Effect of iron chlorine concentration on type of green synthezed iron oxides nanoparticles using pheonixdactylifera l leaves extract
A. Labbia,b, B. Benhaouaa,c, K. Ahmoudab, Y.Meftaha,b, Kh. Benhaouab,c,*
aLab. VTRS, Faculty of Technology, Univ. El-Oued, El oued 39000, Algeria
bFaculty of Exact Sciences, Univ. El-Oued, El oued 39000, Algeria
cUnité de Developpement des Energies Renouvelabes dans les Zones Arides, El oued 39000, Algeria
Iron oxide nanoparticles (NPs) were prepared by green synthesis process, using Pheonix Dactylifera. L. leaves ethanolic extractas polyphynols source and FeCl3 aqueous solution as precursor, where the volume ration was 1:2. The concentration of FeCl3 was varied as follow: (0.01, 0.02, 0.03 and 0.04M). To charactrizethe obtained iron oxide NPs, XRD, SEM, UV-VIS and FTIR techniques were used. XRD analyses show the existence of three essentials compounds of iron oxide NPs: maghemite phase, hematite phase and beta phase. While the grain size of these compoundswas varied in the ranges of 22.91-37.40nm, 20.41-31.32nm and 17.96-25.25nm respectively. SEM images analysis showed that all samples have spherical shaped particles. UV-VIS analysis showed that the variation of FeCl3 concentration hasdirecteffect on theband gap of the product which rangeedin the range 2.162-2.358eV, whereas FTIR study confirms the abundance of Fe-O bonds in all samples.
(Received July 1, 2021; Accepted December 15, 2021)
Keywords
:
Iron oxides nanoparticules, Maghemite Fe2O3, Hematite Fe2O3, beta-Fe2O3, Green synthesis, Pheonix dactylifera. L1. Introduction
In general NPs have an enhanced magnetic, optical, electronic, catalytical and biological properties that differ from those in the massif materials, due to their size and shape characteristics.
In the last years, NPs have taken a lots of interest because of their use in different applications due to their distinguishable properties which offerthem a higher intrinsic reactivity via their surface sites area [1]. Particularly iron oxides NPs are widely used in a specific fields applications, such as biomedical field: treatment of hyperthermia for cancer cells [2, 3],in molecular biology [4, 5]
(DNA and cell purification, protection of human cells from ultraviolet rays),in earth science [6]. In industry, NPs are also used to develop magnetic recording applications [7], magnetic refrigeration [8], catalysis [9], ion recovery [10], magnetic membranes [11], gas detectors [12], bacterial reagents [13, 14], treatment of water from microbial contamination [15, 16].
There are many physical and chemical methods which are implied in NPs synthesis. The two methods are expensive and use special equipment that require high energy and involve hazardous, corrosive and flammable chemicals materials [17]. Moreover, using the above- mentioned methods are likely to arise conglomerates that reduce the surface reactivity and instability of these particles [18]. Also, the sizes, morphologies, shapes, compositions and cristalinty of nano materials, are depend on the used techniques, which are highly affect the products properties. The cited methods sufferd from an inability to control NPs size. Composition and size contrl need others methods such as green one…. It is worth noting that green synthesis is adopted for this purposes due to greater stability of the products and their low costs without toxicity. Stability of the products refers to phytochemical compounds from food sources such as peel [19], fruits [20], and seeds [21]. Palm leaves (Pheonix dactylifera. L) are fewly used to
* Corresponding author: [email protected]
synthesis NPs [22]. Iron oxide NPs greenly synthesized using difrent extract become today as attractif field for researchers[23]. Even though green synthesis of iron nanoparticles has emerged using different parts of the plant and herbal materials (such as stems, roots, leaves, and seeds), which are a simple, low cost, more safety, and environmentally friendly compared to the previous cited methods [24].The metal oxides morphology can be affected by several factors, including: the effect of the ratio between the plant extract and the precursor [22], the effect of extract plant [25],the effect of precursor concentration [26], the effect of precursor type [27], the effect of the solvent [28], the effect of the reaction time [29], the effect of the temperature of the reaction [30], the effect of PH [31], the effect of the annealing time [32], the effect of the annealing temperature [33].
