6H2O and 0.46 mmol of Fe(NO3)3.9H2O was dissolved in 20 mL DI water in two separate beakers. Then we mixed them in 100 mL beaker. A surfactant was added in this step. 5 mL of Tetraethylenepentamine (TEPA) dropped to the above solution, while sonicated under certain power. Finally, the obtained mixture was centrifuged and washed with distilled water and ethanol and dried at 70 ℃. The dried powder was calcinated at 700 °C for 2 h. It should be noticed that Sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) were added with a molar ratio of 1:1 compares to the Tb, in case of using two natural surfactants (cherry and orange juices) 2 mL was added. More detail could be found in Table 1. Photocatalyitic investigation: In order to study the photocatalytic activity of as-prepared TbFeO3 nanostructures, 0.05 g of TbFeO3 nanostructures was dispersed in 50 mL of different dyes (Methyl orange, Acid Blue 92, Acid Black 1, and Acid Brown 214). We put the above mixture in dark place for 6 h to equilibrium the adsorption of dye on the surface of TbFeO3 nanostructures. Then the mixture was irradiated by UV light for 2 h. We read the absorption at a maximum absorption wavelength for each dye every 30 minutes. 3. Results and discussion Here we report a green synthesis of TbFeO3 nanostructures by using sonochemistry. We used cherry and orange juice as a natural surfactant to control the morphology of final perovskite material (TbFeO3) and compare their morphology with those prepared by using SDS and CTAB. We also studied other parameters such as ultrasonic power and time on the morphology and photocatalytic activity of TbFeO3 nanostructures. 4
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X-Ray Diffraction (XRD) pattern of TbFeO3 nanostructures which calcinated at 600 and 700 °C are presented in Fig. 1 a and b. As seen from the presented XRD patterns, amorphous nanostructures were formed when TbFeO3 calcinated at 600 ℃ for 2 h. By increasing calcination temperature to 700 ℃, we observed highly crystalized TbFeO3 nanostructures with orthorhombic crystal system (JCPDS 73-0519). The average crystal size of 17 nm was calculated from scherer equation [27]. Fig. 1c and d shows the XRD patterns for TbFeO3 nanostructures prepared by using SDS and orange juice as surfactant respectively. Fe3O4 was observed as an impurity (JCPDS 01-089-0951) when SDS was used as a surfactant. Fig. 1d clearly illustrates that when orange juice was used as a surfactant, quite pure and highly crystalized TbFeO3 nanostructures were formed. Energy-dispersive X-ray spectroscopy (EDX) of sample 3-6 approves the presence of Tb, Fe, and O in TbFeO3 nanostructures (Fig. 2a-d). Elemental composition of the surface of the TbFeO3 nanostructure was estimated using EDS. The atomic percentage of three elements terbium, iron, and oxygen is listed in Table 2. The surface composition observed was different from the bulk composition targeted. However, from XRD data the phase formation of TbFeO3 was confirmed. In order to study the effect of surfactant on the morphology of TbFeO3 nanostructures, SDS, CTAB, Gerry, and Orange juice were used to prepare TbFeO3 nanostructures and results were illustrated in Fig. 3a-d. Porous TbFeO3 nanostructures were achieved when SDS was used as a surfactant (Fig. 3a). In this case, small particles stack together to form porous structures. By changing the surfactant to CTAB, uniform TbFeO3 nanoparticles were formed (Fig. 3b). Fig. 3c show that using cherry juice as surfactant leads to form sponge like TbFeO3 nanostructures. As seen in Fig. 3d, dense TbFeO3 nanoparticles with 10-20 nm in diameters were achieved when orange juice was used as a surfactant. These scanning electron microscope (SEM) images show that using orange juice as surfactant leads to produce the smallest particles. Since the smallest particles were formed when orange juice was used as the surfactant, orange juice was used to study the effect of other synthesis parameters such as ultrasonic time and power. 5
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TbFeO3 nanostructures were prepared under different sonication time (30, 40, and 50 min) to study the effect of sonication time on the morphology of TbFeO3 nanostructures (Fig. 4a, Fig. 3d and Fig. 4b, respectively). As seen from the results, TbFeO3 nanostructures size decreased from 20- 40 nm (Fig. 4a) to 10- 20 nm (Fig. 3d) by increasing sonication time from 30 to 40 min. More increasing in sonication time to 50 min leads to aggregation of particles and increasing size to 40- 60 nm (Fig. 4 b). Three different ultrasonic powers including 40, 60, and 80 W were used to figure out the effect of power on the morphology of as-synthesized TbFeO3 nanostructures (Fig. 4c, Fig. 3d and Fig. 4d, respectively). TbFeO3 nanorods 100-150 nm in diameters were