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Green synthesis and characterization of Dy2Ce2O7 nanostructures using Ananas comosus with high visible-light photocatalytic activity of organic contaminants
Journal of Alloys and Compounds 763 (2018) 314e321
Contents lists available at ScienceDirect
Journal of Alloys and Compounds journal homepage: http://www.elsevier.com/locate/jalcom
Green synthesis and characterization of Dy2Ce2O7 nanostructures using Ananas comosus with high visible-light photocatalytic activity of organic contaminants Sahar Zinatloo-Ajabshir a, **, Zahra Salehi b, Masoud Salavati-Niasari b, * a b
Department of Chemical Engineering, University of Bonab, P.O. Box. 55517-61167, Bonab, Iran Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P. O. Box. 87317-51167, Iran
a r t i c l e i n f o
a b s t r a c t
Article history: Received 23 March 2018 Accepted 25 May 2018 Available online 26 May 2018
An easy and eco-friendly viable way has been utilized to synthesize nano-scale Dy2Ce2O7 with employing extract of Ananas comosus as new and efficient bio fuel, for the first time. The amount of extract of Ananas comosus has been altered to explore its impact on shape, catalytic yield and dimension of Dy2Ce2O7. The purity, optical features and shape of the resulting Dy2Ce2O7 have been determined with FESEM, EDS, XRD, DRS and TEM. Further, the catalytic yield of various samples of dysprosium cerate has been examined for eriochrome black T degradation under visible illumination. The nano-scale Dy2Ce2O7 synthesized with employing appropriate amount of extract of Ananas comosus as new and efficient bio fuel, exhibited superior photocatalytic yield in the contaminant destruction. © 2018 Elsevier B.V. All rights reserved.
Keywords: Dysprosium cerate Nanostructure Electron microscopy Photocatalytic performance
1. Introduction Investigation of rare earth cerate (Re2Ce2O7) has been gaining importance owing to their wide usages in diverse fields [1e8]. Diverse techniques have been introduced to fabricate the rare earth create [7,9e13]. The introduced techniques have been not costeffective or not eco-friendly viable owing to the application of detrimental chemical compounds, or multiple and complex steps in preparation. So, there is major necessity to omit the detrimental chemical compounds and to introduce clean and efficient strategy for fabrication of the nano-scale rare earth cerate. The yield of compounds in the nanometric scale is quite dependent on their dimension and shape. Hence, their fabrication with controlling over dimension and shape has been gaining importance, in the recent times [14e19]. As clean and favorable strategy for environmental remediation, the application of photocatalysts that efficiently work with employing visible light from natural energy source, has been gaining importance [20e22]. So, there is major necessity to design
and introduce the efficient types of catalysts that work with employing visible light. Until now, there is not any report on easy and clean preparation of the nano-scale Dy2Ce2O7 with employing extract of Ananas comosus as bio fuel. Herein, an alternate, easy and eco-friendly viable way is utilized to synthesize nano-scale Dy2Ce2O7 with employing extract of Ananas comosus as new and efficient bio fuel, for the first time. For production of the nano-scale Dy2Ce2O7, we choose extract of Ananas comosus which contains great values of sugars (sucrose & glucose) that can function as natural and nondetrimental reductant as well as shape and dimension modifier. The amount of extract of Ananas comosus is altered to explore its impact on shape, catalytic yield and dimension of Dy2Ce2O7. In addition, the catalytic yield of various samples of dysprosium cerate is examined for eriochrome black T degradation under visible illumination. 2. Experimental 2.1. Materials and characterization
* Corresponding author. ** Corresponding author. E-mail addresses: [email protected] kashanu.ac.ir (M. Salavati-Niasari).
(S.
https://doi.org/10.1016/j.jallcom.2018.05.311 0925-8388/© 2018 Elsevier B.V. All rights reserved.
Zinatloo-Ajabshir),
salavati@
Ceric ammonium nitrate as well as Dy(NO3)3$5H2O have been procured from Merck. The morphological attributes of the produced dysprosium cerate have been analyzed employing FESEM
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315
Table 1 Reaction conditions for production of various samples of dysprosium cerate. Sample no
Fuel
1 2 3 4 5 6
Extract Extract Extract Extract Extract e
of of of of of
Ananas Ananas Ananas Ananas Ananas
comosus comosus comosus comosus comosus
Amount of extract of pineapple (ml)
Figure of FESEM images
1 2 3 4 5 e
1a and b 1c and d 1e 2a 2b and c 3a and b
Fig. 1. FESEM pictures of samples 1 (a and b), 2 (c and d) and 3 (e).
316
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Fig. 2. FESEM pictures of samples 4 (a) and 5 (b and c).
and TEM micrographs obtained by means of a MIRA3 FEG-SEM plus a JEM-2100 TEM. The crystalline nature of the nano-scale dysprosium cerate has been evaluated by means of a diffractometer of Philips Company with Ni-filtered Cu Ka radiation. The purity rate of the produced dysprosium cerate has been evaluated by means of a Philips XL30 microscope. DRS study has been made on a UVevis spectrophotometer (Shimadzu, UV-2550, Japan).
