Removal of Congo Red Using Iron-Based Nanoparticles Synthesized by Citrus Family Peel Extracts

doi:10.21203/rs.3.rs-1497180/v1

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Removal of Congo Red Using Iron-Based Nanoparticles Synthesized by Citrus Family Peel Extracts

https://doi.org/10.21203/rs.3.rs-1497180/v1

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Iron-based nanoparticles were synthesized without addition of any pH stabilizers, stabilizers and capping agent. The particles were prepared using lemon, tangerine, orange and grapefruit peel extracts. The optimum reaction parameters were determined with UV–Visible spectroscopy, X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmittance electron microscopy (TEM) and Thermogravimetric analysis (TG/DTG) were used. XRD results identified binary formation of Fe₃O₄ and Fe₂O₃ with powder diffraction file numbers of “01-074-1910” and “03-065-0390”, respectively. According to morphological results, the smallest particle size range of 155–225 nm was observed in LP-Fe Np (iron-based nanoparticles synthesized by using lemon peel extract). UV-Vis indicated the iron nanoparticle formation in the range of 220–380 nm. The decomposition processes of the synthesized samples were occurred in multiple stages between 30 and 518°C. The smallest particles were measured at TP-Fe Np as 1.36–30.76 nm in TEM analyses. The adsorption of Congo red on the synthesized nanoparticles were also determined. The highest removal rate was obtained for the GP-Fe Np as 36.5%.

adsorption

bio-based capping agent

iron-based nanoparticle

stabilizer

Nanotechnology involves the production, processing and application of different nanomaterials ranging from 1 to 100 nm. Nanoparticles exhibit unique properties such as large surface area/volume ratio, strong optical and electrical characteristics, not found in bulk-size materials [1–2]. In recent years, green synthesized iron and iron-based nanoparticles used in environmental remediation attract more attention. Many physical and chemical methods have been widely used to date for the bottom-up synthesis of iron nanoparticles. However, these traditional synthesis methods use corrosive, toxic and flammable chemicals and high cost of production and special equipment [3–4]. To solve these problems found in traditional synthesis methods, the biosynthesis of nanoparticles using natural plant extracts has been developed as a sustainable, reliable, cost-effective, simple and environmentally friendly alternative method. Also, the use of high-risk materials such as reducing or capping agents is avoided to eliminate the formation of hazardous wastes [5–6].

Some studies have been reported on the synthesis of iron-based nanoparticles using various plant and fruit extracts and their use as adsorbent such as; tangerine peel [7], Mangifera indica, Murraya koenigii, Azadiracta indica, Magnolia champaca [8], Korla scented pear bark [9], Ananas comosus

(pineapple) and Citrullus lanatus (watermelon) fruit peel extract [10–11], citrus maxima peels [12].

Plant extracts contain abundant chemical components responsible for the biological reduction of phenols, ascorbic acids and metal ions. These components are also beneficial for stabilization of nanoparticles. Fruit peels are among the available sources used for green synthesis, apart from plant leaves. In addition; citrus peels include various phytochemicals such as essential oil, flavonoids, pectin and polysaccharide compounds [13–14]. The highly bioactive flavanone glycosides present in the grapefruit peel make this peel have an excellent capacity to synthesize metal nanoparticles, although it is considered as waste material [15]. Today, worldwide industrial waste of citrus peels accounts for 50% by weight of the entire fruit mass. Almost half of citrus waste consists of peels. These wastes cause environmental pollution and still continue to be a problem in the food industry [16]. The use of fruit peels as raw material is essential for both not to cause any pollution and eliminate the waste resources.

As a member of azo-aromatic group, congo red dye is known as the most harmful and still used dyes in the world. In addition; benzidine, amine and other potentially carcinogenic groups are also included in its structure [17–18]. In most of world, the industrial use of congo red is banned because of its toxic potential. However, wastewater usually contains pollutants and treatment under inappropriate conditions causes many biological and chemical changes. Today, congo red dyestuff is still used by many developing countries. This situation affects adversely the environment and human health [19–20].

In this study, green synthesis method was used to synthesize iron-based nanoparticles using lemon, tangerine, orange and grapefruit peel extracts as reducing and stabilizing reagents. The optimum synthesis reaction parameters were determined for the nanoparticle preparation and the adsorption capacities of nanoparticles produced using four different citrus peel extracts were compared. By using citrus peel extracts as raw material, pollution problems and waste of resources have been prevented and the synthesis process of iron-based nanoparticles has been improved.