The aim of this work is to study the physical properties of iron oxide nanoparticles greenly synthesized by reacting the ethanolic extract of Pheonix dactylifera. L with different iron chloride (FeCl3) salt concentration in aqueous solution. The effect of FeCl3 salt concentration within the extract and the 500°C annealed products for one hours, will be analysed using XRD, UV–VIS, SEM and FTIR.
2. Experimental details
2.1. Preparing and extracting plant materials
Palm leaves (Pheonix dactylifera. L) were collected from local farms in El Oued province, Algeria. Firstly, they are washed several times with tap water and distilled water to remove dust, dirt and impurities suspended to them. The palm leaves are cut into medium pieces and dried at room temperature for 10 days, then grinded to get the palm leaves sheet powder. Extraction operation palm leaves was proceed to have leaves extract by placing 50g of the previous powder with 300ml of ethanol in a 1000ml glass jar with continuous stirring for a full day at room temperature. Finally, this mixture is filtered and considered as liquid ethanolic leaves extract (L.E.L.E) mother sources for use.
2.2. Preparation of iron oxide nanoparticles
For each experimentation, iron oxides NPs are synthesized by mixing 40ml of the (L.E.L.E) with 80ml FeCl3 aqueous solution at known concentrations (0.01, 0.02, 0.03, and 0.04M). The mixture has obeing to continuous stirring, in a water bath system at 70°C, for one hour. Iron oxides particles formation starts when the change in the color of the mixture, from green to dark brown, appears. After that, the blend was dried and the resudial products was washed several times with double distilled water and collected by centrifugation. The collected product was dried again at 90-100°C inside the drying oven. Then the dried product was obeing to a second annealing treatment at 500°C for an hour. Photos of the prepared powders of iron oxides NPs for different FeCl3 concentrations are shown in Fig. 1.
Fig. 1. Photos of the prepared powders for FeCl3 concentrations.
2.3.Characterizationof iron oxides nanoparticles
The band gap energy has been estimated through the optical transmittance spectrum using (UV–VIS spectrophotometer Shimadzu, Model 1800) operating in the wavelength 200-900nm range.To find out iron oxides crystal structureXRD technique was employed using Xray diffractometer (RigakuMiniflex 600) apparatus with a Cu-Kα (λ = 1.5406 Å) operating in the 2θ
angles of 10° to 90° range, and (30keV, 30mA) as conditions of X-ray generation. Chemical bonds of iron oxides NPs were determined by their vibration in 400-4000cm-1 infrared spectrum which was scanned by a device (Nicolet iS5, Thermo Fisher Scientific). The surface investigation was done with scannng electron microscopie (SEM-TESCAN VEGA 3), all measurements are done at room temperature.
3. Results and discussion
3.1. Structural properties
Fig. 2 The XRD patterns of powders treated for 1h at 500°C are shown in Fig.2.XRD peaks show the existence of three iron oxide essentials compounds:
Gamma phase, maghemite (γ-Fe2O3) having a tetragonal crystalline structureaccording to JCPDS No: 00-025-1402 where peaks appearat 2θ: 30°.214, 35°.683, 57°.
307, and 62°.885correspond to lattice plane of (206), (119), (1115) and (4012), respectively;
Alpha phase, hematite (α-Fe2O3) having a rhombohedral crystalline structure JCPDS No: 01-089-0598 where peaks appear at 2θ: 33°.130, 35°.683, 40°.951, 49°.405 and 64°.003 correspond to lattice plane of (104), (110), (113), (024) and (300), respectively;
Beta phase, β-Fe2O3 having a cubic crystalline structure according to JCPDS No:
00-039-0238 appears peaks at 2θ: 33°.082, 38°.296, 55°.129, and 65°.945correspond to lattice plane of (222), (400), (440) and (622), respectively. It is worth noting that for XRD reflection at 38.871° which is related to gamma phase is excluded because of its considerable shift.
10 20 30 40 50 60 70 80 90
0 300 600 900
0.04 M post annealing 1h
0.03 M post annealing 1h 0.02 M post annealing 1h 0.01 M post annealing 1h
Intensity (a.u)
2 theta degree)
JCPDS N: 00.039-0238 JCPDS N: 00.089-0598 JCPDS N: 00.025-1402
Fig. 2. X-ray diffraction patterns of samples 0.01, 0.02, 0.03 and 0.04M.