2.2. Preparation of dysprosium cerate samples An easy and eco-friendly viable way was utilized to synthesize nano-scale dysprosium cerate with employing extract of Ananas comosus as new and efficient bio fuel (sample 3). Initially, appropriate amount of extract of Ananas comosus was slowly mixed with reaction solution involving source of Ce (1.3 mmol) and source of Dy (1.3 mmol) in distilled water and the resulting mixture stirred by means of magnetic stirrer during 17 min (at 45 C). Subsequently, vaporization of the ultimate mixture caused to attain the porous gel. At the end, the dried gel (at 100 C) was heated at 450 C during 210 min. The role of the amount of extract of Ananas
comosus has been determined with changing its quantity from 0 to 5 mL (Table 1).
2.3. Catalytic yield The catalytic yield of various samples of dysprosium cerate has been examined for eriochrome black T degradation under visible illumination. For evaluation of the catalytic yield, 76 mg of each of diverse samples of dysprosium cerate has been suspended in aqueous solution of eriochrome black T (1.9 mg). Each colloidal mixture was stirred during half an hour (in darkness) for achievement of the adsorptionedesorption equilibrium. Subsequently, each colloidal mixture was irradiated by means of 125 W Osram lamp. The following equation has been applied to gain the eriochrome black T pollutant destructing rate:
D:P: ðtÞ ¼
A0 At 100 A0
(1)
where A0 and At are the primary and ultimate quantity of
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317
Fig. 3. FESEM pictures of sample that gained without application of extract of Ananas comosus.
absorbance related to eriochrome black T. 3. Results and discussion An easy and eco-friendly viable way was utilized to synthesize nano-scale dysprosium cerate with employing extract of Ananas comosus as new and efficient bio fuel. The amount of extract of Ananas comosus has been altered to explore its impact on shape, catalytic yield and dimension of Dy2Ce2O7. FESEM pictures of dysprosium cerate samples that gained in presence of 1, 2, 3, 4 and 5 mL of extract of Ananas comosus are denoted in Figs. 1 and 2. Although dysprosium cerate nanoparticles can be produced with increment in the utilized amount of extract of Ananas comosus from 1 to 3 mL, but the uniformity as well as size of dysprosium cerate nanoparticles are very various (Fig. 1). FESEM findings are indicative of the production of the most uniform dysprosium cerate nanoparticles with the smallest grain size in presence of 3 mL of extract of Ananas comosus. High agglomerated micro/nanobundles (Fig. 2a) and irregular microstructures (Fig. 2b and c) can be produced with increment in the utilized amount of extract of Ananas
Fig. 4. TEM pictures of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel.
comosus to 4 and 5 mL. We utilized several amounts of extract of Ananas comosus which contain variant values of sugars (sucrose & glucose) that can function as shape and dimension modifier with generation of steric hindrance impacts and consequently can be reason for production of diverse nano/micro structures of dysprosium cerate. FESEM pictures of sample that gained without application of extract of Ananas comosus denote high agglomerated microstructures/bulk structures (Fig. 3a and b). As a result, the
318
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Fig. 5. XRD pattern of the dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel.
Fig. 6. EDS spectrum of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus.
application of extract of Ananas comosus and variation in its amount can affect shape and dimension of dysprosium cerate. Also, application of 3 mL of extract of Ananas comosus as new and efficient bio fuel can be quite useful to gain the nano-scale dysprosium cerate with the highest uniformity. TEM pictures of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio
fuel are observable in Fig. 4aec for further investigation of its shape and grain size. Corresponding pictures are indicative of dysprosium cerate nanoparticles with size varied between 8 and 25 nm. Crystalline nature and purity rate of the dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel have been explored with XRD (see Fig. 5). Diffraction peaks that are observable are in excellent agreement with pure fluorite (standard) dysprosium cerate [9]. The computed crystallite sizes of the dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel with Scherer's equation of about 15 nm. EDS spectrum of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel is observable in Fig. 6 for further investigation of its purity rate. Corresponding spectrum denotes only the existence of main constituents like O, Ce and Dy. So, findings are indicative of the fabrication of pure dysprosium cerate via an easy and eco-friendly viable way (see Fig. 1e, Scheme 1). TGA plot corresponding to the dried porous gel (before heating stage) is exhibited in Fig. 7. 7% mass reduction is observable before 170 C can be indicative of deletion of H2O. The other mass reduction (36%) is occurred in 170e450 C can reveal the combustion reaction that takes place between sugar in juice of Ananas comosus and nitrates and thereupon fabrication of the nano-scale dysprosium cerate. DRS spectrum of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel is observable in Fig. 8 for investigation of its optical attributes. Corresponding spectrum is indicative of the peak at 450 nm. The energy gap is the dominant parameter affecting the photocatalytic yield. The determined vale of energy gap pertaining to the dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel from Tauc's plot ((ahn)2 against hn) of about 2.67 eV. Hence, the easy activation of the dysprosium create sample as photocatalyst with visible illumination for destroying pollutants, can be confirmed with findings. The catalytic yield of various samples of dysprosium cerate that gained in presence of several quantities of extract of Ananas comosus, has been examined for eriochrome black T degradation under visible illumination (see Figs. 9 and 10). There is no destruction without usage of visible illumination or various samples of dysprosium cerate, as observable in Figs. 9 and 10. After just 1 h, 91.7% destruction occurs in the presence of sample 3 while there is 80.1% destruction in the case of sample 4, and sample 5 can only destruct 71% of the eriochrome black T. Further, after 60 min of illumination, the destruction ratio of eriochrome black T for sample 6 is about 33%. That is to say, the catalytic yield of sample 3 under visible illumination is the most desirable than that of other samples. The excellent catalytic yield of sample 3 can be pertaining to its grain size and shape (see Figs. 1e3). The fine size and great surface area of the dysprosium cerate that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel can effectively raise its catalytic yield [23,24]. As a result, the application of extract of Ananas comosus and variation in its amount can affect catalytic yield of dysprosium cerate. Further, to explore its chemical stability, the dysprosium cerate that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel has been recycled and reutilized nine times in the destruction of eriochrome black T under the identical condition (see Fig. 11). In the lifetime test, dysprosium cerate (sample 3) only reveals slight reduction in efficiency. Findings affirm that dysprosium cerate
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Scheme 1. Schematic diagram pertaining to preparation of the nano-scale Dy2Ce2O7.
