Fabrication of Silver Oxide and Nickel Oxide Nanoparticles by Green Synthesis Method Using Malva Sylvestris Plant Extract
محورهای موضوعی : ChemistryAzam Beheshtian 1 , Mohammad Hadi Givianrad 2 , Hossain-Ali Rafiee-Pour 3 , Parviz Aberoomand Azar 4
1 - Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran
2 - Department of chemistry, Science and Research Branch, Islamic Azad University, Tehran Iran
3 - Department of Cell and Molecular Biology, Faculty of Chemistry, University of Kashan, Kashan,
Iran
4 - Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran
کلید واژه: nanoparticles, Quercetin, green chemistry, Nickel oxide, silver oxide, malva sylvestris extract,
چکیده مقاله :
This paper reports the green preparation of silver oxide and nickel oxide nanoparticles. The malva sylvestris extract was used as the green reductant and capping agent. The prepared nanoparticles were characterized using XRD, SEM, FT-IR, and EDX analysis. The XRD analysis discloses that the prepared silver oxide nanoparticles comprise both Ag2O and Ag metal phases. In addition, it was found that the prepared nickel oxide nanoparticles have an amorphous structure. The FT-IR results show the presence of metal-oxide bonds at the wavenumber range 750-600 cm-1. Also, the green synthesis of the metal oxide nanoparticles was confirmed by the existence of the organic functional groups on the surface of the prepared samples. The SEM images show the spherical nanoparticles in the size range below 50 nm for both prepared nanoparticles. These results reveal the superior ability of the malva sylvestris extract to prepare the fine metal oxide nanoparticles. In this research, synthesized Ag2O nanoparticles (Ag2O NPs) and NiO nanoparticles (NiO NPs) were used as modifiers for carbon paste electrode (CPE) and their effect on the electrochemical determination of Quercetin (QCT) was investigated by using differential pulse voltammetry (DPV).
This paper reports the green preparation of silver oxide and nickel oxide nanoparticles. The malva sylvestris extract was used as the green reductant and capping agent. The prepared nanoparticles were characterized using XRD, SEM, FT-IR, and EDX analysis. The XRD analysis discloses that the prepared silver oxide nanoparticles comprise both Ag2O and Ag metal phases. In addition, it was found that the prepared nickel oxide nanoparticles have an amorphous structure. The FT-IR results show the presence of metal-oxide bonds at the wavenumber range 750-600 cm-1. Also, the green synthesis of the metal oxide nanoparticles was confirmed by the existence of the organic functional groups on the surface of the prepared samples. The SEM images show the spherical nanoparticles in the size range below 50 nm for both prepared nanoparticles. These results reveal the superior ability of the malva sylvestris extract to prepare the fine metal oxide nanoparticles. In this research, synthesized Ag2O nanoparticles (Ag2O NPs) and NiO nanoparticles (NiO NPs) were used as modifiers for carbon paste electrode (CPE) and their effect on the electrochemical determination of Quercetin (QCT) was investigated by using differential pulse voltammetry (DPV).
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Fabrication of silver oxide and nickel oxide nanoparticles by green synthesis method using Malva Sylvestris plant extract
Abstract
In this paper, we report the green preparation of silver oxide and nickel oxide nanoparticles. The malva sylvestris extract was used as the green reductant and capping agent. The prepared nanoparticles were characterized using XRD, SEM, FT-IR, and EDX analysis. The XRD analysis discloses that the prepared silver oxide nanoparticles are composed of both Ag2O and Ag metal phases. In addition, it was found that the prepared nickel oxide nanoparticles have an amorphous structure. The FT-IR results show the presence of metal-oxide bonds at the wavenumber range 750-600 cm-1. Also, the green synthesis of the metal oxide nanoparticles was confirmed by the existence of the organic functional groups on the surface of the prepared samples. The SEM images show the spherical nanoparticles in the size range below 50 nm for both prepared nanoparticles. These results reveal the superior ability of the malva sylvestris extract for preparing the fine metal oxide nanoparticles. In this research, synthesized Ag2O nanoparticles (Ag2O NPs) and NiO nanoparticles (NiO NPs) were used as modifiers for carbon paste electrode (CPE) and their effect on electrochemical determination of Quercetin (QCT) was investigated by using differential pulse voltammetry (DPV).