(γ: γ-Fe2O3, α: α-Fe2O3, β: β-Fe2O3).
The lattices constant (a and c), for the tetragonal phase structure, are determined by the relations [34]:
𝟐𝒅𝒉𝒌𝒍𝐬𝐢𝐧(𝜽) = 𝒏𝝀 (1) and
𝟏
𝒅𝒉𝒌𝒍𝟐=𝒉𝟐+𝒌𝟐
𝒂𝟐 +𝒍𝟐
𝒄𝟐 (2)
where ‘dhkl’and (hkl) are the inter-planer distance and Miller indices, respectively. The values of lattice parameter ‘a’ and ‘c’ arelisted in Table1.Values of a and c are (a =b =8.3383Å, c = 25.0151Å) for instance in the case of 0.04M sample; they are the most close to the values of standard JCPDS data card, (a0 =b0 = 8.3400Å, c0 =25.0200Å).
The lattice constants (a and c), for the rhombohedral phase structure, are determined by the relations [35]:
𝟏 𝒅𝒉𝒌𝒍𝟐= 𝟒
𝟑𝒂𝟐(𝒉𝟐+ 𝒌𝟐+ 𝒉𝒌) +𝒍𝟐
𝒄𝟐 (3)
The values of lattice parameter ‘a’ and ‘c’ are illustrated in Table 1. Values of a andc are (a = b = 5.0339Å and c = 13.7892Å) in the case of 0.03M sample; they are the most close to the values of standard JCPDS (a0 =b0= 5.0380 Å and c0 = 13.7760Å).
For the beta phase structure, the lattice constant a is determined by the following relations of cubic unit [36]:
𝟏 𝒅𝒉𝒌𝒍𝟐= 𝟏
𝒂𝟐(𝒉𝟐+ 𝒌𝟐+ 𝒍𝟐) (4) Values of a, are illustrated in Table 1. In the case of 0.01M sample, a is about 9.4022Å which is closely equal to 9.4040 Å of the JCPDS No: 00-039-0238 one.
The crystalline sizes of the powders, with different concentrations, are given in Table 1, they are calculated using Scherrer’s formula[37]:
𝑫 = 𝟎.𝟗 𝝀
𝜷𝒄𝒐𝒔𝜽 (5) where D, β, λ, and θ are the crystallite size, the full width at half-maximum (FWHM) of diffraction peaks, the X-ray wavelength (1.5406Å) and Bragg angle, respectively. For gamma and beta Fe2O3
phases the most intense diffraction peaks are only taken in consideration which are (119) and (222), respectively. Whereas for alpha phase the crystallite size averages were taken with the help of the two peaks (104) and (110). The calculated crystallite sizes from the considered peaks are listed in Table 1. For more focus on the effect of concentration on the gain size of the products, it was remarked that the later has the same effect on all phases gain size variation as exhibited in Fig.3.
Table 1.Crystallographic data obtained from XRD.
Sample Phases present
Grain size (nm)
Calculated d (Å)
Standard d (Å)
Lattice parameter a (Å), b (Å), c (Å) 0.01 M γ-Fe2O3 37.39043 2.51576 2.51400 a = b = 8.3438, c = 25.0314
α-Fe2O3 31.32887 2.71418 2.70329 a = b =5.0315, c = 13.8775
β-Fe2O3 25.25763 2.71418 2.71400 a = 9.4022
0.02 M γ-Fe2O3 25.94565 2.51383 2.51400 a= b = 8.3374, c = 25.0123 α-Fe2O3 22.24205 2.70650 2.70329 a = b =5.0361, c = 13.8101
β-Fe2O3 18.54299 2.70650 2.71400 a = 9.3756
0.03 M γ-Fe2O3 22.91024 2.51698 2.51400 a= b = 8.3374, c =24.9904 α-Fe2O3 20.43640 2.70409 2.70329 a = b =5.0339, c = 13.7892
β-Fe2O3 17.96256 2.70409 2.71400 a = 9.3671
0.04 M γ-Fe2O3 34.36907 2.51679 2.51400 a= b =8.3383, c = 25.0151 α-Fe2O3 26.89509 2.70397 2.70329 a = b =5.0336,c = 13.7892
β-Fe2O3 19.42119 2.70397 2.71400 a = 9.3668
0,01 0,02 0,03 0,04 15
20 25 30 35 40
Grain size(nm)
Concentration(M) Grain size of g Grain size of a Grain size of c
Fig. 3. Grain size with various concentration (γ: γ-Fe2O3,α: α-Fe2O3, β:β- Fe2O3).