Fig. 7. TGA plot corresponding to the dried porous gel (before heating stage).
(sample 3) is quite stable in the eriochrome black T destruction process. Accordingly, application of 3 mL of extract of Ananas comosus as new and efficient bio fuel can be quite useful to gain the nano-scale dysprosium cerate with the most desirable catalytic yield as well as excellent stability. 4. Conclusions Synthesis of nano-scale Dy2Ce2O7 with employing extract of Ananas comosus as new and efficient bio fuel was demonstrated to be an easy and eco-friendly viable way. No expensive and detrimental modifiers or templates were employed to gain the nanoscale Dy2Ce2O7. The amount of extract of Ananas comosus has been altered to explore its impact on shape, catalytic yield and dimension of Dy2Ce2O7. Further, the catalytic yield of various samples of dysprosium cerate has been examined for eriochrome black T degradation under visible illumination. It is denoted that the application of extract of Ananas comosus and variation in its amount can affect shape, catalytic yield and dimension of dysprosium cerate. The nano-scale Dy2Ce2O7 with excellent stability
Fig. 8. DR-UV-vis spectrum (a) and plot to determine the band gap (b) of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus (sample 3).
synthesized by means of 3 mL of extract of Ananas comosus as new and efficient bio fuel, exhibited superior photocatalytic yield in the contaminant destruction. The great capability of the nano-scale dysprosium create as photocatalyst that work with employing visible illumination for destroying pollutants with goal of
320
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Fig. 10. Photocatalytic eriochrome black T destruction of various samples of dysprosium cerate gained with and without application of extract of Ananas comosus (samples 3 and 6).
Fig. 11. Cycling runs in the eriochrome black T destruction in the presence of the nanoscale dysprosium cerate (sample 3) under visible illumination.
Acknowledgements Authors are grateful to the council of Iran National Science Foundation (INSF) and University of Kashan for supporting this work by Grant No (159271/822990). References
Fig. 9. Photocatalytic eriochrome black T destruction of various samples of dysprosium cerate that gained in presence of several quantities of extract of Ananas comosus (samples 3e5).
environmental remediation, can be confirmed with findings. The offered strategy is time and energy-efficient and can be applied as a desirable alternative for large-scale fabrication of the nano-scale dysprosium create with high visible-light photocatalytic activity.
