GREEN SYNTHESIS AND CHARACTERIZATION OF ZERO VALENT IRON NANO PARTICLES FROM THE PEEL EXTRACT OF MUSACEAE (BANANA) Satarupa Sahu M-tech Scholar Dept of Chemical Engineering N.I.T, Raipur, Chhatisgarh Chandrakant Thakur Assistant Professor Dept of Chemical Engineering N.I.T, Raipur, Chhatisgarh S.Noyel Victoria Assistant Professor Dept of Chemical Engineering N.I.T, Raipur, Chhatisgarh ABSTRACT Recently, the research trend is centralised towards the green synthesis of nano particles involving plant extract with minimal impact and cost. In this presented research work, a novel route for synthesis of iron nano particles using the peel extract of banana has discovered. Characterization of synthesized nano particles was done using XRD, FTIR, EDX and SEM techniques. The change of colour from brown to black was significant for synthesis of nano particles. From this present study, it is confirmed that the nano particle synthesised from banana peel extract is very eco-friendly as well as cost effective and thus can be used as effective alternative for the large scale production of iron nano particles. Keywords Iron nano particle; Banana peel; Green chemistry; Nano technology; Characterization INTRODUCTION Nanotechnology implies the manipulation of matter at the atomic, molecular level by the utilization of materials, devices and systems in order to have nano meter-length products [5]. Nano particles because of its specific physicochemical characteristics such as smaller size, higher surface area to volume ratio, higher reactivity are highly implemented in various fields of biotechnology, sensors, medical treatment, catalysis reactions, optical devices, DNA labelling, drug manufacturing [9]. Although the manufactured nano particles by lithography, UV irradiation, laser ablation, ultrasonic fields, aerosol technologies and photochemical reduction techniques have produced excellent results, still they are expensive for production and involvement of the hazardous chemicals leads to environmental concern. Hence, research trend is shifting towards the evolution of eco-friendly and reasonable methods for production of zero valent iron nano particles [7] with minimal toxicity level of the synthesised product, manageable environmental impact of the by-products and also the cost of production [8]. To achieve this goal, anti toxic solvents (mostly water), air tide reacting vessals and green techniques without contact of reaction media and air (hydrothermal, magnetic, ultrasonic, microwave, biological methods), and lower temperatures can be employed [4].The technique of manufacturing nano particles from naturally occurring products and by-products such as various plant extracts, soil, sand, biodegradable polymers, waste and microorganisms is called green synthesis of nano particle [6]. Green chemistry aims to reduce pollution at source and to prevent waste than to treat or clean up waste after it is formed. Green synthesis offer better manipulation and control of crystal growth over physical and chemical methods. This technique has opened a novel synthetic route in research to have better control of shape and size for various nano technological applications [10]. The present research work has demonstrated a greener route for synthesis of zero valent iron nano particles (ZVINP) using the peel extract of banana. Reaction between aqueous Ferric Chloride solution and banana peel extract, led to rapid formation of highly stable, crystalline zero valent iron nano particles. The production rate was very high that it justifies implication of green technology over physical method in the synthesis of metal nano particles to be cheeper and safer. In the following sections, the synthesis of iron nanoparticles based upon the change in color and its characterization by SEM, XRD, FTIR and EDX are described. Figure 1 showing banana peel. 12
Plant Description: Bionomial Name: Musa paradisiaca Common Name: Banana peel Plant part taken: peel Family Name: Musaceae Figure 1. Banana peel 2. EXPERIMENTAL METHODS 2.1 Reagents All chemicals (sodium borohydride, nitric acid and ferric chloride hexa hydrate) used in this work were purchased from Kasliwala Brothers, Raipur. Banana peels were collected from local market, homes. All Borosil lined glass wares were purchased from Kasliwala Brothers, Raipur. Before conducting experiments, all glass wares should be washed with dilute nitric acid and distilled water. 2.2 Preparation of Banana peel Extract To prepare the banana peel extract; banana peels were collected from homes, markets, etc. About 75 percent of the weight of a banana is water. Banana peel contains various components and minerals as follows in Table 1. Table 1.Component present in banana peel Components Percentage Minerals Amount present present Lipids 1.7 Potassium 78.10mg/g Proteins 0.9 Manganese 76.20mg/g Crude fiber 31 Sodium 24.30mg/g Carbohydrate 59 Calcium 19.20mg/g The collected peels were washed with tap water followed by distilled water many times in order to remove contaminants. The banana peels were cut in to small pieces of size (3-5) cm and dried in an air oven at 100 0 C for 24 hours. The moisture content was reduced to a higher extent after 24 hours which can be observed from the significant color change i.e from yellowish to brownish black [1]. The oven dried peels were crushed in mixture and screened through 125μm ASTM sieve. 