3.2.Surface morphology
The surface morphology of iron oxide powders are studied using SEM images,for different maghification 5µm for the first concentration and 1µm for the rest, Fig. 4a-d shows the results with different concentrationofFeCl3: 0.01,0.02,0.03 and 0.04M, respectively. It is clear that iron oxides NPs are mainly present as granules with spherical shaped particles.The agglomeration of particules behaves as in the case of XRD. They begun with spherical shaped particles of about 1.2 µm then decreases to 0.8- 0.5µm for concentration of 0.02, 0.03M and increases to attain 1 µm for the concentration of 0.04M. To have idea about the composition of NPs, EDAX for one sample is reported in this study; it reveals that the samples are composed of iron and oxygen in atomic rate of 2, as shown in the EDAX table below (Fig. 4e ), which means a non stichiometric compostion of the elaborated iron oxides NPs. As it was shown from the XRD study that the co-existance of three types of iron oxides NPs which are γ, α and β-Fe2O3 and the same behaving of the grain seize (XRD) and the agglomeration under its spherical shaped particles (MEB) within the FeCl3
concentration; it may be proclaimed that the co-existance of the three species was at the origin of the spherical shapes.
(a) (b) (c )
(d ) (e)
Fig. 4: Scanning electron microscopic images of iron oxide NPs powders:(a) 0.01, (b)0.02, (c)0.03 and (d) 0.04M., (e) EDAX of arbitrary choosen sample.
3.3. Optical properties
In order to investigate the band gap of the iron oxide NPs powders, Tauc’srelation is used [38]:
𝜶𝒉𝝂 = 𝑨(𝒉𝝂 − 𝑬𝒈)𝒏 (6) where α, h, ν, and Eg are the absorption parameter, Planck constant, the photon frequency and gap energy, respectively; A is a constant and n is taken 1/2 based on consideration that γ-Fe2O3 and α- Fe2O3 have direct gap [38, 39]. The optical absorption data was used to generate plots of(αhν)2vs(hν), as shown in Fig.5. leading to band gap energy which was estimatedby extrapolating the streigh line of (αhν)2 to hν axis. Optical values of the elaborated samples are given in Table 2. As shown leading to band gap energy of 2.162 , 2.295, 2.358, and 2.218eV for concentrations0.01, 0.02, 0.03, and 0.04M, respectively. Those values are in agreement with several previous works [39-42].
1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8 3,0 3,2 3,4 3,6 3,8 0
20 40 60 80 100 120 140 160 180 200
h)eV.cm-1)
heV) 0.01M post anneling 1h 0.02M post anneling 1h 0.03M post anneling 1h 0.04M post anneling 1h
Fig. 5. Band gap (Eg) estimation from Tauc's relation for iron oxide NPs Powders.
Table 2. Optical gap of green synthesized iron oxide NPs.
Concentration (M) Optical gap Eg(eV)
0.01 2.162
0.02 2.295
0.03 2.358
0.04 2.218
3.4. FTIR
Fig.6 shows FTIR spectrum of the synthesized samples with different precursor concentrations. The bands in the range of 400-900 cm-1 are related to Fe-O lattice vibration. As exhibits in the figure bands at 562, 633 and 692 cm-1 are related at maghemite phase formation whereas bands at 542, 573cm-1 describes the formation of hematite phase [43] and band 528cm-1 is related at beta phase [44]. The peak 800 cm−1 is related to O-H out of plane bond [43].
Absorption peaks at 1106 and 3420 cm-1 also appeared, may be they assigned to C-O vibration mode [45], and to O-H stretching vibration [46].