[1] B.C.H. Steele, A. Heinzel, Materials for fuel-cell technologies, Nature 414 (2001) 345e352. [2] G. Meng, G. Ma, Q. Ma, R. Peng, X. Liu, Ceramic membrane fuel cells based on solid proton electrolytes, Solid State Ionics 178 (2007) 697e703. [3] Z.G. Liu, J.H. Ouyang, K.N. Sun, Electrical conductivity improvement of Nd2Ce2O7 ceramic Co-doped with Gd2O3 and ZrO2, Fuel Cell. 11 (2011) 153e157. € ver, Lanthanumece[4] X. Cao, R. Vassen, W. Fischer, F. Tietz, W. Jungen, D. Sto rium oxide as a thermal barrier-coating material for high-temperature applications, Adv. Mater. 15 (2003) 1438e1442. [5] Z. Salehi, S. Zinatloo-Ajabshir, M. Salavati-Niasari, New simple route to prepare Dy2Ce2O7 nanostructures: structural and photocatalytic studies, J. Mol. Liq. 222 (2016) 218e224. [6] Y. Ling, J. Chen, Z. Wang, C. Xia, R. Peng, Y. Lu, New ionic diffusion strategy to fabricate proton-conducting solid oxide fuel cells based on a stable La2Ce2O7 electrolyte, Int. J. Hydrogen Energy 38 (2013) 7430e7437. [7] Z. Salehi, S. Zinatloo-Ajabshir, M. Salavati-Niasari, Novel synthesis of Dy2Ce2O7
S. Zinatloo-Ajabshir et al. / Journal of Alloys and Compounds 763 (2018) 314e321
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
nanostructures via a facile combustion route, RSC Adv. 6 (2016) 26895e26901. S. Zinatloo-Ajabshir, Z. Salehi, M. Salavati-Niasari, Preparation, characterization and photocatalytic properties of Pr2Ce2O7 nanostructures via a facile procedure, RSC Adv. 6 (2016) 107785e107792. C. Wang, Y. Wang, A. Zhang, Y. Cheng, F. Chi, Z. Yu, The influence of ionic radii on the grain growth and sintering-resistance of Ln2Ce2O7 (Ln ¼ La, Nd, Sm, Gd), J. Mater. Sci. 48 (2013) 8133e8139. F.W. Bezerra Lopes, C.P. de Souza, A.M. Vieira de Morais, J.-P. Dallas, J.R. Gavarri, Determination of RE2Ce2O7 pyrochlore phases from monaziteeallanite ores, Hydrometallurgy 97 (2009) 167e172. V. Besikiotis, C.S. Knee, I. Ahmed, R. Haugsrud, T. Norby, Crystal structure, hydration and ionic conductivity of the inherently oxygen-deficient La2Ce2O7, Solid State Ionics 228 (2012) 1e7. C. Wang, W. Huang, Y. Wang, Y. Cheng, B. Zou, X. Fan, J. Yang, X. Cao, Synthesis of monodispersed La2Ce2O7 nanocrystals via hydrothermal method: a study of crystal growth and sintering behavior, Int. J. Refract. Metals Hard Mater. 31 (2012) 242e246. nchez-Bautista, A.J. Dos santos-García, J. Pen ~ a-Martínez, J. CanalesC. Sa V azquez, The grain boundary effect on dysprosium doped ceria, Solid State Ionics 181 (2010) 1665e1673. F. Razi, S. Zinatloo-Ajabshir, M. Salavati-Niasari, Preparation and characterization of HgI2 nanostructures via a new facile route, Mater. Lett. 193 (2017) 9e12. S. Zinatloo-Ajabshir, M.S. Morassaei, M. Salavati-Niasari, Facile fabrication of Dy2Sn2O7-SnO2 nanocomposites as an effective photocatalyst for degradation and removal of organic contaminants, J. Colloid Interface Sci. 497 (2017) 298e308. M.N. Alam, S. Das, S. Batuta, N. Roy, A. Chatterjee, D. Mandal, N.A. Begum,
[17]
[18]
[19] [20]
[21]
[22]
[23]
[24]
321
Murraya koenegii spreng, Leaf extract: an efficient green multifunctional agent for the controlled synthesis of Au nanoparticles, ACS Sustain. Chem. Eng. 2 (2014) 652e664. F. Beshkar, S. Zinatloo-Ajabshir, S. Bagheri, M. Salavati-Niasari, Novel preparation of highly photocatalytically active copper chromite nanostructured material via a simple hydrothermal route, PLoS One 12 (2017) e0158549. S. Zinatloo-Ajabshir, S. Mortazavi-Derazkola, M. Salavati-Niasari, Simple sonochemical synthesis of Ho2O3-SiO2 nanocomposites as an effective photocatalyst for degradation and removal of organic contaminant, Ultrason. Sonochem. 39 (2017) 452e460. M. Zheng, Y. Liu, S. Zhao, W. He, Y. Xiao, D. Yuan, Simple shape-controlled synthesis of carbon hollow structures, Inorg. Chem. 49 (2010) 8674e8683. M. Sun, D. Li, W. Li, Y. Chen, Z. Chen, Y. He, X. Fu, New photocatalyst, Sb2S3, for degradation of methyl orange under visible-light irradiation, J. Phys. Chem. C 112 (2008) 18076e18081. Y.Y. Lee, J.H. Moon, Y.S. Choi, G.O. Park, M. Jin, L.Y. Jin, D. Li, J.Y. Lee, S.U. Son, J.M. Kim, Visible-light driven photocatalytic degradation of organic dyes over ordered mesoporous CdxZn1exs materials, J. Phys. Chem. C 121 (2017) 5137e5144. S. Cui, G. Shan, L. Zhu, Solvothermal synthesis of I-deficient BiOI thin film with distinct photocatalytic activity and durability under simulated sunlight, Appl. Catal. B Environ. 219 (2017) 249e258. J.b. Zhong, J.z. Li, F.m. Feng, Y. Lu, J. Zeng, W. Hu, Z. Tang, Improved photocatalytic performance of SiO2eTiO2 prepared with the assistance of SDBS, J. Mol. Catal. A Chem. 357 (2012) 101e105. H. Wang, C. Xie, W. Zhang, S. Cai, Z. Yang, Y. Gui, Comparison of dye degradation efficiency using ZnO powders with various size scales, J. Hazard Mater. 141 (2007) 645e652.
