Materials Letters 258 (2020) 126748
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UV light enabled photocatalytic activity of a-Fe2O3 nanoparticles synthesized via phase transformation Mohd Imran a, Ahmed Abutaleb a, Mohammed Ashraf Ali a, Tansir Ahamad b, Akhalakur Rahman Ansari c, Mohammad Shariq d, Dinesh Lolla e, Afzal Khan f,⇑ a
Department of Chemical Engineering, Faculty of Engineering, Jazan University, P.O. Box. 706, Jazan 45142, Saudi Arabia Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia Center of Nanotechnology, King Abdulaziz University, Jeddah 21589, Saudi Arabia d Department of Physics, Faculty of Science, Jazan University, P.O. Box. 706, Jazan 45142, Saudi Arabia e Biosciences and Water Filtration Division, Parker-Hannifin Corporation, Oxnard, CA 93030, USA f State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China b c
a r t i c l e
i n f o
Article history: Received 8 August 2019 Received in revised form 19 September 2019 Accepted 27 September 2019 Available online 27 September 2019 Keywords: Hematite Nanoparticles Phase transformation Photocatalyst UV irradiation FTIR
a b s t r a c t In this work, hematite (a-Fe2O3) nanoparticles (NPs) were synthesized by co-precipitation method involving chemical precipitation of aqueous salts of iron (Fe2+/Fe3+) using NaOH aqueous solution. The synthesis of a-Fe2O3NPs via phase transformation and its photocatalytic application under ultra violet (UV) light is rarely reported. The maximum removal of methylene blue (MB) dye (92%) was achieved at pH 10 and 200 mg amount of catalyst, whereas the concentration of dye was 10 ppm. The removal percentage of MB dye was found to vary with pH of the solution, concentrations of dye, and amount of a-Fe2O3 NPs for certain interval of time. Moreover, plot of ln(Ct/C0) Vs time exhibited almost a linear relationship between them which suggested the pseudo-first order kinetics reaction of photocatalytic degradation of MB. Ó 2019 Elsevier B.V. All rights reserved.
1. Introduction The photocatalytic degradation is one of the promising and efficient methods in confronting with environmental pollution especially the wastewater treatment. This method involves the generation of hydroxyl radicals which act as the primary oxidant for degrading organic pollutants. Various materials have been used as photocatalysts so far [1–4]. Asaithambi et al. [1] investigated the photocatalytic activity of the pure and Ni doped SnO2 NPs using MB dye under visible light irradiation. Balu et al. [2] reported the enhanced photocatalytic activity of core–shell structured SiO2@aFe2O3 nanocomposite on SnS2 flowers. Azeez et al. [3] investigated the photocatalytic activity of TiΟ2 NPs under different pH conditions (pH = 1.6, 7.0 and 10). Wang et al. [4] synthesized hexagonal BaAl2O4 catalyst using a gamma-ray irradiation assisted polyacrylamide gel method. Recently, Lassoued et al. [5] reported the photocatalytic activity of a-Fe2O3 NPs, under visible irradiation, and achieved 89% photocatalytic degradation of MB dye. Similarly, Vu ⇑ Corresponding author. E-mail address:
[email protected] (A. Khan). https://doi.org/10.1016/j.matlet.2019.126748 0167-577X/Ó 2019 Elsevier B.V. All rights reserved.
