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Characterization and application of biosynthesized iron oxide nanoparticles using Citrus paradisi peel: A sustainable approach

https://doi.org/10.1016/j.inoche.2020.108116Get rights and content

Highlights

  • First report on Biosynthesis of Iron oxide nanoparticles using peel extracts of Citrus paradisi.

  • Cost-effective, non toxic and environmentally benign method is proposed.

  • Iron oxide nanoparticles are mostly spherical shape with an average size of 28–32 nm.

  • The as-synthesised iron oxide nanoparticles can be used nanoadsorbent for removal of toxic dyes.

Abstract

In the present study, iron oxide nanoparticles (FeONPs) were firstly synthesized using non-edible peel extracts of Citrus paradisi, which is abundantly available in the Andean Region, Latin America. Characterizations techniques like Visual, U.V.–Vis spectroscopy, Dynamic Light Scattering (DLS), Transmission electron microscopy (TEM) with Selected area electron diffraction (SAED), X- ray diffraction (XRD) and Thermogravimetric analysis (TGA) were performed for characterization of as-prepared material in terms of size, morphology, composition and structure. Furthermore, based on the Fourier-transform infrared spectroscopy (FTIR) analysis, a possible synthesis mechanism was proposed for the synthesis of FeONPs. The DLS shows that the FeONPs with average size of 27.1 ± 13.9 nm and TEM analysis confirms that the FeONPs are mostly spherical shape, aggregating in nature with an average size of 28–32 nm, respectively. XRD confirmed the existence of Fe3O4, α-Fe2O3 and γ-Fe2O3 nanoparticle mixture, whereas TG analysis indicated that the nanoparticles contain 76% metal,16% adsorbed moisture and 8% capping ligand. Finally, as prepared iron nanoparticles exhibited antioxidant activities against 1, 1-diphenyl-2-picrylhydrazyl (>15%, 100 µg) and also they were used for the treatment of different synthetic dyes (Methyl Rose, MR; Methylene Blue, MB and Methyl Orange, MO) to evaluate their adsorbity. The different decolourization percentages were obtained for the dyes MR (96.65%, 50 mg/L), MB (80.76%, 10 mg/L) and MO (89.64%,10 mg/L), respectively for 6 h at 25 °C. As a result, the use of agricultural waste as Citrus paradisi peel in nanoscience offers a sustainable, low cost, non toxic and friendly to the environment compared to other synthetic methods.

Introduction

In recent years, Nanotechnology holds an important field of applied science and technology concerned with food production, manufacturing technologies, electronics, cosmetics, household appliances, textiles, health as well as environmental remediation [1]. It involves the manipulation, fabrication and application of a different shape nanomaterials with the size ranging from 1 to 100 nm and exhibits unique properties (large surface area to volume ratio) not found in bulk-sized materials [2]. Till date, numerous physical and chemical methods are being used extensively for the bottom-up synthesis of nanoparticles. However, the chemicals used in these procedures leave very reactive and toxic residues and pollute the environment [3]. Researchers continue efforts to develop facile, effective, sustainable and reliable green chemistry processes for the production of nanomaterials. Therefore, biogenic synthesis of nanoparticles using fungi, bacteria, algae, and higher plants have emerged as potential nanofactories which are cost effective and environment friendly as well as valuable alternative and attractive methods [4].

Iron oxide nanoparticles (FeONPs) have attracted numerous applications in the field of food science, sensors, adsorbent, catalysis, data storage, electronic devices, environment, engineering, drug-delivery technology, biomedical research, magnetic recording devices, etc. [5]. Throughout the past decade, biosynthesis of FeONPs using various plant extracts have been investigated by many researchers such as leaf of Camellia sinensis [6] and Azadirachta Indica [7], fruit of Terminalia chebula [8] and Passiflora tripartita [9], peel of Punica Granatum [10] and Pisum sativum [11], bran of Sorghums [12], seed of Syzygium cumini [13], flower of Avicennia marina [14] and Hibiscus sabdariffa [15], root of [16], biomass of Medicago sativa [17]. However, ecofriendly synthesis of FeONPs using discarded plant material with improved antioxidant and adsorbent activities is gaining importance in biotechnology applications and need to be studied in greater detail.