Contents lists available at ScienceDirect
Journal of Alloys and Compounds journal homepage: http://www.elsevier.com/locate/jalcom
Green synthesis and characterization of Dy2Ce2O7 nanostructures using Ananas comosus with high visible-light photocatalytic activity of organic contaminants Sahar Zinatloo-Ajabshir a, **, Zahra Salehi b, Masoud Salavati-Niasari b, * a b
Department of Chemical Engineering, University of Bonab, P.O. Box. 55517-61167, Bonab, Iran Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P. O. Box. 87317-51167, Iran
a r t i c l e i n f o
a b s t r a c t
Article history: Received 23 March 2018 Accepted 25 May 2018 Available online 26 May 2018
An easy and eco-friendly viable way has been utilized to synthesize nano-scale Dy2Ce2O7 with employing extract of Ananas comosus as new and efficient bio fuel, for the first time. The amount of extract of Ananas comosus has been altered to explore its impact on shape, catalytic yield and dimension of Dy2Ce2O7. The purity, optical features and shape of the resulting Dy2Ce2O7 have been determined with FESEM, EDS, XRD, DRS and TEM. Further, the catalytic yield of various samples of dysprosium cerate has been examined for eriochrome black T degradation under visible illumination. The nano-scale Dy2Ce2O7 synthesized with employing appropriate amount of extract of Ananas comosus as new and efficient bio fuel, exhibited superior photocatalytic yield in the contaminant destruction. © 2018 Elsevier B.V. All rights reserved.
Keywords: Dysprosium cerate Nanostructure Electron microscopy Photocatalytic performance
1. Introduction Investigation of rare earth cerate (Re2Ce2O7) has been gaining importance owing to their wide usages in diverse fields [1e8]. Diverse techniques have been introduced to fabricate the rare earth create [7,9e13]. The introduced techniques have been not costeffective or not eco-friendly viable owing to the application of detrimental chemical compounds, or multiple and complex steps in preparation. So, there is major necessity to omit the detrimental chemical compounds and to introduce clean and efficient strategy for fabrication of the nano-scale rare earth cerate. The yield of compounds in the nanometric scale is quite dependent on their dimension and shape. Hence, their fabrication with controlling over dimension and shape has been gaining importance, in the recent times [14e19]. As clean and favorable strategy for environmental remediation, the application of photocatalysts that efficiently work with employing visible light from natural energy source, has been gaining importance [20e22]. So, there is major necessity to design
and introduce the efficient types of catalysts that work with employing visible light. Until now, there is not any report on easy and clean preparation of the nano-scale Dy2Ce2O7 with employing extract of Ananas comosus as bio fuel. Herein, an alternate, easy and eco-friendly viable way is utilized to synthesize nano-scale Dy2Ce2O7 with employing extract of Ananas comosus as new and efficient bio fuel, for the first time. For production of the nano-scale Dy2Ce2O7, we choose extract of Ananas comosus which contains great values of sugars (sucrose & glucose) that can function as natural and nondetrimental reductant as well as shape and dimension modifier. The amount of extract of Ananas comosus is altered to explore its impact on shape, catalytic yield and dimension of Dy2Ce2O7. In addition, the catalytic yield of various samples of dysprosium cerate is examined for eriochrome black T degradation under visible illumination. 2. Experimental 2.1. Materials and characterization
* Corresponding author. ** Corresponding author. E-mail addresses: [email protected] kashanu.ac.ir (M. Salavati-Niasari).
(S.
https://doi.org/10.1016/j.jallcom.2018.05.311 0925-8388/© 2018 Elsevier B.V. All rights reserved.
Zinatloo-Ajabshir),
salavati@
Ceric ammonium nitrate as well as Dy(NO3)3$5H2O have been procured from Merck. The morphological attributes of the produced dysprosium cerate have been analyzed employing FESEM
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315
Table 1 Reaction conditions for production of various samples of dysprosium cerate. Sample no
Fuel
1 2 3 4 5 6
Extract Extract Extract Extract Extract e
of of of of of
Ananas Ananas Ananas Ananas Ananas
comosus comosus comosus comosus comosus
Amount of extract of pineapple (ml)
Figure of FESEM images
1 2 3 4 5 e
1a and b 1c and d 1e 2a 2b and c 3a and b
Fig. 1. FESEM pictures of samples 1 (a and b), 2 (c and d) and 3 (e).
316
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Fig. 2. FESEM pictures of samples 4 (a) and 5 (b and c).
and TEM micrographs obtained by means of a MIRA3 FEG-SEM plus a JEM-2100 TEM. The crystalline nature of the nano-scale dysprosium cerate has been evaluated by means of a diffractometer of Philips Company with Ni-filtered Cu Ka radiation. The purity rate of the produced dysprosium cerate has been evaluated by means of a Philips XL30 microscope. DRS study has been made on a UVevis spectrophotometer (Shimadzu, UV-2550, Japan).