formed when ultrasonic power was 40 W (Fig. 4c). TbFeO3 nanoparticles with diameters of 40- 60 nm were formed by setting ultrasonic power on 60 W (Fig. 3d). When ultrasonic power was 80 W, aggregated TbFeO3 nanorods were assembled (Fig. 4d). Transmission electron microscopy (TEM) images of sample 6 are presented in Fig. 5a- d. TEM results show that uniform TbFeO3 nanoparticles with 5- 10 nm in size were formed under following condition: surfactant= orange juice, power = 60 W, sonication time = 40 min, and calcination temperature= 700 ℃. Diffuse Reflectance Spectroscopy (DRS) was applied to carry out the optical properties of TbFeO3 nanostructures. Fig. 6a-d shows the DRS of as-prepared TbFeO3 nanostructures by using different surfactants. Fig. 6a shows the DRS spectrum of TbFeO3 nanostructures prepared by using SDS. Calculated band gap was 1.6 eV. By changing surfactant to CTAB, band gap increased to 1.8 eV (Fig. 6b). However, using cherry juice leads to decrease in the band gap to 1.7 eV (Fig. 6c). As seen from. Fig. 6d, when orange juice was used band gap increased to 1.9 eV. These results show good agreement with SEM and XRD results, which using orange juice leads to produce the smallest particles. Fourier-transform infrared spectroscopy (FTIR) spectrum of as-prepared TbFeO3 nanostructure prepared by using orange juice is shown in Fig. 7. The peaks at 3442 cm-1 and 1621 cm-1 could be assigned to the O-H 6
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stretching vibrational mode. The peak at 540 and 557 cm-1 is due to the Fe-O stretching vibrations [26]. The weak band, noise type vibrations, seen at 2800 cm−1 presented in the spectra belong to the atmospheric carbon dioxide appearing in many spectra. Since TbFeO3 nanostructure was calcinated at 700 ℃. Adsorption-desorption curve, BET, and BJT of sample 6 were illustrated in Fig. 8a-c. As seen from the figure, Adsorption-desorption curve shows that TbFeO3 nanostructure prepared by using orange juice exhibit a narrow range of uniform mesopores. A narrow loop is a clear sign of delayed condensation on the adsorption branch. BET result shows that specific area for TbFeO3 nanostructure was 20 m2.g-1 (Fig. 8b). From the BJH result which illustrated in Fig. 8 c, pore size is about 20 nm. We evaluated the photocatalytic activity of TbFeO3 nanostructure by study the degradation of Methyl orange (as mono Azo dye), Acid Blue 92 (mono Azo), Acid Black 1 (as Double azo class dye), and Acid Brown 214 (as Triazo dye) under UV light for 2 h. Structure of as used dyes are presented in Fig. 9. Fig. 10 shows the degradation efficiency of these four dyes by using sample 3, 4, 5, and 6 as a catalyst under UV light for 2 h. Photocatalyst test was carried out in 10 ppm dye concentration and neutral pH. Degradation efficiency for sample 3-6 and MO dye was 40 ± 0.5, 75 ± 0.3, 78 ±4, and 98 ± 0.4%, respectively (Fig. 10a). Using SDS as the surfactant leads to the lowest photocatalytic activity while using orange juice as surfactant shows the maximum degradation efficiency during 2 h of irradiation. The same recipe was used to study the degradation of Acid Blue 92 (Fig. 10 b). Sample 3 degrades 29 ± 0.7 % of Acid Blue 92 under UV light for 2 h. By changing the photocatalyst to sample 4, degradation efficiency increased to 61 ± 0.6%. When cherry juice was used as a surfactant in synthesis process of catalyst (sample 5), degradation efficiency of 48 % was achieved. The highest removal efficiency for removal of Acid Blue 92 was achieved by changing surfactant to orange juice (sample 6). Fig. 10 c illustrates the degradation yield for Acid Black 1. Samples 3-6 degrade 19 ± 0.3, 48 ± 0.8, 39 ± 0.5, and 51 ± 0.9 %, of Acid Black 1 in 2 h irradiation, respectively. Finally, Acid Brown 214 was used as organic pollution with 10 ppm in concentration (Fig 10d). Sample 6 shows the highest photocatalytic activity and 7
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degrades 60 ± 0.4 % of Acid Brown 214 in 2 h. These indicate that using oranges juice as surfactant lead to improving photocatalytic activity. This could happen because smaller and uniform TbFeO3 nanoparticles were formed when orange juice was used as the surfactant. To best of our knowledge, this is the highest degradation efficiency reported so far. For example, H.Yang et. al. report that TbFeO3 degrades 30 % of methyl orange under 40 W visible light irradiation for 6 h, while our prepared TbFeO3 degraded 90 % of methyl orange [28]. Peisong Tang et al. report 40 % of MO was decomposed after 120 min by using TbFeO3 under visible light [29]. In order to study the effect of pollution concentration on degradation efficiency, sample 6 was used as the most efficient photocatalyst. We studied the degradation of three concentration of Acid Blue 92 (5, 10, and 15 ppm). 