2.1. Materials

Citrus family peels of lemon, tangerine, orange and grapefruit were provided from Erdemli region of Mersin, Yuregir region of Adana, Serik region of Antalya and Finike region of Antalya, respectively. The prepared fruit peels were extracted using a WF-MID1 model magnetic stirrer of the Weightlab Instruments brand, at a stirring speed of 500 rpm, at a temperature of 75°C and for 1 hour. The produced yellow-orange extracts were filtered using a Macherey-Nagel (Düren, Germany) blue filter. The extracts filtered extracts after filtration were stored in a sealed container at + 4°C.

Iron sulphate heptahydrate (FeSO₄.7H₂O, purity of % 99.5) used as the Fe source was supplied from Merck (Darmstadt, Germany) and a 0.1 M solution was used. The dye of Congo red used in the adsorption experiments was purchased from AFG Bioscience dyestuff.

2.2 Green Synthesis of Iron-Based Nanoparticles

For the synthesis procedure, the Fe source was reacted with the lemon peel extract at the ratio of 1:2 [21]. The effects of reaction temperature (25, 40, 60 and 80°C), reaction time (1, 2, 4 and 6 hours), solution medium (100% water, 100% ethanol and 50–50% water-ethanol) were experimented to determine the optimum parameters. After the reaction was completed, the colour of the solution turned black from blue-green. The solution was filtered and dried in an oven (Ecocell 111, Germany) at 105°C for 12 hours. After the optimum parameters were determined for lemon peel extract, the same procedure was applied for the tangerine, orange and grapefruit peel extracts.

The samples were encoded as LP-Fe Np, TP-Fe Np, OP-Fe Np and GP-Fe Np for the nanoparticles produced by the peel extracts of using lemon, tangerine, orange and grapefruit, respectively.

2.3 Adsorption Experiments

Congo red solution was used in 50 mg/L concentration. 0.01 g of produced powder form nanoparticles (LP-Fe Np, TP-Fe Np, OP-Fe Np, GP-Fe Np) were added to 50 mL of Congo red solution and stirred at 500 rpm for 1.5 hour on a magnetic stirrer. After the adsorption was completed, the solution was filtered.

The dye removal rates of the synthesized nanoparticles were calculated by determining the concentration change of Congo red in the solution. The removal rate (η, %) and the amount of equilibrium adsorption (q_e, mg/g) were calculated according to the formula given in Eqs. 1 and 2 [22–23].

η = $\frac{\text{C}\text{o}-\text{C}\text{e}}{\text{C}\text{o}}\times 100$ (1)

$${q}_{e}=\frac{\text{C}\text{o}-\text{C}\text{e}}{\text{m}}\times V$$

C_O and C_e represent the initial and equilibrium concentrations of Congo red (mg/L) in aqueous solution. m and V are the mass of adsorbent (mg) and volume of solution (L).

2.4. Characterization Experiments of Iron-Based Nanoparticles

The samples were identified by using PANalytical X'pert Pro XRD (PANalytical B.V., Almelo, The Netherlands) with the Cu-Kα tube (λ = 0.153 nm) at the values of 45 kV of voltage, 0.03° of step size, 0.5 s of step time, 40 mA of current, 0.06°C/s of scan speed and 7–90° of 2 theta (θ) range. Lambda 35 model UV-Visible spectrophotometer of Perkin Elmer was used for the analysis of characteristic adsorbance values for the Fe atom in the 190–1100 nm range. ZEISS EVO LS 10 model Scanning Electron Microscope (ZEISS EVO LS 10, Germany) was used to examine the morphology of the samples at the magnification value of 30000X. The surface morphologies of the particles were characterized using a Hitachi High Tech brand TEM (HT 7700, Japan) device at the magnification value of 80000X, 120.0 kV voltage and Zoom-1 HR-1 lens mode. The thermal properties of the nanoparticles were characterized using the TG/DTG (SII 6000 Exstar TG/DTG 6300, Japan) device belonging to the SII Nanotechnology brand. The thermal behaviour of the samples was carried out at 30°C – 800°C temperature and 10 min/^oC heating rate in nitrogen atmosphere.

3.1 XRD Analyses Results

In XRD results, the samples were identified as the mixture of different iron and iron oxide phases. The observed phases were identified as Fe₃O₄ with the powder diffraction file number (pdf no.) of "01-074-1910", Fe₂O₃ with the pdf no. of "03-065-0390" and Fe with the pdf no. of “01-089-4186”. Crystallographic parameters the obtained phases were given in Table 1.