2.2. Preparation of dysprosium cerate samples An easy and eco-friendly viable way was utilized to synthesize nano-scale dysprosium cerate with employing extract of Ananas comosus as new and efficient bio fuel (sample 3). Initially, appropriate amount of extract of Ananas comosus was slowly mixed with reaction solution involving source of Ce (1.3 mmol) and source of Dy (1.3 mmol) in distilled water and the resulting mixture stirred by means of magnetic stirrer during 17 min (at 45 C). Subsequently, vaporization of the ultimate mixture caused to attain the porous gel. At the end, the dried gel (at 100 C) was heated at 450 C during 210 min. The role of the amount of extract of Ananas
comosus has been determined with changing its quantity from 0 to 5 mL (Table 1).
2.3. Catalytic yield The catalytic yield of various samples of dysprosium cerate has been examined for eriochrome black T degradation under visible illumination. For evaluation of the catalytic yield, 76 mg of each of diverse samples of dysprosium cerate has been suspended in aqueous solution of eriochrome black T (1.9 mg). Each colloidal mixture was stirred during half an hour (in darkness) for achievement of the adsorptionedesorption equilibrium. Subsequently, each colloidal mixture was irradiated by means of 125 W Osram lamp. The following equation has been applied to gain the eriochrome black T pollutant destructing rate:
D:P: ðtÞ ¼
A0 At 100 A0
(1)
where A0 and At are the primary and ultimate quantity of
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317
Fig. 3. FESEM pictures of sample that gained without application of extract of Ananas comosus.
absorbance related to eriochrome black T. 3. Results and discussion An easy and eco-friendly viable way was utilized to synthesize nano-scale dysprosium cerate with employing extract of Ananas comosus as new and efficient bio fuel. The amount of extract of Ananas comosus has been altered to explore its impact on shape, catalytic yield and dimension of Dy2Ce2O7. FESEM pictures of dysprosium cerate samples that gained in presence of 1, 2, 3, 4 and 5 mL of extract of Ananas comosus are denoted in Figs. 1 and 2. Although dysprosium cerate nanoparticles can be produced with increment in the utilized amount of extract of Ananas comosus from 1 to 3 mL, but the uniformity as well as size of dysprosium cerate nanoparticles are very various (Fig. 1). FESEM findings are indicative of the production of the most uniform dysprosium cerate nanoparticles with the smallest grain size in presence of 3 mL of extract of Ananas comosus. High agglomerated micro/nanobundles (Fig. 2a) and irregular microstructures (Fig. 2b and c) can be produced with increment in the utilized amount of extract of Ananas
Fig. 4. TEM pictures of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel.
comosus to 4 and 5 mL. We utilized several amounts of extract of Ananas comosus which contain variant values of sugars (sucrose & glucose) that can function as shape and dimension modifier with generation of steric hindrance impacts and consequently can be reason for production of diverse nano/micro structures of dysprosium cerate. FESEM pictures of sample that gained without application of extract of Ananas comosus denote high agglomerated microstructures/bulk structures (Fig. 3a and b). As a result, the
318
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Fig. 5. XRD pattern of the dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel.
Fig. 6. EDS spectrum of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus.
application of extract of Ananas comosus and variation in its amount can affect shape and dimension of dysprosium cerate. Also, application of 3 mL of extract of Ananas comosus as new and efficient bio fuel can be quite useful to gain the nano-scale dysprosium cerate with the highest uniformity. TEM pictures of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio
fuel are observable in Fig. 4aec for further investigation of its shape and grain size. Corresponding pictures are indicative of dysprosium cerate nanoparticles with size varied between 8 and 25 nm. Crystalline nature and purity rate of the dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel have been explored with XRD (see Fig. 5). Diffraction peaks that are observable are in excellent agreement with pure fluorite (standard) dysprosium cerate [9]. The computed crystallite sizes of the dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel with Scherer's equation of about 15 nm. EDS spectrum of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel is observable in Fig. 6 for further investigation of its purity rate. Corresponding spectrum denotes only the existence of main constituents like O, Ce and Dy. So, findings are indicative of the fabrication of pure dysprosium cerate via an easy and eco-friendly viable way (see Fig. 1e, Scheme 1). TGA plot corresponding to the dried porous gel (before heating stage) is exhibited in Fig. 7. 7% mass reduction is observable before 170 C can be indicative of deletion of H2O. The other mass reduction (36%) is occurred in 170e450 C can reveal the combustion reaction that takes place between sugar in juice of Ananas comosus and nitrates and thereupon fabrication of the nano-scale dysprosium cerate. DRS spectrum of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel is observable in Fig. 8 for investigation of its optical attributes. Corresponding spectrum is indicative of the peak at 450 nm. The energy gap is the dominant parameter affecting the photocatalytic yield. The determined vale of energy gap pertaining to the dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel from Tauc's plot ((ahn)2 against hn) of about 2.67 eV. Hence, the easy activation of the dysprosium create sample as photocatalyst with visible illumination for destroying pollutants, can be confirmed with findings. The catalytic yield of various samples of dysprosium cerate that gained in presence of several quantities of extract of Ananas comosus, has been examined for eriochrome black T degradation under visible illumination (see Figs. 9 and 10). There is no destruction without usage of visible illumination or various samples of dysprosium cerate, as observable in Figs. 9 and 10. After just 1 h, 91.7% destruction occurs in the presence of sample 3 while there is 80.1% destruction in the case of sample 4, and sample 5 can only destruct 71% of the eriochrome black T. Further, after 60 min of illumination, the destruction ratio of eriochrome black T for sample 6 is about 33%. That is to say, the catalytic yield of sample 3 under visible illumination is the most desirable than that of other samples. The excellent catalytic yield of sample 3 can be pertaining to its grain size and shape (see Figs. 1e3). The fine size and great surface area of the dysprosium cerate that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel can effectively raise its catalytic yield [23,24]. As a result, the application of extract of Ananas comosus and variation in its amount can affect catalytic yield of dysprosium cerate. Further, to explore its chemical stability, the dysprosium cerate that gained in presence of 3 mL of extract of Ananas comosus as new and efficient bio fuel has been recycled and reutilized nine times in the destruction of eriochrome black T under the identical condition (see Fig. 11). In the lifetime test, dysprosium cerate (sample 3) only reveals slight reduction in efficiency. Findings affirm that dysprosium cerate
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Scheme 1. Schematic diagram pertaining to preparation of the nano-scale Dy2Ce2O7.
