Fabrication of Conifer Gum Based Metal Nano Particles for Pollution Control Applications

In recent decades, the analysis of nanoparticles is of greater importance for their applications in various elds. This present work also focuses the novel biological green material to synthesize the copper and cobalt oxide nanoparticles. The copper oxide (CuO) and cobalt oxide (Co 3 O 4 ) nanoparticles (nps)have been synthesized by biological strategy utilizing AH (Araucaria heterophylla) gum extract. The characterization techniques, i.e. UV, GC-MS, FT-IR, XRD, SEM, HR-TEM provide concrete information about the morphology, crystalline nature and structure of the synthesized nanoparticles. The high resolution TEM and SAED images conrm the formation of spherical shaped (Co 3 O 4 ) and oval shaped (CuO) isolated nanoparticles. The catalytic adequacy of the developed catalyst, copper oxide (CuO) and cobalt oxide (Co 3 O 4 ) nanoparticles was analyzed for the degradation of dyes: Methylene Blue (MB), Congo Red (CR), Acid Violet (AV).The kinetic investigations for the reduction of synthetic dyes by the nanoparticles were assessed and the reduction contemplates are very much tted with the pseudo second order kinetic model with less time.The antibacterial and antifungal activity of the prepared nanoparticles have been evaluated against Escherichiacoli, Staphylococcus aureus, Bacillus subtilis, Aspergillusniger and Candida albicans. synthesize


Introduction
As of late, there is an extensive enthusiasm on metal nanoparticles as a result of their trademark property, which are totally not quite the same as the mass. Nanoparticles are exceptionally encouraging in light of the fact that they utilize imaginative materials with new electronic, attractive and warm properties. They have expansive surface to volume proportion and it display expanded surface reactivity contrasted with mass materials, which gives them to go about as a decent impetus [A. Muthu Kumara Pandian et al. 2021]. Recent research recommended that when metal particles turned out to be little in size, their redox properties vary from mass metal. In this manner, nano particles have pulled in consideration from both essential and mechanical perspectives in view of their quantum measure impact which is from the decrease of free electrons [Jinming Liu et al. 2020]. Synthesis of nanoparticles is of extraordinary signi cance, as particles developed from a couple of hundred molecules have properties unique in relation to the mass. Various techniques i.e., physical, compound, natural strategies have been utilized for the readiness of metal nanoparticles [Zhongliang Ma et al. 2018]. There is a need to create eco-accommodating procedures to maintain a strategic distance from the utilization of hazardous/cancer-causing synthetic substances in the process are termed as the "green synthesis". Green combination of metal nanoparticles have points of interest over the existing different strategies and methods as a result of its modest, eco-accommodating, effectively utilized for huge scale blend and it needn't bother with high weight, temperature and poisonous synthetic concoctions for the union [Reza Mohammad inejad et al. 2016]. The different bio molecules found in the plant extricates, incorporate polysaccharides, polyphenols, aldehydes, ketones, proteins, catalysts, amino acids, peptides that can decrease the metal particle and balance out the nanoparticles with required shapes and sizes [Ahmed Barhoum et al. 2020].
Among the different metal nanoparticles, copper nanoparticles are conceivably appealing, on the grounds that they are powerful in different properties like optical, electrical, thermal properties [Xiulin Shu et al. 2020]. Because of their prevalent quality, they are utilized as sensors, energy storage devices and it is mostly utilized as an antimicrobial operators and antifungal specialists [S. Pavithradevi et al. 2017]. Furthermore, besides, copper nanoparticles have high thermal and electrical conductivity. Copper nanoparticles have additionally been utilized as an option for gold, silver and platinum nanoparticles in numerous different elds, for example, thermal and microelectronics [  In the present work the antibacterial and antifungal activities of the synthesized copper oxide (CuO) and cobalt oxide (Co3O4) nanoparticles were tried. The microbes utilized in the antibacterial movement were Escherichia coli, Staphylococcus aureus, Bacillus subtilis,Salmonellaparatphi.Staphylococcus aureusand Bacillus subtilisare gram positive microorganisms. Escherichia coli and Salamonellaparatyphiare the gram negative bacteria. S.aureus and E.coli are known to develop a few of the bacterial diseases in the network. The organisms utilized for the antifungal activity are Aspergillusniger and Candida albicans. Metal nanoparticles are fabricated based green approach using AH gum and will tested for antimicrobial, antifungal apart from dye adsorption phenomena described in the article.