4500 4000 3500 3000 2500 2000 1500 1000 500 528
800 700 600
60 70 80 90
Transparency( a.u)
Wave number (cm-1)
562542 692 800
633 573 1106
Wave number (cm-1 )
Transparency( a.u)
0.01 M post annealing 1h 0.02 M post annealing 1h 0.03 M post annealing 1h 0.04 M post annealing 1h
Fig. 6. FTIR spectrum of iron oxides NPspowdes for (0.01-0.04M) post annealing at 500°C.
4. Conclusion
In this work, Iron oxide NPs powders were synthesized by green synthesis method using the extract of pheonix dactylifera.L with a triple iron chlorine solution. The effect of salt concentration in the extract for concentrations: 0.01M, 0.02M, 0.03M, and 0.04M of post heat treatment at 500°C on their structural and optical properties have been studied. XRD analyses affirmed the formation of three iron oxide NPs essentials compounds: maghemite phase, hematite phase, and beta phase whereas the grain size varies upon iron chlorine concentration and it was arranged in 22.91-37.40nm, 20.41-31.32nm and 17.96-25.25nm respectively. SEM images showed that all samples having spherical shaped particles. Withdirect band gap in the range of 2.162- 2.358eV. FTIR spectrum affirms the abundance of Fe-O bond.
References
[1] X. Zhang, S. Lin, Z. Chen, M. Megharaj, R. Naidu, Water Research 45(11),3481 (2011).
[2] S. Mornet, S. Vasseur, F. Grasset, P. Veverka, G. Goglio, A. Demourgues, J. Portier, E. Pollert, E. Duguet, Progress in Solid State Chemistry 34(2-4),237 (2006).
[3] J. Petr, B. Teste, S. Descroix, J.M. Siaugue, P. Gareil, A. Varenne, Electrophoresis 31(16), 2754 (2010).
[4] H. Parrot-Lopez, F. Perret, B. Bertino-Ghera, Annales pharmaceutiques françaises 68, 12(2010).
[5] S. Laurent, D. Forge, M. Port, A. Roch, C. Robic, L. Vander Elst, R.N. Muller, Chemical reviews 108(6),2064 (2008).
[6] K.-J. Lee, J.-H. An, J.-S. Shin, D.-H. Kim, C. Kim, H. Ozaki, J.-G. Koh, Nanotechnology 18(46),465201 (2007).
[7] R.J. Veitch, IEEE transactions on magnetics 37(4),1609 (2001).
[8] G. Bisio, G. Rubatto, P. Schiapparelli, Energy conversion and management40(12), 1267 (1999).
[9] M.-H. Liao, D.-H. Chen, Journal of Molecular Catalysis B: Enzymatic18(1-3),81 (2002).
[10] M. Takafuji, S. Ide, H. Ihara, Z. Xu, Chemistry of materials 16(10),1977 (2004).
[11] E. Sourty, D. Ryan, R. Marchessault, Cellulose5(1),5 (1998).
[12] K. Široký, J. Jirešová, L. Hudec, Thin Solid Films245(1-2),211 (1994).
[13] M. Arakha, S. Pal, D. Samantarrai, T.K. Panigrahi, B.C. Mallick, K. Pramanik, B. Mallick, S. Jha, Scientific reports5(1),1 (2015).
[14] P. Xu, G.M. Zeng, D.L. Huang, C.L. Feng, S. Hu, M.H. Zhao, C. Lai, Z. Wei, C. Huang, G.X. Xie, Science of the Total Environment 424(1),1 (2012).
[15] K. Al-Saad, M. Amr, D. Hadi, R. Arar, M. Al-Sulaiti, T. Abdulmalik, N. Alsahamary, J. Kwak, Arab Journal of Nuclear Sciences and Applications 45(2),335 (2012).
[16] W. Yan, A.A. Herzing, C.J. Kiely, W.-x. Zhang, Journal of Contaminant Hydrology 118(3-4), (2010).
[17] T. Shahwan, S.A. Sirriah, M. Nairat, E. Boyacı, A.E. Eroğlu, T.B. Scott, K.R. Hallam, Chemical Engineering Journal 172(1),258 (2011).
[18] D. O’Carroll, B. Sleep, M. Krol, H. Boparai, C. Kocur, Advances in Water Resources 51(1), 104 (2013).
