Biosynthesis, Characterization, Adsorption and Antimicrobial studies of Vanadium Oxide Nanoparticles Using Punica Granatum Extract

. One of the fundamental


Introduction
For the development of green technology, science and technology are developing at the fastest rate.One of the fascinating fields that produce and use materials with interatomic structural properties is nanotechnology 1 .
In the 21st century, nanotechnology has become a significant scientific advancement.Nanoparticles are described as Published Online First: July, 2023 https://dx.doi.org/10.21123/bsj.2023.8114P-ISSN: 2078-8665 -E-ISSN: 2411-7986 Baghdad Science Journal desired morphology (shape, size, and crystalline nature), which can be used for various applications, including catalysis, biomedical, cheaper electrode, and biosensor 4 .Besides their distinct chemical and physical characteristics, nanoparticles functioned as a link between bulk materials and molecule or atomic structure 5 .As a result, they are the finest choice for many crucial applications, including biotechnology, trace substance identification, medicine, and electrochemistry.Vanadium pentoxide (V2O5) has recently seen an increase in interest as a semiconductor for solar cells, batteries, and gas sensing 6 .Bactericidal properties of metal oxide nanoparticles have been established.They can be used as suspensions for wastewater treatment and to prepare practical application surfaces 7 .The antibacterial mechanisms of metal oxide nanoparticles such as CuO, ZnO, MgO, TiO2, and CeO2 have been extensively researched because of their widespread application.Although the release of soluble ions is responsible for the antibacterial action of metal nanoparticles 8 , the mechanism of metal oxide nanoparticles can be very different.By producing reactive oxygen species (ROS) and destroying the genetic material, CuO destroys bacteria 9 .As a result of heavy contamination from industrial/agricultural effluents and artificial pollution risks, many developing countries have faced significant issues in ensuring a sustainable drinking water supply for their populations in recent years 10 .Innovative treatment methods based on technology are necessary for a sustainable drinking water supply.The ideal choice for futuristic adsorbents to remove water toxins is nano-sized metal oxides since these substances have the qualities of simplicity, adaptability, efficacy, and high surface reactivity 11 .In the present study, we have developed a facile green synthesis method for preparing V2O5NPs using Punica Granatum extract.The objective of this research was to achieve the goals of green synthesis for potential application and antibacterial activity used as an adsorbent to metal ions.

Materials and Methods
Collection of sample a local source of Punica granatum collected and marked.Hydrated vanadium sulfate is used VOSO4.H2O were acquired from England, NaOH from Alpha India's Alpha Chemical, ethanol from sakma aldaraj, copper, cobalt, and Nickel sulfate.All compounds are used.To create and identify the compounds, various spectroscopic and microscopic techniques were applied, following a Centrifuge type PLC, a Magnetic Stirrer, a Sensitive Electronic Balance type RADWAG, model As 220C1, and an Electric Oven type (FAITHFUL) model -WHL.25 AB and a Shaking Water Bath type (SCL FINETEDI), PHtype UV-visible tape measure (160/Uv) Shimadzu, FT-IR (8500S) type spectroscopy, X-ray (XRD) diffraction type PW1730 (Phillips/ Holland) were examined in the laboratories of the (center of examinations).SEM type FESEM-EDS Model MIRAIII, manufacturer TESCAN and country of manufacture Czech, Application of an X-ray energy dispersion device (EDX).TEM with the model number EM10C-100Kv.AFM, the magnitude of the zeta potential.

Preparation of Punica Granatum extract
A Fresh pomegranate peel has been gathered and cleaned with deionized water to remove dust particles.The dry pomegranate peel is gently combined in a mixer to create homogenous powders.Then, 20 g of leaves were pulverized and mixed with 200 ml of deionized water, then heated for 30 minutes at 90 °C with stirring.The solution was filtered and stored in the fridge.