Preparation of gum extract and metal nanoparticles
The collected plant gum was washed in distilled water to remove residues and powdered to get the dark brown powder and stored in humid free atmosphere. 0.1 wt. %gum in double distilled water was used for the preparation of copper and cobalt oxide nanoparticles.0.1M cobalt nitrate (Co (NO 3 ) 2 .6H 2 O) was dissolved in distilled water and mixed with gum extract and kept under constant magnetic stirrer for around 30 min. After that 0.2M NaOH solution were added drop wise to the above blended solution and while the addition of NaOH solution the pink colored solution was changed to olive green and to light brown. After the entire addition of NaOH solution, stirring was proceeded for around 2 hr at room temperature. The dark brown color cobalt hydroxide precipitate settles down and the excess solution found on the top disposed off very carefully and the brown color precipitate which was separated, washed with distilled water for a few times. Also, it was warmed in a mu e furnace at 400°C for 3 hr. Finally, the black color cobalt oxide Co 3 O 4 ) precipitate was obtained. Similarly, the copper oxide (CuO) nanoparticles were set up by the above strategy utilizing copper nitrate (Cu(NO 3 ).3H 2 O) and NaOH solution (1:2M proportion). The brown colored precipitate was separated and washed with distilled water for few times and heated in a mu e furnace at 400 ο C for 3 hr. At last, the brownish black color copper oxide (CuO) precipitate was obtained for further investigations. Microscope with an Energy dispersive X-ray spectrometer (JSM 6390 LV) at magni cation of 30,000. The lms of the samples were set up on a carbon covered copper network by setting a little measure of the sample and after that allowed to dry earlier estimations. Qualitative con rmation of the metal nanoparticles composition was measured by various techniques. Fourier-transform infrared spectroscopy (FTIR) were recorded with a FT/IR-4600typeA, JASCO to detect functional groups of Co 3 O 4 , CuO nanoparticles. X-ray diffraction (XRD) recorded for Co 3 O 4 , CuO to understand crystal indices, structure and size of the nanoparticles using X-ray diffractometer (Shimadzu, XRD 6000) with Cu kα radiation (λ = 0.1548 nm) at 40 kV and 80 mA in the region of 2θ from 10 o to 90 o . Size, morphology and crystalline nature of Co 3 O 4, CuO nanoparticles were investigated by high resolution through transmission electron microscope (TEM) and selected area electron diffraction (SAED) were also recorded on a Technai G20-stwin using an accelerating voltage of 200 kV and different magni ed images have been displayed.

Degradation of Organic Dyes
Degradation of Methylene Blue (MB), Acid Violet-49 (AV) and Congo red (CR) dyes utilizing the green-integrated copper and cobalt oxide nanoparticles as catalyst in the presence of sodium borohydride (NaBH 4 ). The 20mg of synthesized nanoparticles was added to different concentrations (10, 20, 25, 30, 40, 50ppm) of aqueous dye solution with freshly prepared NaBH 4 and the response analyzed by UVVIS spectrophotometer. Color change observed once the reaction completes, i.e. colored solution changes in to colorless. In the present examination,   Table 1 presents the data associated with each of the lines in the spectrum.