91 % of Acid Blue 92 was degraded in 2 h of irradiation when the concentration was 5 ppm (Fig. 11a). By increasing the concentration of organic pollution to 10 ppm, degradation efficiency decreased to 64 ± 0.6 % under the same irradiation time (Fig. 11b). Fig. 11c illustrates that sample 6 degrades 42 ± 0.4 % of Acid Blue 92 when the concentration was 15 ppm. We figure out the effect of pH on the degradation yield by using Acid Blue 92 as organic pollution. Results for degradation of Acid Blue 92 by sample 6 in acidic (pH= 3), neutral (pH=6.8) , and basic condition are summarized in Fig. 12. 100 ± 0.7 % of Acid Blue 92 was degraded when pH adjust to 3 by using HNO3 (Fig. 12a). In neutral pH (pH=6.8) degradation percentage was 64 (Fig. 12 b), while about 92 ± 0.5 % of Acid Blue 92 was degraded in basic pH (pH=10) (Fig. 12c). It is a very tough task to explain the effect of pH on the efficiency of dye photodegradation because of its multiple roles. Highest degradation efficiency was achieved at acidic pH. This could happen because of strong adsorption of the Acid Blue 92 on the TbFeO3 particles as a result of the electrostatic attraction of the positively charged TbFeO3 with the negatively charged dye (Acid blue 92) [30, 31]. In addition higher degradation efficiency achieved at basic pH compare to the neutral pH. This
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could be happen because of easer formation of hydroxyl radicals at basic pH levels [30, 32]. Hydroxyl radicals can be formed by the reaction between hydroxide ions and positive holes. As seen from XRD results, sample 3 has impurity (Fe3O4) that why it shows the lowest photocatalytic activity. In the other hand, sample 6 shows the highest photocatalytic activity probably due to the highly crystallinity, purity and smaller particle size. Degradation happens according to the following mechanism: TbFeO3 absorbed photons and generates electron and holes. It results in the promotion of an electron in the conductive band (eCB−) and formation of a positive hole in the valence band (hVB+) [33]. The hVB+ and eCB− are powerful oxidizing and reducing agents, respectively. The hVB+ reacts with organic compounds and oxidize them. The hVB+ can also oxidize organic compounds by reacting with water to generate Hydroxyl radical (•OH). •OH produced by has the second highest oxidation potential (2.80 V) could oxidize most of organic compounds [34]. Electron in conductive band can react with O2 forming an anion radical (O2.-). Further reaction can lead to the formation of hydrogen peroxide which lead to the formation of •OH [35]. All these generated radicals oxidize organic compounds. 4. Conclusion In conclusion, TbFeO3 nanostructures were prepared by the green and simple method. Base on the results, using orange juice as surfactant leads to produce very pure and highly crystalized TbFeO3 nanostructure with uniform shape and size. In the other hand, Fe3O4 was observed as an impurity when chemical surfactant such as SDS was used in the synthesis of TbFeO3 nanostructure. It seems SDS reduces Fe+3 ion to Fe2+ in the presence of ultrasonic waves. The effect of different parameters such as calcination temperature, type of surfactant, ultrasonic power and time on the morphology of TbFeO3 nanostructure were studied. TbFeO3 nanostructures prepared under the following condition show the highest photocatalytic activity: calcination temperature= 700 ℃, surfactant= orange juice, ultrasonic power= 60 W, and ultrasonic time= 40 min. As prepared TbFeO3 9
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nanostructures were used to treat water contain Methyl orange, Acid Blue 92, Acid Black 1, and Acid Brown 214. In addition, the effect of the concentration of contaminant and its pH on the degradation efficiency were studied. TbFeO3 nanostructures show higher photocatalytic activity in an acidic environment and lower contaminant concentration. Acknowledgements Authors are grateful to the council of Iran National Science Foundation; INSF (97017837) and University of Kashan for supporting this work by Grant No (159271/122).
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[33] M. Boroski, A. C. Rodrigues, J. C. Garcia, L. S. Sampaio, Combined Electrocoagulation and TiO2 Photoassisted Treatment Applied to Wastewater Effluents from Pharmaceutical and Cosmetic Industries. Journal of Hazardous Materials 162 (2009) 448–454. [34] A. Sobczyński, Ł. Duczmal, W. Zmudziński, Phenol destruction by photocatalysis on TiO2: an attempt to solve the reaction mechanism, Journal of Molecular Catalysis A: Chemical 213 (2004) 225-230. [35] J. Fernandez, J. Kiwi, C. Lizama, J. Freer, J. Baeza, H.D. Mansilla, Factorial experimental design of Orange II photocatalytic discolouration , J. Photochem. Photobiol. A, 151 (2002) 213-219.