Grapefruit (Citrus paradisi) is a hybrid, probably originating from a natural cross-hybridization between pummelo and sweet orange. They have attracted much attention because of their nutritional and antioxidant properties. They are unique, having red pigment in the juice vesicles and relatively high levels of flavanones, narirutin and naringin and their aglycone compounds. The other dominant bioactive compounds present in grapefruits include hydroxyl cinnamic acids (ferulic and p-coumaric acids) and hydroxybenzoic acids (vanillic and gallic acids) are the main phenolic acids, limonoids, carotenoids, and furocoumarins [18], [19]. Furthermore, the fruit peel and seed contains high levels of bioactive flavanones glycosides (naringin and narirutin) which makes the peel has an excellent capacity to synthesize metal nanoparticles although it is considered a waste material [20].

Citrus peels are one of the most under utilized and geographically diverse biowaste residues. At present, the worldwide industrial citrus wastes account for 50 wt% of the original whole fruit mass, and almost 1/2 of the citrus wastes is peel. The management of these wastes that produce odor and soil pollution still remains a major problem in the food industry [21]. Thus, the utilization of Citrus paradisi peel in nanoscience for the production of nanoparticles could be sustainable process for providing a non-food-based market for agro-waste and could be useful in various scientific domains. To the best of our knowledge, there is no report on using Citrus paradisi peel extract (CPPE) as a precursor/ reductant for synthesizing FeONPs. The main advantage of this method was the relatively easy to handle, wide distribution ranges and cost-effective, as well as environmentally benign and sustainable. The obtained FeONPs have been examined by using U.V.–Vis spectroscopy, Dynamic Light Scattering (DLS), Transmission electron microscopy (TEM) with Selected area electron diffraction (SAED), X- ray diffraction (XRD) and Thermogravimetric analysis (TGA). In addition to this antioxidant activity against 1, 1-diphenyl-2-picrylhydrazyl and nanoadsorbent activity for the removal of synthetic dyes were also studied.

Section snippets

Materials

All chemicals were reagent grade and used without any purification. FeCl3.6H20 (99.0%) and methylene blue (MB, 99.5%) were purchased from Spectrum, USA. Methyl orange (MO, 99.88%), and methyl red (MR, 99.88%) were purchased from Aldrich, USA. Milli-Q water was used in all experiments. All glassware was washed with acid/base solution followed by Milli Q water and finally dried in a hot air oven.

Preparation of peel extract of C. paradisi (CPPE)

In this experiment grapefruit (Citrus paradisi L.) were purchased from Sangolqui popular market near

Visual and UV–Vis spectroscopy

The Visual and UV–vis spectrum of the properly diluted CPPE–FeONPs was measured at room temperature and presented in the Fig. 2. Addition of CPP extracts to ferric (III) chloride produced a color change in the solution from yellow to light orange and finally to black color, indicating the formation of iron-containing nanoparticles. This phenotypic change correlated well with the change in absorption spectra data, such that the absorption peak at 350–400 nm of the FeONPs was appeared after the

Conclusion

In conclusion, iron oxide nanoparticles were firstly biosynthesized using non-edible peel extracts of Citrus paradisi. Visual and UV–Vis analysis suggested the formation of FeONPs by transforming yellow colour to black and recommended synthetic method are low cost, non toxic and friendly to the environment. The hydrodynamic size distribution from DLS and particle size from TEM analysis are in good aggreement with each other. XRD showed the formation of α-Fe2O3, γ-Fe2O3 and Fe3O4 in polymorphic

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

This scientific work has been funded by the Universidad de las Fuerzas Armadas ESPE, Ecuador, and Prometeo Project of the National Secretariat of Higher Education, Science, Technology and Innovation (SENESCYT), Ecuador and TATA College, India.

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