Keywords: green chemistry; silver oxide; nickel oxide; nanoparticles; malva sylvestris extract; Quercetin
1. Introduction
In recent years, great attention has been devoted to nanomaterials and their applications in the field of manufacturing high-tech products [1, 2]. Nanomaterials have been utilized as a major part of modern technology such as catalysis, energy conversion, hydrogen production, medical treatment, solar harvesting technology, etc. [3-5].
The controlling structure and morphology of nanomaterials are the most important issue which has been considered by many research groups. In this regard, the physicochemical properties of the nanomaterials could be tuned using the appropriate preparation method [6, 7].
Generally, the preparation approach of nanomaterials is divided into two categories of chemical and physical processes [8]. In the physical process, the nanomaterials are synthesized using non-solvent based methods such as ball milling, laser ablation, etc. On the contrary, the preparation of nanoparticles in the solvent media lies in the chemical synthetic approach. The chemical preparation of nanomaterial is associated with using poisonous reagents that not only have potential hazards to environment but also substantially increase the cost of production. Therefore, utilization of cost-effective and environmentally-friendly reagents has received much attention [8-10].
The green chemistry is a substitute for the conventional method of preparation nanomaterials. In green preparation approach, the biological reagents are used as reductant or stabilization agents [11]. The tuning physicochemical properties of the nanomaterials by using the biological reagents is much easier compared to that of using the chemical agents which is due to the mid-reactive and non-toxic nature of biological agents [12].
The common biological materials which have been used for the green synthesis include micro-organism (bacteria, algae and fungus) and plant extracts (steam, flower, leaf and seed). The metal and metal oxide nanoparticles have been synthesized using the bacteria media [8]. For instance, Korbekandi et al. used Lactobacillus casei for synthesis Ag nanoparticles [13]. The spirulina platensis bacteria was used for preparation of CuO nanoparticles [14].
The plant extracts contain bioactive materials such as polyphenols, tannin, proteins, glycosides and flavonoid which are able to reduce and stabilize metal ions to form fine nanoparticles. In this regard, Aloevera plant extract was used to prepared Au and Ag nanoparticles [15]. Thema et al. prepared NiO nanoparticles using Agathosma betulina extract [16]. Logambal et al. reported the green synthesis of CuO nanoparticles using Couroupita guianensis extract [17].
One of the most interesting plants which are rich in the polyphenole is malva sylvestris. The medical properties of malva sylvestris have been acknowledged as anti-inflammatory and antioxidant agent. Also, the abundance of polyphenol compounds in the malva sylvestris makes it appropriate for green synthesizing of nanoparticles [18, 19].
Owing to superior characteristics such as electronic, optical and catalytic properties, the metal oxides nanoparticles are widely used. In this regard, NiO and Ag2O have received much attention as a result of their excellent catalytic properties. For example, Wang et al. studied the catalytic properties of Ag/Ag2O/CeO2 composite for photocatalytic hydrogen production [20]. Guo et al. prepared the Ag2O modified CuO nanosheet and studied their catalytic properties for water oxidation [21]. Also, Zahra et al. reported the NiO/ZrO2 mixed oxides for oxygen evolution reaction [22].
In this report, we prepared the silver oxide and nickel oxide nanoparticles using the green synthesis approach. The malva sylvestris extract was used as reductant and capping agents for the preparation of silver oxide (Ms- Ag2O NPs ) and nickel oxide nanoparticle (Ms- NiO NPs). The prepared samples were characterized using XRD, SEM, and FT-IR analysis. Further, the carbon paste electrode was modified with Ms- Ag2O NPs (Ms- Ag2O/CPE) and Ms- NiO NPs (Ms- NiO/CPE) separately. The Ms- Ag2O/CPE and Ms- NiO/CPE were used to investigate the electrochemical behavior of QCT by differential pulse voltammetry (DPV) technique.
2. Experimental
2.1. Preparation of plant extract from Malva sylvestris
First, 10 g of the malva sylvestris leaves were grinded using mortar to form fine powder. Then, the powder was dispersed into 100 mL of deionized water and heated at 80 °C for 2 hours. The mixture was separated using filter paper and then light yellow filtrate solution was collected for using in nanoparticles synthesis.