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Figure Caption Fig. 1. XRD pattern of As-prepared TbFeO3 Nanostructures: a) sample 1 (blue pattern), b) sample 2 (red pattern), c) sample 3 (black pattern), and d) sample 6 (purple pattern). When orange juice was used as a surfactant (sample 6), quite pure and highly crystalized TbFeO3 nanostructures (JCPDS 73-0519) were formed. The asterisks show the peaks for Fe3O4 (JCPDS 01-089-0951). Fig. 2. EDX results of a) sample 3, b) sample 4, d) sample 5, and d) sample 6. These results approve the presence of Tb, Fe, and O elements. Fig. 3. SEM images of TbFeO3 Nanostructures prepared by using a) Sodium dodecyl sulfate (sample 3), b) cetyltrimethylammonium bromide (sample 4), c) Cherry juice (sample 5), and d) Orange juice (sample 6) as surfactant. More uniform particles were formed when cetyltrimethylammonium bromide and orange juice were used as surfactant, respectively. Fig. 4. a and b show the effect of sonication time on the morphology of TbFeO3 Nanostructures: a) sample 7 and b) sample 8. c and d show the effect of ultrasonic power on the morphology of as synthesized TbFeO3 Nanostructures: c) sample 9 and d) sample 10. Fig. 5. TEM images of some different area of sample 6 (Fig 5 a-d). Fig 5 a-d show that size distribution for sample 6 is narrow and show uniform particles size. Fig. 6. DRS of a) sample 3, b) sample 4, c) sample 5, and d) sample 6. When orange juice was used as surfactant, we observed broad absorption peak. These results indicate type of surfactant dramatically change the optical properties of TbFeO3 Nanostructures.
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Fig. 7. FT-IR spectrum of TbFeO3 Nanostructures prepared by orange juice (sample 6). The peaks at 3442 cm-1 and 1621 cm-1 could be assigned to the O-H stretching vibrational mode. The peak at 557 cm-1 is due to the Fe-O stretching vibrations. Fig. 8. a) Adsorption-desorption curve, b) BET, and c) BJT of sample 6. A narrow loop is a clear sign of delayed condensation on the adsorption branch. BET result shows that specific area for TbFeO3 nanostructure was 20 m2.g-1. From the BJH result which illustrated in Fig. 8 c, pore size is about 20 nm. Fig. 9. Chemical structure of Methyl orange, Acid Blue 92, Acid Black 1, and Acid Brown 214. Fig. 10. Photocatalysis results for the degradation of Methyl orange, Acid Blue 92, Acid Black 1, and Acid Brown 214 by using sample 3, 4, 5, and 6 as catalyst under UV light for 2 h. a) Methyl orange, b) Acid Blue 92, c) Acid Black 1, and d) Acid Brown 214 Fig. 11. The effect of concentration of organic pollution (Acid Blue 92) on the degradation efficiency. a) 5 ppm, b) 10 ppm, c) 15 ppm. Fi g. 12. The effect of pH on the degradation yield by using Acid Blue 92 as organic pollution and sample 6 as catalyst. a) Acidic, b) neutral and c), basic.
Table Caption Table 1. Detail for the synthesis of TbFeO3 nanostructures.
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Fig. 1
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Fig. 2
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Fig. 3
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Fig. 4
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Fig. 5 22
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Fig. 6
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Fig. 7
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Fig. 8
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Fig. 9 26
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Fig 10
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Fig. 11
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Fig. 12
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Table 1 Sample No
Calcination
Surfactant
Neutral surfactant
Ultra time
Ultra power
1
600
-
-
40
60
2
700
-
-
40
60
3
700
SDS
-
40
60
4
700
CTAB
-
40
60
5
700
-
cherry
40
60
6
700
-
orange
40
60
7
700
-
orange
30
60
8
700
-
orange
50
60
9
700
-
orange
40
40
10
700
-
orange
40
80
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Table 2 Sample No
Atomic %
Atomic %
Atomic %
Tb
Fe
O
3
6.94
4.82
88.24
4
13.31
8.76
77.92
5
20.13
4.89
74.98
6
8.80
12.45
78.75
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TbFeO3 nanostructures were prepared by a green and simple sonochemistry method.
Using orange juice in synthesis of TbFeO3 nanostructures leads to produce a very pure.
As-prepared TbFeO3 nanostructures were used to remove dyes in water.
We studied the effect of the concentration of contaminant and pH on the degradation efficiency.