et al. [6] reported the photocatalytic activity of a-Fe2O3 nanospindles under UV irradiation, and achieved 78% photocatalytic degradation of MB dye after 6 h. In this work, we have synthesized a-Fe2O3 NPs by co-precipitation method via phase transformation of magnetite (Fe3O4). The magnetite transforms into maghemite (c-Fe2O3) if calcined above 200 , and it gets converted into the hematite phase above 500 °C [7–11]. Although it is quiet challenging to transform all the NPs into the a-Fe2O3 NPs completely, however, this can be achieved by controlling pH, concentration, types of iron salts, alkali solution, and reaction time. This work of photocatalytic activity of a-Fe2O3 NPs under UV light irradiation demonstrates the enhancement in the photocatalytic degradation rate of MB dye as compared to the previous reports. 2. Experimental Aqueous solutions of FeSO4.7H2O and FeCl3.6H2O (SigmaAldrich) were prepared by adding deionized water. Subsequently, 1 M solution of NaOH was added drop wise with the help of burette into the mixture of vigorously stirred iron salts. The whole
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mixture was stirred for another 1 h with the help of magnetic stirrer. The black precipitate of Fe3O4 collected with the help of a strong magnet, and washed with a mixture of deionized water and alcohol. After washing the mixture five times, precipitate was dried in an oven for 24 h at 100 °C. Finally, the precipitate was calcined in a muffle furnace at 550 °C for 4 h, and hematite NPs were obtained via phase transformation. As-synthesized NPs were characterized by various techniques (see Supporting information). Photocatalytic degradation of MB dye was carried out in a safeFAST Top 212 D device equipped with a UV lamp of 19 W (Philips; light intensity = 60.0 mW cm 2). An amount of 100 mg of photocatalyst was transferred into a 100 ml solution of (10 mg/L) MB dye. The UV lamp was localized above the beaker containing the solution. This suspension was centrifuged at 3000 rpm for 15 min to separate the photocatalyst NPs. 3. Results and discussions Fig. 1a & b show the low and high magnification TEM images of NPs, and the average particle size was observed to be ~42 nm. The lattice planes of one of the NPs are seen in HR-TEM image (Fig. 1c). The interplanar spacing was found to be 0.27 nm which corresponds to the most intense plane (1 0 4) of a-Fe2O3 NP. Fig. 1d shows the SAED pattern having many co-centric rings which confirmed the polycrystalline nature of the as-synthesized NPs. Fig. 2a shows the XRD pattern of the as-synthesized NPs, which also confirmed the polycrystalline nature of NPs like the TEM result (Fig. 1d). The important peaks positioned at 24.07°, 33.13°, 35.66°, 40.85°, 49.50°, 54.16°, 57.49°, 62.54°, 64.01°, 72.13° and 75.59° correspond to (0 1 2), (1 0 4), (1 1 0), (1 1 3), (0 2 4), (1 1 6), (0 1 8), (2 1 4), (3 0 0), (1010) and (2 2 0) lattice planes of pure a-Fe2O3 NPs (JCPDS card no. 33–0664) [5,12–14]. The UV–Vis spectrum of a-Fe2O3 NPs was observed in UV range (Fig. 2b). The light absorption in the UV range indicates the semiconducting nature of a-Fe2O3 NPs that can work effectively as
photocatalyst. The PL spectrum of the sample shows three different excitation and emission spectra (Fig. 2c). A very strong PL peak located at ~370 nm (~3.35 eV) comprises Fe (3d) and O (2p) states in valance band, and Fe (4 s) states in conduction band. The recombination of electron and hole in the exciton produces a red emission at ~370 nm attributed to the large particle size. The other weak intensity peaks at ~468 nm (~2.65 eV) and ~570 nm (~2.17 eV) aroused due to Fe3+ ligand field transition, and may be attributed to the small particles size of the sample [15]. Fig. 2d shows the N2 adsorption–desorption isotherms of the assynthesized a-Fe2O3 NPs with a hysteresis loop, indicating the presence of mesoporous structures. The BET surface area was found to be 84.2 m2/g which can effectively enhance the catalytic performance by providing more adsorption sites. It was observed that the rate of photocatalytic degradation of MB dye increased with increasing the pH of the solution (Fig. 3a). As the pH of the medium was increased, there was a corresponding increase in the concentration of OH– ions. These OH– ions were adsorbed on the surface of the semiconducting a-Fe2O3 NPs, made them negatively charged. This led to attraction between semiconductor surface and cationic dye, and resulted in increased rate of photocatalytic degradation of MB dye. The maximum degradation (72.4%) was observed at pH 10 after 16 h. Moreover, the photocatalytic degradation of MB dye was found to increase on decreasing the concentration from 10 to 2 ppm (Fig. 3b). As the concentration of dye was decreased, more molecules of photocatalyst were available to expose their surface area for excitation and consecutive energy transfer. This led to increase in the photocatalytic degradation of MB dye. Furthermore, it was observed that the rate of photocatalytic degradation of the MB dye increased initially with an increase in the amount of photocatalyst, but it became virtually constant after a certain amount (Fig. 3c). Around 92% degradation was achieved by using 200 mg amount of photocatalyst after 16 h. As the amount of photocatalyst increased, the exposed surface area of photocatalyst also increased. After a certain limit, the saturation point is
Fig. 1. (a,b) Low and high magnification TEM images (c) HR-TEM image, and (d) SAED pattern of a-Fe2O3 NPs.