2.2. Preparation of silver oxide and nickel oxide nanoparticles
A certain amount of silver nitrate (0.1 g) was dissolved into 25 mL of the malva sylvestris extract. The solution was heated at 60 °C for 6 hours. The prepared dark brown solid was collected using centrifugation at 6000 rpm for 15 min. The collected solid was washed several times using deionized water/ethanol solution and finally dried in an oven at 100 °C for 5 hours. The same procedure was followed for preparation of NiO nanoparticles using Ni(NO3)2.6H2O precursor.
2.3. Preparation of Ms- Ag2O/CPE and Ms- NiO/CPE
The Ms- Ag2O/CPE and Ms- NiO/CPE electrodes were prepared by mixing the certain amounts of graphite powder (0.5 g) and Ms- Ag2O NPs or Ms- NiO NPs (0.004 g) separately in mortar for 30 min. After preparation of homogenous powder, a certain amount of paraffin oil (6 to 8 drops) was added to create carbon paste. Then, the well mixed pastes were packed stiffly into a syringe with 2 mm diameter and 10 mm depth. A copper wire was put into the each of packed carbon pastes to establish electrical connections.
2.4. Characterization
The crystallinity and phase structure of the prepared silver oxide and nickel oxide nanoparticles were studied using X-ray diffraction (XRD) analysis (Philips X’pert Pro MPD, Cu Kα radiation λ = 1.54 Å). The morphology of the prepared nanoparticles were studied using the scanning electron microscopy (SEM) (TESCAN Mira3) equipped with energy dispersive detector to determine the components and elemental analysis of the prepared nanoparticles. The FT-IR spectra of the prepared samples were recorded on a Shimadzu Varian 4300 spectrometer. The electrochemical behaviors of QCT at the surfaces of Ms- Ag2O/CPE and Ms- NiO/CPE and CPE were studied by DPV method.
3. Results and discussion
Fig. 1a, b show the XRD analysis for the prepared silver oxide and nickel oxide nanoparticles. The XRD pattern reveals that the prepared silver oxide nanoparticles include both Ag2O and Ag phases. As shown in Fig. 1a, the prepared silver oxide using the malva sylvestris represents the diffraction peaks at 2θ = 33.27°, 38.39°, 56.21° and 77.57° which are attributed to the hexagonal phase of Ag2O (marked with •). Moreover, the cubic phase of Ag metal (marked with ♣) is clearly observed at 44.51°, 66.69° and 77.57° [23]. Due to electron donation ability of flavonoid groups, the reduction of silver ions into silver metal is attributed to the presence of these compound in malva sylvestris extract. The hydroxyl groups in flavonoid act pivotal role for chelating silver ions and also reducing them by donation of electrons [24].
This reaction is similar to that of the reduction reaction in presence of citrate ions, as follows [25]:
2Ag+ + C6H5O73- 2Ag0 + H+ + CO2 + C5H4O52-
In addition, Fig. 1b shows the diffraction peaks for the prepared nickel oxide nanoparticle using the malva sylvestris extract. The amorphous nature of the prepared nickel oxide was confirmed using the XRD analysis. Besides, there is a broad peak around 2θ = 34.78° which is featured the NiO phase (047-1049) [26].
Fig. 1. XRD patterns of the prepared silver oxide (a) and nickel oxide (b).
Fig. 3 shows the SEM images for the prepared silver oxide and nickel oxide nanoparticles using the malva sylvestris extract. As is clear form Fig. 2a and b, the silver oxide nanoparticles have spherical morphology with the average size below 50 nm. However, the nickel oxide nanoparticles represent the agglomerated particles with a size of hundreds nanometer (Fig.2c). But, Fig. 2d reveals that the agglomerated particles are composed of finer spherical particles in the size range below 50 nm.
Fig. 2. SEM images and EDX spectra of the green synthesized of silver oxide (a, b, e) and nickel oxide (c, d, f) nanoparticles using the malva sylvestris extract.
In addition, Fig.2e, f show the EDX spectra for the prepared silver oxide and nickel oxide, respectively. From Fig. 2e, the green synthesized silver oxide nanoparticles are mainly comprised of Ag (97.99 wt%) and O (2.01 wt%) elements without any observable metal impurity. Similarly, Fig. 2f, discloses the elemental analysis for the green synthesized for the nickel oxide nanoparticles. The prepared nanoparticles are constructed of Ni (72.70 wt%) and O (27.30 wt%) elements without any metal impurity. The presence of carbon is attributed to the malva sylvestris extract used for preparation of nanoparticles.