Catalytic activity of synthesized CuO and Co 3 O 4 nanoparticles
Organic dyes (non-degradable) are broadly utilized as a shading agent for various matrices, material, paper, plastic and nourishment enterprises. Numerous reports are recommended that metal and metal oxide nanoparticles are utilized as catalyst to reduce hazardous dyes from water through photo degradation process. Here, catalytic reduction ability of green synthesized CuO and Co 3

Kinetics studies of catalytic reduction
Catalytic degradation is a quickly growing innovation for waste water treatment, including an extensive variety of organic poisons. In this way, understanding the kinetics and mechanisms of catalytic degradation of synthetic dues is a fundamental part of evaluation. The degradation phenomena was inspected by two active models, pseudo rst order and pseudo second order.
The pseudo rst order equation can be communicated by, log ( qe-qt ) = log qe -k1t / 2.303 Where k1 is the pseudo rst order rate constant (min-1), qe and qt are the amount of colors (MB, AV-49 and CR) reduced (mg/g) at equilibrium and at time t (min) required for the reduction procedure. The plot of log (qe-qt) against time t should give the direct relationship from which k1 and qe can be ascertained by the slope and intercept acquired from the chart individually.
The pseudo second order equation is given beneath: Where k2is the pseudo second order rate constant (g/mg/min), qe and qt are the measures of dyes (MB, AV-49 and CR) diminished (mg/g) at equilibrium and at time t (min) required for the reduction procedure. The plot of t/qt against time gives the slope of 1/qe and an intercept of 1/k2qe2.  Table 2The plots were observed to be in great concurrence with the correlation coe cients. The gured q e (hypothetical) values are very much coordinated with the trial q e qualities and R 2 are additionally high, which speaks to the relevance of pseudo second order to clarify the reduction procedure. The outcomes got a rm that the second order kinetic equation is the best tting model for both the cobalt and copper oxide nanoparticles.

Effect of the mixture of the two organic dyes
The e uents from the industries contain few synthetic organic dyes, which are discharged directly into the water source. Here an attempt was made to study the effect of mixture of (MB and AV) were examined. Catalytic degradation of the mixture of two synthetic dyes (MB and AV) was exceptionally good, i.e mixed dyes were degraded 96% and 98% with 20mg of the copper and cobalt oxide nanoparticles separately. Similar in line, catalytic degradation of the blend of two synthetic dyes (MB and CR) provides85% and 88 % degradation with the 20mg of the copper and cobalt oxide nanoparticles separately. The outcomes acquired when these dyes are treated alone in similar parameters and concurrent presence of two organic dyes in solution did not decline catalytic reduction process. Degradation rates acquired for both mono and bi-component framework were similar. It is recommended that both copper and cobalt oxide nanoparticles can be capable to form complex frameworks with excess of one

Effect of the gum extract
Reduction of organic dyes (MB, AV-49 and CR-(20ppm), by the regular green uid concentrate of Araucaria heterophylla gum extract (1% solution) with the presence of copper and cobalt oxide nanoparticles. The absorbance data demonstrate the concentrate to degrade dyes (MB, AV-49 and CR) solution and 120 mins time date shows appreciable decline in dyes absorbance. Therefore, copper and cobalt oxide nanoparticles may act as an electron exchange mediator between the extract and the dyes molecule solutions by executing as a redox catalyst, which is assigned as an electron transfer impact (Fig. 9). Copper and cobalt oxide nanoparticles act as an electron exchange mediator between the extract and the methylene blue dye solution. Fig. 9 reveals the dye removal of methylene blue by the gum extract within the sight of various quantity (20mg and 50mg) of copper and cobalt oxide nanoparticles.

Antibacterial and antifungal activity
The antibacterial and antifungal activities of the synthesized cobalt oxide (Co3O4) and copper oxide (CuO) nanoparticles shown in Fig. 15 were studied and the results obtained are compared with the standard cipro oxacin.
In this present work, the antibacterial activity was tested in the Escherichiacoli, Salmonella paratphibacteria (gram negative) and Staphylococcus aureus, Bacillus subtilis (gram positive). The antibacterial activities of Co3O4 and CuO nanoparticles against the above mentioned bacteria were studied by determining the inhibition zone which was shown in the

Conclusion
In this present work, the effective copper oxide (CuO) and cobalt oxide (Co3O4)   FT-IR spectra of cobalt oxide and copper oxide nanoparticles.      The percentage of the dye removal obtained on the reduction of methylene blue dye solution by the gum extract in the presence of different amounts (20mg and 50mg) of cobalt oxide (a) and copper oxide (b) nanoparticles.    The catalytic performance and reusability of (a) cobalt and (b) copper oxide