Table 1

Crystallographic parameters the obtained phases
Mineral Name	Magnetite	Iron Oxide	Iron
Powder Diffraction File Number	01-074-1910	03-065-0390	01-089-4186
Chemical Formula	Fe₃O₄	Fe₂O₃	Fe
Crystal System	cubic	tetragonal	cubic
a (Å)	8.3900	8.3396	2.9315
b (Å)	8.3900	8.3396	2.9315
c (Å)	8.3900	8.3221	2.9315
α (°)	90.0000	90.0000	90.0000
β (°)	90.0000	90.0000	90.0000
γ (°)	90.0000	90.0000	90.0000

The XRD scores of the synthesized iron-based nanoparticles were shown in Table 2. According to the XRD results, the major effect of reaction time on crystal formation was seen. The reaction mechanism was sensitive to temperature. It was concluded that, lower temperatures should be selected at longer reaction times. Also, zero-valent iron phase was observed at the reaction time of 4 hours. The optimum reaction medium was selected as water. The particles were synthesized at higher crystallinity in the use of lemon peel extract. XRD pattern of samples synthesized using four different fruit peels were presented in Fig. 1. According to the Fig. 1, the highest peaks were observed in the LP-Fe-NP at the 2θ values of 18.34°, 26.02°, 28.73° and 35.83°.

Table 2

XRD scores of synthesized iron-based nanoparticles
Effect of temperature	Temperature (°C)		20	40	60		80
	-		*	*	*		*
Effect of time	Reaction time (h)		1	2	4		6
	Pdf file no.	01-074-1910	*	22	8		21
		03-065-0390		9	9		5
		01-089-4186		-	20		-
Effect of extract type	Peel extract type		LP-Fe Np	TP-Fe Np		OP-Fe Np	GP- Fe Np
	Pdf file no.	01-074-1910	25	9		15	16
		03-065-0390	9	6		11	7
Effect of solvent type	Solvent type		water	water and ethanol mixture (50%-50%)			ethanol
	Pdf file no.	01-074-1910	22	25			*
		03-065-0390	9	9
* Amorphous formation

3.2 UV-Visible Spectroscopy Results

UV-visible spectra of the synthesized iron-based nanoparticles were recorded between 190 and 1110 nm at room temperature. Due to the surface plasmon resonance, the iron nanoparticles characteristic peaks exhibited in the 250–350 nm band range [24]. The UV-visible spectroscopic analyses result of LP-Fe Np, TP- Fe Np, OP- Fe Np and GP- Fe Np are given in Fig. 1. By adding iron sulphate heptahydrate solution to the yellow and orange extracts, colour changes close to black was observed. This confirms the formation of iron-based nanoparticles [25]. According to the obtained results, the characteristic adsorbance values of LP- Fe Np observed between 250 and 300 nm whereas the peaks of TP- Fe Np, OP- Fe Np and GP- Fe Np were seen in the 220–380 nm range. The band values between 350 and 380 nm for the TP- Fe Np, OP- Fe Np and GP- Fe Np codded samples can be explained with the remain functional grouping in peel extracts.

Figure 2. UV–visible spectra of the synthesized samples

3.3 SEM Analysis Results

The morphologies of nanoparticles fabricated by using different peel extracts were presented in Fig. 3. According to these results; it has been concluded that LP-Fe Np has the smallest particle size with 155–228 nm, and GP-Fe Np has the largest particle size with 225–755 nm, and the use of lemon peel extract contributed on crystal formation. Morphologies of OP-Fe Np and GP-Fe-Np can be explained with the agglomerated multi-angular particles, similar with LP-Fe Np. The particle sizes were varied between 161 and 225 nm for OP-Fe Np whereas the sizes were in the range of 464–619 nm for TP-Fe Np. In the study reported by Feng and Lim, the close contact of iron nanoparticles was attributed to the magnetic properties of the iron species [26]. According to the SEM results, the production in which lemon peel extract is used as a raw material was selected as optimum.

3.4 TEM Analysis Results

TEM analysis results indicated the presence of mostly agglomerated structures in all four fruit peels. The present agglomeration may be due to the magnetic nature of the iron oxide structures and excessive phytochemicals that increase particle growth at the surface. The formation of larger and varying sizes of iron nanoparticles as a result of agglomeration has been reported [27].

TEM images of iron/ iron oxide nanoparticles produced by using different citrus family peel extracts were shown in Fig. 4. In Fig. 4, agglomeration and amorphization of nano-level particles were commonly observed. While particle formation was observed slightly more in the samples prepared with lemon and tangerine peel extracts, a clear image could not be obtained in the samples prepared with orange and grapefruit peel extracts due to agglomeration and amorphization. Accordingly, the measured grain sizes are in the range of 12–16 nm in the LP-Fe Np sample, and 1.36–30.76 nm in the TP-Fe Np sample, and they are in the form of polygonal particles that are close to spherical.