In order to study the functional groups on the surface of the green prepared nanoparticles using malva sylvestris, the prepared samples were analyzed using FTIR spectroscopy, shown in Fig. 3a and b. Clearly, the presence of C-O, C=O and N-H groups were confirmed on the surface of both samples at around 1048, 1658 and 1411 cm-1, respectively. These characteristic absorption peaks affirm the residual organic species on the surface of nanoparticles which are also an indisputable evidence for successful preparation of sample via green synthetic route. The stretching vibration for hydroxyl groups is observed at around 3350-3400 cm-1. The absorption peaks related to the metal-oxygen bonds for Ag-O and Ni-O are appeared at 758 and 630 cm-1, respectively [27, 28].
Fig. 3. FT-IR spectra of the prepared of silver oxide (a) and nickel oxide (b) nanoparticles.
Table 1 summarizes the recent literature on green synthesis of metal oxide nanoparticles and reveals the potential of the malva sylvestris extract for synthesizing of metal oxide nanoparticles.
Table 1. The comparison between the malva sylvestris-mediated green synthesize of nanoparticles and previously reported green synthesize of metal oxide nanoparticles.
Nanoparticle | Plant extract | Particle size (nm) | Refrence |
Ag/Ag2O and NiO | Malve sylvestris | < 50 | This work |
NiO | Agathosma Betulina | 26 | [16] |
NiO | Aegle marmelos | 8-10 | [29] |
NiO/MgO | Pomegranate | --------- | [30] |
CuO | Gloriosa superba | 5-10 | [31] |
CuO | Allium sativum | 20-40 | [32] |
Ag/Ag2O | Eupatorium Odoratum | 8-20 | [33] |
4. Application of synthesized Ag2O NPs and NiO NPs as modifier of carbon paste electrode
In recent decades, metal oxides (MOX) nanoparticles have attracted great attention, due to their chemical characteristics and functional properties such as high electrical and thermal conductivity and they have considered important as modifiers for electrochemical sensors.[34] On the other hand, Quercetin (QCT) is a kind of flovanol which consists naturally in various plants. QCT shows antibacterial, anti-allergic, antioxidant and antitumor activities due to its scavenging property but overdoses of QCT can lead to serious diseases such as kidney cancers and stomach upset.[35] Therefore, it is important to detect QCT levels with high degree of accuracy and sensitivity and fast, low cost and available electrochemical methods are one of the best methods for these determinations.[36-37] In this research, synthesized Ag2O NPs and NiO NPs were used as modifiers for carbon paste electrode (CPE) and their effect on electrochemical determination of QCT was investigated by using differential pulse voltammetry (DPV).
As shown in Fig. 4a and b compared to unmodified carbon paste electrode, the electrochemical response was greatly improved for QCT electrooxidation. As well as, Ag2O NPs compared to NiO NPs has a slightly superior effect on the electrochemical response of QCT which can be due to its higher electrical conductivity. According to obtained results, it is clear that addition of Ag2O and NiO nanoparticles exerts a significant catalytic effect on the electrochemical reduction of QCT leading to decrease of overpotential in the process and an enhancement in the peak current is observed. Therefore, Ag2O nanoparticles and NiO nanoparticles modified carbon paste electrode propose for the determination of QCT as electrochemical sensors.
Fig. 4: DPV voltammograms of 0.1 M phosphate buffer solution at (pH 6) in the presence of QCT at the CPE and CPEs modified with Ag2O NPs (a) and NiO NPs (b) synthesized via Malva Sylvestris extract.
5. Conclusions
In summary, we have presented a green approach for preparing silver oxide and nickel oxide nanoparticles. The malva sylvestris extract was used to prepared samples. The crystallinity and phase structure of the prepared samples were studied using XRD analysis which revealed hexagonal phase of Ag2O for the prepared silver oxide nanoparticles. In addition, the existence of Ag metal phase was proved in the sample. Besides, the amorphous structure was confirmed for the prepared nickel oxide nanoparticles. The ability of malva sylvestris extract to prepare metal oxide nanoparticles was revealed using SEM analysis which showed nanospherical particle with size of around 50 nm for both prepared nanoparticles. The prepared silver oxide and nickel oxide nanoparticles were used to detect QCT. The DPV results for Ms- Ag2O/CPE and Ms- NiO/CPE CPE electrochemical sensors display an excellent electrochemical response for QCT.
Acknowledgment
The authors would like to acknowledge the financial support of this work by the Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran
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