Fig. 7. TGA plot corresponding to the dried porous gel (before heating stage).
(sample 3) is quite stable in the eriochrome black T destruction process. Accordingly, application of 3 mL of extract of Ananas comosus as new and efficient bio fuel can be quite useful to gain the nano-scale dysprosium cerate with the most desirable catalytic yield as well as excellent stability. 4. Conclusions Synthesis of nano-scale Dy2Ce2O7 with employing extract of Ananas comosus as new and efficient bio fuel was demonstrated to be an easy and eco-friendly viable way. No expensive and detrimental modifiers or templates were employed to gain the nanoscale Dy2Ce2O7. The amount of extract of Ananas comosus has been altered to explore its impact on shape, catalytic yield and dimension of Dy2Ce2O7. Further, the catalytic yield of various samples of dysprosium cerate has been examined for eriochrome black T degradation under visible illumination. It is denoted that the application of extract of Ananas comosus and variation in its amount can affect shape, catalytic yield and dimension of dysprosium cerate. The nano-scale Dy2Ce2O7 with excellent stability
Fig. 8. DR-UV-vis spectrum (a) and plot to determine the band gap (b) of dysprosium cerate sample that gained in presence of 3 mL of extract of Ananas comosus (sample 3).
synthesized by means of 3 mL of extract of Ananas comosus as new and efficient bio fuel, exhibited superior photocatalytic yield in the contaminant destruction. The great capability of the nano-scale dysprosium create as photocatalyst that work with employing visible illumination for destroying pollutants with goal of
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Fig. 10. Photocatalytic eriochrome black T destruction of various samples of dysprosium cerate gained with and without application of extract of Ananas comosus (samples 3 and 6).
Fig. 11. Cycling runs in the eriochrome black T destruction in the presence of the nanoscale dysprosium cerate (sample 3) under visible illumination.
Acknowledgements Authors are grateful to the council of Iran National Science Foundation (INSF) and University of Kashan for supporting this work by Grant No (159271/822990). References
Fig. 9. Photocatalytic eriochrome black T destruction of various samples of dysprosium cerate that gained in presence of several quantities of extract of Ananas comosus (samples 3e5).
environmental remediation, can be confirmed with findings. The offered strategy is time and energy-efficient and can be applied as a desirable alternative for large-scale fabrication of the nano-scale dysprosium create with high visible-light photocatalytic activity.