3.5 Thermal Analysis Results

Thermal analysis was performed to determine the thermal behaviour of decomposition temperature and decomposition mechanism of samples. The thermal curves of TG and DTG for samples were presented in Fig. 5 and thermal analyses result of sample was given in Table 3. Total mass losses were determined as 59.1% for LP-Fe Np, 58% for TP-Fe Np, 60.4% for OP-Fe Np and 58.6% for GP-Fe Np.

Table 3

Thermal analyses result of samples
	Reaction Step	T_initial (°C)	T_final (°C)	T_max (°C)	Mass loss (%)
LP-Fe Np	1	96.85	135.72	114.94	11.5
	2	171.90	287.44	244.52	18.7
	3	309.79	348.85	328.25	11.2
	4	428.28	518.42	466.11	17.7
TP-Fe Np	1	76.08	130.92	111.07	11.2
	2	146.02	198.48	181.07	9.3
	3	219.47	265.01	240.52	10.0
	4	309.45	350.06	323.37	13.2
	5	431.89	499.61	458.83	14.3
OP-Fe Np	1	93.79	137.17	116.89	11.1
	2	156.85	264.6	185.06	22.8
	3	309.60	349.49	325.58	11.8
	4	434.38	495.87	459.18	14.7
GP-Fe Np	1	57.61	133.19	92.54	12.1
	2	140.27	187.94	173.66	6.1
	3	200.66	270.61	241.91	12.3
	4	297.61	349.74	316.35	14.1
	5	416.83	518.97	463	14

In the thermal decomposition of iron-based nanoparticles, the process occurred in multiple steps. The weight losses and steps approximately until 120°C can be explained with the removal of the existing moisture in sample. Next stages after moisture removal can be interpreted with the elimination or degradation of encapsulating biomolecules [25].

3.6 Adsorption Results

The removal rate (η, %) and the amount of equilibrium adsorption (q_e, mg/g) of synthesized iron-based nanoparticles were estimated by using the data obtained from UV-visible spectroscopic results and the results were given in Table 4. According to the adsorption results, η values varied in the range of 36.50–30.19% whereas q_e variables were estimated between 0.09126 and 0.07547 mg/g. The highest values of η and q_e for Congo red removal were found as 36.50% and 0.09126 in the sample of GP- Fe Np, respectively. The removal rates for the samples synthesized by using different peel extracts declined in the following order: GP- Fe Np > LP- Fe Np > TP- Fe Np > OP- Fe Np.

Table 4

The removal rate (η, %) and the amount of equilibrium adsorption (qe, mg/g) of samples
Sample	η (%)	q_e (mg/g)
GP- Fe Np	36.50	0.09126
LP-Fe Np	35.63	0.08909
TP-Fe Np	31.95	0.07987
OP-Fe Np	30.19	0.07547

Iron-based nanoparticles were fabricated by the addition of various citrus family peel extracts without using any pH stabilizer and hazardous capping agent. The prepared powders were characterized with UV-vis spectroscopy, XRD, SEM, TEM and TG/DTA analyses. The operation parameters of reaction were also optimized in hydrothermal conditions. For the optimum conditions, adsorption capacities for the congo red was studied. The results signified that the suitability of the using peel extracts for the nanoparticle synthesis and the availability of the synthesized particles for the congo red adsorption from the wastewater. In this way, it will contribute to the literature in line with the existence of an environmentally friendly production from natural fruit peels that does not require any processing and high energy consumption.

Funding: This study was financially supported by the Coordination Unit for Scientific Research Projects, Yildiz Technical University. (Project No: FYL-2021-4130)

Conflict of interest: Not applicable

Availability of data and material: The data that support the findings of this study are available on request from the authors.

Code availability: Not applicable

Authorscontributions: TA carried out the experiments and wrote the manuscript, FTSD carried out the experiments and wrote the manuscript, EMD supervised the work and edited the manuscript.

Ethics approval: Not applicable

Consent to participate: Not applicable

Consent for publication: Not applicable

ACKNOWLEDGEMENTS

This research was supported by the Coordination Unit for Scientific Research Projects, Yildiz Technical University. (Project No: FYL-2021-4130)

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Removal of Congo Red Using Iron-Based Nanoparticles Synthesized by Citrus Family Peel Extracts

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Version 1

Abstract

Figures

1. Introduction

2. Experimental Procedure

2.1. Materials

2.2 Green Synthesis of Iron-Based Nanoparticles

2.3 Adsorption Experiments

2.4. Characterization Experiments of Iron-Based Nanoparticles

3. Results And Discussion

3.1 XRD Analyses Results

3.2 UV-Visible Spectroscopy Results

3.3 SEM Analysis Results

3.4 TEM Analysis Results

3.5 Thermal Analysis Results

3.6 Adsorption Results

4. Conclusion

Declarations

References

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