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Fig. 2. (a) XRD pattern (b) UV–Vis spectrum (c) PL spectrum and (d) N2 adsorption-desorption isotherms of a-Fe2O3 NPs.
Fig. 3. Effects of (a) pH (b) dye concentration and (c) amount of catalyst on the degradation of MB under UV irradiation, respectively, and (d) recycle test of a-Fe2O3 NPs.
reached. The recycling test was done at the favorable condition (pH 10, 200 mg NPs and 10 ppm conc. of MB solution). The effect of photodegradation of each cycle is shown in Fig. 3d, where aFe2O3 NPs exhibited good reusability during four photodegradation
cycles. A plot of ln (Ct/C0) versus time was found to be almost linear (Fig. 4a-c) which indicates that the MB photocatalytic degradation reaction followed the pseudo-first order kinetics (see Supporting information) [5,16,17].
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Fig. 4. Plot of ln(Ct/C0) Vs time with respect to the effects of (a) pH (b) dye concentration and (c) amount of a-Fe2O3 NPs, respectively.
4. Conclusions
References
In conclusion, a-Fe2O3 NPs were synthesized by coprecipitation method using two iron salts via phase transformation at 550 . These as-synthesized a-Fe2O3 NPs were used for photocatalytic degradation of MB dye under UV light irradiation. The photocatalytic degradation of MB dye was observed to increase with increase in pH of the MB solution. 92% of photocatalytic degradation of MB dye was achieved at pH 10 using 200 mg of photocatalyst for 10 ppm MB dye concentration. The photocatalytic degradation of MB dye was found to follow the pseudo-first order kinetics reaction.
[1] S. Asaithambi, R. Murugan, P. Sakthivel, M. Karuppaiah, S. Rajendran, G. Ravi, J. Nanosci. Nanotechnol. 19 (2019) 4438. [2] S. Balu, K. Uma, G.T. Pan, T. Yang, S. Ramaraj, Mater 11 (2018) 1030. [3] F. Azeez, E. Al-Hetlani, M. Arafa, Y. Abdelmonem, A.A. Nazeer, M.O. Amin, M. Madkour, Sci. Rep. 8 (2018) 7104. [4] S. Wang, H. Gao, L. Fang, Y. Wei, Y. Li, L. Lei, Z. Phys. Chem. (2019), https://doi. org/10.1515/zpch-2018-1308. [5] A. Lassoued, M.S. Lassoued, B. Dkhil, S. Ammar, A. Gadri, J. Mater. Sci.: Mater. Elect. 29 (2018) 8142. [6] X.H. Vu, L.H. Phuoc, N.D. Dien, T.T. Pham, L.D. Thanh, J. Elect. Mater. 48 (2019) 2978. [7] M.I. Dar, S.A. Shivashankar, RSC Adv. 4 (2014) 4105. [8] R. Sharma, V.V. Agrawal, A.K. Srivastava, L. Nain, M. Imran, S.R. Kabi, R.K. Sinha, B.D. Malhotra, J. Mater. Chem. B 1 (2013) 464. [9] M. Imran, A.R. Ansari, A.H. Shaik, S. Hussain, A. Khan, M.R. Chandan, Mater. Res. Exp. 5 (2018) 036108. [10] M. Imran, A.H. Shaik, A.R. Ansari, A. Aziz, S. Hussain, A.F. Abouatiaa, A. Khan, M. R. Chandan, RSC Adv. 8 (2018) 13970. [11] A. Abutaleb, Mater. Res. Exp. 6 (2019) 046101. [12] J. Hua, J. Gengsheng, Mater. Lett. 63 (2009) 2725. [13] T. Almeida, M. Fay, Y.Q. Zhu, P.D. Brown, J. Phys. Chem. C 113 (2009) 18689. [14] A.S. Teja, P.Y. Koh, Prog. Cryst. Growth 55 (2009) 22. [15] L.E. Mathevula, L.L. Noto, B.M. Mothudi, M. Chithambo, M.S. Dhlamini, J. Luminesc. 192 (2017) 879. [16] R. Ameta, J. Vardia, P.B. Punjabi, S.C. Ameta, Ind. J. Chem. Tech. 13 (2006) 114. [17] A. Rameshwar, K. Dileep, J. Priyanka, Acta Chim. Pharmaceutica Indica 4 (2014) 20.
Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgements The authors would like to thank SABIC Company and Jazan University for financial support (Grant No. SABIC 3/2018/1). Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.matlet.2019.126748.