[1] B.C.H. Steele, A. Heinzel, Materials for fuel-cell technologies, Nature 414 (2001) 345e352. [2] G. Meng, G. Ma, Q. Ma, R. Peng, X. Liu, Ceramic membrane fuel cells based on solid proton electrolytes, Solid State Ionics 178 (2007) 697e703. [3] Z.G. Liu, J.H. Ouyang, K.N. Sun, Electrical conductivity improvement of Nd2Ce2O7 ceramic Co-doped with Gd2O3 and ZrO2, Fuel Cell. 11 (2011) 153e157. € ver, Lanthanumece[4] X. Cao, R. Vassen, W. Fischer, F. Tietz, W. Jungen, D. Sto rium oxide as a thermal barrier-coating material for high-temperature applications, Adv. Mater. 15 (2003) 1438e1442. [5] Z. Salehi, S. Zinatloo-Ajabshir, M. Salavati-Niasari, New simple route to prepare Dy2Ce2O7 nanostructures: structural and photocatalytic studies, J. Mol. Liq. 222 (2016) 218e224. [6] Y. Ling, J. Chen, Z. Wang, C. Xia, R. Peng, Y. Lu, New ionic diffusion strategy to fabricate proton-conducting solid oxide fuel cells based on a stable La2Ce2O7 electrolyte, Int. J. Hydrogen Energy 38 (2013) 7430e7437. [7] Z. Salehi, S. Zinatloo-Ajabshir, M. Salavati-Niasari, Novel synthesis of Dy2Ce2O7
S. Zinatloo-Ajabshir et al. / Journal of Alloys and Compounds 763 (2018) 314e321
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
nanostructures via a facile combustion route, RSC Adv. 6 (2016) 26895e26901. S. Zinatloo-Ajabshir, Z. Salehi, M. Salavati-Niasari, Preparation, characterization and photocatalytic properties of Pr2Ce2O7 nanostructures via a facile procedure, RSC Adv. 6 (2016) 107785e107792. C. Wang, Y. Wang, A. Zhang, Y. Cheng, F. Chi, Z. Yu, The influence of ionic radii on the grain growth and sintering-resistance of Ln2Ce2O7 (Ln ¼ La, Nd, Sm, Gd), J. Mater. Sci. 48 (2013) 8133e8139. F.W. Bezerra Lopes, C.P. de Souza, A.M. Vieira de Morais, J.-P. Dallas, J.R. Gavarri, Determination of RE2Ce2O7 pyrochlore phases from monaziteeallanite ores, Hydrometallurgy 97 (2009) 167e172. V. Besikiotis, C.S. Knee, I. Ahmed, R. Haugsrud, T. Norby, Crystal structure, hydration and ionic conductivity of the inherently oxygen-deficient La2Ce2O7, Solid State Ionics 228 (2012) 1e7. C. Wang, W. Huang, Y. Wang, Y. Cheng, B. Zou, X. Fan, J. Yang, X. Cao, Synthesis of monodispersed La2Ce2O7 nanocrystals via hydrothermal method: a study of crystal growth and sintering behavior, Int. J. Refract. Metals Hard Mater. 31 (2012) 242e246. nchez-Bautista, A.J. Dos santos-García, J. Pen ~ a-Martínez, J. CanalesC. Sa V azquez, The grain boundary effect on dysprosium doped ceria, Solid State Ionics 181 (2010) 1665e1673. F. Razi, S. Zinatloo-Ajabshir, M. Salavati-Niasari, Preparation and characterization of HgI2 nanostructures via a new facile route, Mater. Lett. 193 (2017) 9e12. S. Zinatloo-Ajabshir, M.S. Morassaei, M. Salavati-Niasari, Facile fabrication of Dy2Sn2O7-SnO2 nanocomposites as an effective photocatalyst for degradation and removal of organic contaminants, J. Colloid Interface Sci. 497 (2017) 298e308. M.N. Alam, S. Das, S. Batuta, N. Roy, A. Chatterjee, D. Mandal, N.A. Begum,
[17]
[18]
[19] [20]
[21]
[22]
[23]
[24]
321
Murraya koenegii spreng, Leaf extract: an efficient green multifunctional agent for the controlled synthesis of Au nanoparticles, ACS Sustain. Chem. Eng. 2 (2014) 652e664. F. Beshkar, S. Zinatloo-Ajabshir, S. Bagheri, M. Salavati-Niasari, Novel preparation of highly photocatalytically active copper chromite nanostructured material via a simple hydrothermal route, PLoS One 12 (2017) e0158549. S. Zinatloo-Ajabshir, S. Mortazavi-Derazkola, M. Salavati-Niasari, Simple sonochemical synthesis of Ho2O3-SiO2 nanocomposites as an effective photocatalyst for degradation and removal of organic contaminant, Ultrason. Sonochem. 39 (2017) 452e460. M. Zheng, Y. Liu, S. Zhao, W. He, Y. Xiao, D. Yuan, Simple shape-controlled synthesis of carbon hollow structures, Inorg. Chem. 49 (2010) 8674e8683. M. Sun, D. Li, W. Li, Y. Chen, Z. Chen, Y. He, X. Fu, New photocatalyst, Sb2S3, for degradation of methyl orange under visible-light irradiation, J. Phys. Chem. C 112 (2008) 18076e18081. Y.Y. Lee, J.H. Moon, Y.S. Choi, G.O. Park, M. Jin, L.Y. Jin, D. Li, J.Y. Lee, S.U. Son, J.M. Kim, Visible-light driven photocatalytic degradation of organic dyes over ordered mesoporous CdxZn1exs materials, J. Phys. Chem. C 121 (2017) 5137e5144. S. Cui, G. Shan, L. Zhu, Solvothermal synthesis of I-deficient BiOI thin film with distinct photocatalytic activity and durability under simulated sunlight, Appl. Catal. B Environ. 219 (2017) 249e258. J.b. Zhong, J.z. Li, F.m. Feng, Y. Lu, J. Zeng, W. Hu, Z. Tang, Improved photocatalytic performance of SiO2eTiO2 prepared with the assistance of SDBS, J. Mol. Catal. A Chem. 357 (2012) 101e105. H. Wang, C. Xie, W. Zhang, S. Cai, Z. Yang, Y. Gui, Comparison of dye degradation efficiency using ZnO powders with various size scales, J. Hazard Mater. 141 (2007) 645e652.