2.3 Synthesis of Zero Valent Iron Nano particles Zero valent iron nano particle (ZVINP) was prepared by reduction method using peel extract, two main chemicals which were FeCl 3 and NaBH 4 followed by the method proposed by [2].In the experiment, 0.05gm of peel extract, equal volume of 0.94M sodium boro-hydride (NaBH 4 ) and 0.18M of ferric chloride (FeCl 3 ) were added to a 250ml beaker and NP particles were synthesized in the laboratory via the following reaction: 4Fe 3+ (aq)+3bh - 4+9H 2 O 4Fe 0 (s) + 3H 2 BO 3 +12H + (aq)+ 6H 2 (g) (1) The borohydride solution was added in drop wise manner into the iron chloride with intense mixing in ultra sonicator. Mixing for a period of a 15 20 min produces the maximum yield of black iron nano particles coated banana peel (NBP). Particles were then separated from the solution by using What-mann filter paper 13
(0.2 mm). The solid particles were washed many times with absolute ethanol to remove all water and dried in oven. Figure 2 showing particles of ZVINP. Figure.2 ZVINP powder 3. RESULT AND DISCUSSION 3.1 Characterization of banana peel and ZVINP SEM plots of the two adsorbents synthesized reveal that both contain the morphological properties that should be necessary for metal adsorption to take place. Figure 3 shows heterogenous porous surface of banana peel with a mean particle diameter of 10μm. Figure 4 is showing a much smoother surface of ZVINP with a mean particle diameter of 1μm. Figure 3. Schematic diagram showing the SEM plot of banana peel Sharp peaks were not observed in XRD plot of the ZVINP which indicated that the product is of amorphous nature (Figure 6). The diffraction patterns of banana peel (Figure 5) at 26.11 0, 50.3068 0 and 68.11 0 values correspond to inter layer distances of 3.067, 1.770 and 1.252Å respectively. The average particle size d of the banana peel was estimated to be 2.02 Å by using the standard Debye Scherrer equation. d = kλ β cos θ (2) where d is the particles size, k is the Debye Scherrer constant (0.89),λ is the X-ray wavelength (0.15406 nm) and β is the full width at half maximum, θ is the Bragg angle. Figure 4. Schematic diagram showing the SEM plot of ZVINP 14
Figure 5. Schematic diagram showing the XRD plot of banana peel FTIR plot of banana peel(figure 7) shows presence of functional groups such as OH group, C-H group, C-H group, N-H group, OH group, and aromatic ether group, epoxy group at 3411, 2926, 2880, 2289, 1619, 1399.1258, and 1035 respectively. FTIR plot of ZVINP(Figure8) shows presence of functional groups such as primary amine, C=C group,-oh group, -C-O- group, epoxy group at 3464, 1635, 1405, 1022, 913 respectively. Figure 6. Schematic diagram showing the XRD plot of ZVINP EDS plot shows that banana peel (Figure 9) contains higher percentage of carbon, silicon i.e 53.51, 39.79 respectively where as ZVINP(Figure 10) contains higher percentage of iron i.e 55.91. Figure 7.Schematic diagram showing the FTIR plot of banana peel 15
Figure 8.Schematic diagram showing the FTIR plot of ZVINP Figure 9.Schematic diagram showing the EDX plot of banana peel Figure 10.Schematic diagram showing the EDX plot of ZVINP 16
4. CONCLUSION The extract of banana peel is capable of producing zero valent iron nano particle. The color change was very prominent when ferric chloride was added to reducing agent i.e peel extract. The rapid rate of nano particle formation by green technology justifies implication of green technology over physical method in the biosynthesis of metal nano particles to be cheeper and safer. SEM plot and XRD of ZVINP show amorphous nature. FTIR plot of ZVINP shows presence of functional groups such as primary amine, C=C group,-oh group, -C-O- group, epoxy group. EDS plot shows that banana peel contains higher percentage of carbon, silicon where as NBP contains higher percentage of iron. REFERENCES [1] Darge, A., 2015, Treatment of Industrial Wastewater by using Banana Peels and Fish Scales, International Journal of Science and Research (IJSR) ISSN (Online): 2319-7064 [2] Azzam, A.M., 2016, Removal of Pb, Cd, Cu and Ni from aqueous solution using nano scale zero valent iron particles, Journal of Environmental Chemical Engineering 4 (2016) 2196 2206. [3] Al-Saadi, A., Yu, C.H., Shih, S., Qiu, L., Tam, K.Y., S.C. Tsang, S.C., 2009, Immobilization of BSA on silica coated magnetic iron nano particle, Journal of Physics. Chem. C-113 (2009) 537 543. [4] Carma, R.S., 2012, Greener approach to nanomaterials and their sustainable applications. Curr. Opin. Chem. Eng. 1, 123 128 [5] Chiu, D.T., 2010, Interfacing droplet micro fluidics with chemical separation for cellular analysis, Anal Bioanal Chem., 397, 3179-83. [6] Iravani, S., 2011, Green synthesis of metal nanoparticles using plants. Green Chem. 13, 2638 2650 [7] Narayanan, K.B., and Sakthivel, N., 2010, Biological synthesis of metal nanoparticles by microbes. Adv. Colloid Interface Sci. 156, 1 137 [8] Sanchez-Mendieta, V., and Vilchis-Nestor, A.R., 2012, Green synthesis of noble metal (Au, Ag, Pt) nanoparticles, assisted by plant-extracts. In Noble Metals (Yen-Hsun, S., ed.), pp. 391 408, INTECH [9] Yasin, S., Lin Liu, L., andyao,j.,2013, Biosynthesis of Silver nanoparticles by Bamboo Leaves Extract and Their Antimicrobial Activity, Journal of Fibre Bioengineering and Informatics Vol. 6:1, 77-84. [10] Oxana, V.K.,2013, The greener synthesis of nanoparticles Trends in Biotechnology April 2013, Vol. 31, No. 4 17