Preparation of V2O5 NPs
The biosynthesis technique was used to synthesize vanadium oxide (V2O5) nanoparticles.Accordingly, 100 ml of pomegranate peel extract was added slowly (one drop per second) to 0.012 moles, 50 ml of VOSO4.H2O, and stirred for 30 minutes.Then, 40 ml of 1 N NaOH was added to the solution.The pH value turned to 12.A dark green precipitate was obtained; the precipitate was washed with deionized water (all steps done with a centrifuge, then decantation).Then, it dried for four h at 110 °C in the oven and then calcined for four h at 300 °C.A yellowish powder of vanadium oxide nanoparticles was obtained.

Study of Adsorption
A stock solution was made by dissolving 10g of CoCl2.6H2O in one Liter of distilled water to get 10000 ppm.For NiCl2.4H2O and CuCl2.2H2O, the stock was prepared by dissolving 5g in one Liter of distilled water.Hence the stock concentration was 5000 ppm for each.

Adsorption Process
Adsorption kinetics was carried out by putting 0.1 gm of the adsorbent nanoparticle into 50 ml of the 1000 ppm metal ion solution in the shaker water bath at 30°C and shaking rate 150 rpm; the adsorbent was separated from the solution at definite times by centrifuging then decantation, the remaining clear solution was measured by visible spectrophotometer to determine the remaining concentration after adsorption using the calibration curve.

Biological Activity
The disc diffusion method in a nutrient medium (jellose medium) type Muller Hinton agar was used to test the antimicrobial activity of the synthetic V2O5 NPs against two reference bacterial strains, (G+) Staphylococcus aureus and (G-) Escherichia coli, as well as Candida albicans fungal.The same method was used to test the antifungal activity using the nutrient medium (agar) potato dextrose.

FT-IR spectrum analysis
FT-IR spectrum analysis was performed on the vanadium oxide Fig. 1.The characteristic V2O5 peaks were located at 1026.13 cm -1 and 825 cm -1 , respectively.These values correspond to the stretching vibration of terminal oxygen bonds, V=O (825 cm -1 ), and the vibration of doubly coordinated oxygen (bridge oxygen) bonds, V-O-V (1038 cm -1 ).Both bands at 597.94 and 420.48 cm -1 were brought about by the V-O stretching mode 12 .

UV-Visible
The UV-Visible spectrum was used to investigate the prepared V2O5 Nps optical characteristics.Fig. 2 shows the UV-Vis absorption spectrum of the biosynthesis V2O5 Nps dissolved in deionized water.The transition holes process between V and O caused the absorption peak to appear in this spectrum at 332 nm, as a bonus, the quantum confinement property.The energy gap was calculated using the equation Eg = 1239.83/ λ and was 3.7344 eV.  1 13 .

Figure 3. XRD of V2O5 Nps.
The average crystal size was calculated using the Debye Scherrer equation, which was discovered to be 34.39 nm in Table 1.

EDX
The EDX spectrum Fig. 4, of V2O5 Nps, shows vanadium (V) and oxygen (O), showing their typical peaks in the spectrum.The results confirm that the generated nanoparticles are highly pure.Additionally, the estimates obtained from the EDX measurement agree with the elemental theoretical computations 14 .

SEM and TEM
SEM and TEM images of V2O5 NPs clearly showed the nanostructured unconsolidated forms with low proportions of rods shown in Fig. 5 and 6.From the TEM image, the V2O5 nanoparticles appeared unconsolidated in a nanoscale form.It is also noted that there are high percentages of pores in the samples, which distinguishes them in adsorption applications.From TEM image 15 , it has been concluded that the morphology of V2O5 nanoparticles was agglomerated together.The shape of the sample cannot be determined precisely due to the accuracy of the measurement.However, it seems to us that it contains measurements of the

AFM
AFM surface analysis must be carefully examined since numerous factors, such as deformations or image artifacts resulting from a tip and contamination, might produce incorrect results.Whether to operate in contact or without contact is one of these crucial elements.The intensity of the surface contact between the tip and the sample, known as the contact mode, permanently damages V2O5 Nps nanoparticles.Since the tip is placed very close to the sample but not in contact with it, the non-contact mode is only required for this work.
After metallization, Fig. 7 depicts the creation of three-dimensional spherical clusters of V2O5 Nps in terms of optical behavior.The surface contains pores and high roughness and tends to the amorphous shape in the sample, which increases its porosity due to the green synthesis of the nanomaterial [17][18] .In the Height Accumulation Distribution Report of V2O5 NPs, we note that the size of the prepared oxide nanoparticles ranges between 10.00 and 20.00, which confirms that vanadium oxide prepared using pomegranate peel extract is a nano oxide 19