[19] Y. Wei, Z. Fang, L. Zheng, L. Tan, E.P. Tsang, Materials Letters 185(1),384 (2016).
[20] E. Rostamizadeh, A. Iranbakhsh, A. Majd, S. Arbabian, I. Mehregan, Journal of Nanostructure in Chemistry, 1 (2020).
[21] R. Rahmani, M. Gharanfoli, M. Gholamin, M. Darroudi, J. Chamani, K. Sadri, Journal of Molecular Structure1196(1),394 (2019).
[22] D. Berra, S. Laouini, B. Benhaoua, M. Ouahrani, D. Berrani, A. Rahal, Digest Journal of Nanomaterials and Biostructures13(4),1231 (2018).
[23] A. Bouafia, S.E. Laouini, A. Khelef, M.L. Tedjani, F. Guemari, Journal of Cluster Science, 1 (2020).
[24] K.M. Kumar, B.K. Mandal, K.S. Kumar, P.S. Reddy, B. Sreedhar, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy102(1),128 (2013).
[25] N.Y. Stozhko, M.A. Bukharinova, E.I. Khamzina, A.V. Tarasov, M.B. Vidrevich, K. Z. Brainina, Nanomaterials9(12),1655 (2019).
[26] R.B. Ayed, M. Ajili, N.K. Turki, Physica B: Condensed Matter 563(1),30 (2019).
[27] X. Qin, Y. Ju, S. Bernhard, N. Yao, Journal of materials research 20(11),2960 (2005).
[28] A.U. Limaye, J.J. Helble, Journal of the American Ceramic Society 86(2),273 (2003).
[29] V. Karade, T. Dongale, S.C. Sahoo, P. Kollu, A. Chougale, P. Patil, P. Patil, Journal of Physics and Chemistry of Solids 120(1),161 (2018).
[30] A. Samy, A.E. El-Sherbiny, A. Menazea, Egyptian Journal of Chemistry 62,29 (2019).
[31] M.S.F.A. Zamri, N. Sapawe, Materials Today: Proceedings 19(1),1321 (2019).
[32] A. Jafari, S.F. Shayesteh, M. Salouti, K. Boustani, Journal of Magnetism and Magnetic Materials379(1),305 (2015).
[33] T.M. Laid, K. Abdelhamid, L.S. Eddine, B. Abderrhmane, Journal of Molecular Structure 1229(1),129497 (2021).
[34] C. Kittel, P. McEuen, P. McEuen, Wiley New York, 1996.
[35] L. Dghoughi, B. Elidrissi, C. Bernede, M. Addou, M.A. Lamrani, M. Regragui, H. Erguig, Applied Surface Science253(4),1823 (2006).
[36] A. Sadanandan, M.J. Mathew, AIP Conference Proceedings, AIP Publishing LLC,1, 20157(2019).
[37] M. Abdullah, K. Khairurrijal, Jurnal Nanosains & Nanoteknologi1(1),28 (2009).
[38] J. Tauc, R. Grigorovici, A. Vancu, physica status solidi B15(2),627 (1966).
[39] P. Mallick, B. Dash, Nanosci. Nanotechnol.3(5),130 (2013).
[40] R.N. Goyal, D. Kaur, A.K. Pandey, Materials Chemistry and Physics 116(2-3),638 (2009).
[41] J. Liu, H. Yang, X. Xue, Materials Letters229,156 (2018).
[42] Z. Wei, X. Wei, S. Wang, D. He, Materials Letters 118,107 (2014).
[43] M. Ates, I.C. Cimen, I. Unal, B. Kutlu, B. Ertit Tastan, D. Danabas, O. Aksu, Z. Arslan, Environmental toxicology 35(3),385 (2020).
[44] W.J. Aziz, M.A. Abid, D.A. Kadhim, M.K. Mejbel, Materials Science and Engineering IOP Publishing881(1),12099(2020).
[45] A.T. Khalil, M. Ovais, I. Ullah, M. Ali, Z.K. Shinwari, M. Maaza, Green Chemistry Letters and Reviews10(4),186 (2017).
[46] J. Ding, Q. Zhong, S. Zhang, Journal of Molecular Catalysis A: Chemical393,222 (2014).