Adsorption Studies
In comparing the adsorption behavior of the prepared metal oxide nanoparticles, the adsorption time profile was illustrated for each ion.Co (II) shows a continuous growth of the adsorption which means the process is far from equilibrium, and this behavior urges to suggest that this is not a simple type of adsorption; instead, it is a precipitation process in which metal oxide Nanoparticles act as crystallization nuclei which initiate the crystallization of the cobalt chloride salt.For Ni (II) and Cu (II), the plateau of equilibrium is more apparent, especially for Ni (II) Fig. 9.The V2O5 surface is the largest one in an alternative form.This arrangement may be due to the convergences of the atomic radius of the V element with that of Adsorbate metal ions, which make them incorporate easily with active lattice sites of the metal oxide [20][21][22] .

Figure 9. Adsorption time evolution of the metal ions on the V2O5 surfaces.
It is very clear from the above figures that the adsorption rate of Ni(II) is the highest one in the time scale and conditions of our experiment at all surfaces, while Co(ii) and Cu(II) ions are close in magnitude.The factors that affect the rate of the adsorption process are (i) charge, (ii) size, and (iii) electronic interactions.The first factor (charge) is the same in all ions, so it cannot be the significant factor that causes this difference.The size factor contributes to the diffusion process in the solution bulk and adsorbent mass as well 23 , for these ions follow the order Co(II)>Ni(II)>Cu(II).However, the variance is very small for bare ions.Considering the coordination and solvation shell, the difference will be negligible, especially in the solution.It will be considered after the initial adsorption in the diffusion stage in the metal oxide lattice and will take a different pattern.We think the electronic interaction factor is the primary important factor that causes this behavior.The magnetic moment of the unpaired electrons in the metal ions interacts with the magnetic moments of the unpaired electrons in the metal oxide.By this hypothesis, Co (II) must have the highest adsorption rate, followed by Ni (II) and then Cu (II).However, the observed decrease of the Co (II) adsorption rate and unlimited linear growth of the adsorbed portion indicate there is still another process taking place with the adsorption process, which is the Co (II) oxidation by metal oxide [24][25][26] .The table below shows how to find the adsorption ratios for each ion on the surface of nano-vanadium oxide, which is equal to (M+2 = Co, Ni, and Cu) ions was 56.66%, 77.00%, and 27.23%.

Antimicrobial Studies
The agar well diffusion method was used to test the antibacterial activity of the produced V2O5 27 and V2O5 nanomaterial against the bacteria E. coli, S. aureus, and the fungus Candida in different concentrations of 25%, 50%, and 75% 28 .The control as an antibiotic was streptomycin media, and the control was a DMSO solvent medium.The antimicrobial activities of the nanoplates were assessed by evaluating the zone of growth inhibition against the employed pathogens and adjusting the concentration of the manufactured V2O5 nanoplates.Concentrations of 75%, 50%, and 25% of V2O5 nanomaterial to demonstrate the antibacterial effectiveness of V2O5 nanomaterial in terms of zone of growth inhibition against the E.coli, S .aureus and the fungus Candida pathogens were the results of inhibition of vanadium oxide nanoparticles against positive and negative bacteria were compared with the standard drug Amoxicillin and the results of fungus inhibition with the standard drug Metronidazole.Shown in Tables 2,3 and Figs.10,11.

Conclusion
V2O5NPs were synthesized by the biosynthesis method of V2O5NPs rhombohedra phase with a diameter (34.39) nm obtained using VOSO4.H2O.The morphology of V2O5NPs was as an aggregation of thin sheet clusters.They have antimicrobial activity inhibiting the growth of S. aureus, E. coli, and a very high inhibition with Candida albicans fungal.V2O5NPs were removed simultaneously with three metal ions (M +2 = Co, Ni, and Cu) from water contaminated with them.

Figure 11 .
Figure 11.Zone of growth inhibition against E.coli and S .aureus.