DESC:FIELD
The present application relates to a catalyst composition and a process for degradation of chemical contaminants in waste water. Particularly, the catalyst composition comprises ozone (O3) microbubble (MB) and at least one metal nanoparticle for degradation of the chemical contaminants in waste water.

DEFINITIONS
As used in the present disclosure, the following terms are generally intended to have the meaning as set forth below, except to the extent that the context in which they are used indicate otherwise.

MB (Microbubble) ozonation refers to the oxidation reaction based on the microbubble (MB) of the ozone gas (O3).

BACKGROUND
The background information herein below relates to the present disclosure but is not necessarily prior art.

A variety of elements, substances and the chemical compounds such as prescription and non-prescription medications, hormones, antibiotics, personal care products and the like may serve as contaminants. The contaminants are the remnants that are generally not degraded of its own or are in-efficiently degraded upon disposal. The in-efficiently degradation contributes to the wastewater contaminated. Therefore, the contaminants are the leading cause of pollutants in the wastewater. Thus, there is an emerging global concern of wastewater contaminated with such pharmaceutical.

The known processes for treating wastewater contaminated with pharmaceutical compounds are the electrochemical process, Membrane bioreactors, biological treatment, Bio filtration, oxidation, etc. A reference may be made to “Water Research, Volume 10, Issue 5, 1976, Pages 377-386, ISSN 0043-1354, https://doi.org/10.1016/0043-1354 (76)90055-5” for the hydroxyl radicals for degrading the chemicals. The Hydroxyl radicals are formed upon the hydroxide-ion catalyzed decomposition of ozone in water as is shown by the relative rates with which the organic substrates compete with each other for consuming the oxidative intermediates. The hydroxyl radical reaction is applied to describe oxidations initiated by ozonation. Another reference “Journal of Environmental Chemical Engineering, Volume 12, Issue 6, 2024,114421”, describes Ozone-microbubble (MB)-enhanced oxidation of pharmaceuticals and personal care products in municipal secondary effluents. The oxidizing capacity ratio of microbubble (MB) to mill bubble for PPCP’s was between 1.26 and 3.50 times, and ozone-resistant PPCPs removal was enhanced more than ozone-reactive PPCPs by microbubble (MB) ozonation. The above mentioned solution to the wastewater treatment results in incomplete removal of the contaminant, and it has complex handling procedures.

The other drawbacks and limitation of the wastewater treatment is their energy-intensive procedures, high chemical usage, high-cost resistance, and inadequate persistence (et al.Lee, Yunho; von Gunten, UrsWater Research (2010), 44(2), 555-566). Further, the wastewater treatment plants involve the utilization of multiple treatment phases, each aimed at effectively extracting contaminants and impurities from the wastewater prior to its introduction into the ecosystem. Therefore, the known process of wastewater treatment are slow, have weak selectivity towards contaminants, based on the lower lifetime of the electrodes, has high chemical consumption, and even run on a high cost of electricity, and provides a low recycle ability of the water used for treatment.

There is, therefore, felt a need that mitigates the drawbacks mentioned hereinabove or at least provide a suitable alternative.

OBJECTS
Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows:

An object of the present disclosure is to provide a catalyst composition, and a process for degradation of chemical contaminants in waste water.

Another object of the present disclosure is to provide a metal NP coated ozone (O3) microbubble (MB), wherein the size of ozone (O3) microbubble is in the range of 40 to 60 µm.

Still another object of the present disclosure is to provide an oxidative ozone (O3) catalyst i.e. ozone (O3) microbubble (MB) of 40 µm formed at the ozone (O3) flow rate 0.25 L/min.

Still another object of the present invention is to provide a process of catalytic magnetic nanoparticle coated MB prepared by ultrasonication for the oxidative degradation of the chemical contaminants.

Yet another object of the present disclosure is to provide a metal NP coated ozone MB catalyst, in particular FeNP coated Ozone MB for MB Ozonation.

An object of the present disclosure is to ameliorate one or more problems of the background or to at least provide a useful alternative.

Other objects and advantages of the present disclosure will be more apparent from the following description, which is not intended to limit the scope of the present disclosure.

SUMMARY
The present application relates to a metal coated catalytic composition and a process for degradation of chemical contaminants in waste water. The metal coated catalytic composition comprising of Ozone (O3) microbubble (MB) having a predetermined size; and at least one metal nanoparticle selected from cobalt (Co), iron (Fe) and magnesium (Mg) nanoparticles (NP). The metal NP coated ozone (O3) microbubble (MB) s generates radical for catalysis. The size of ozone (O3) microbubble (MB) is in the range of 40 to 60 µm. The ozone (O3) microbubble (MB) is formed at the ozone (O3) flow rate in the range of 0.15 L/min to 0.50 L/min, in particular 0.25 L/min.

The metal for the metal NP is a transition metal selected from cobalt (Co), iron (Fe) and magnesium (Mg), wherein the transition metal is a substrate having high stability to ozone (O3); and activates ozone (O3) surface for radical generation. The radical generation from the metal coated ozone (O3) microbubble (MB) is up to 15% of molar mass of ozone (O3), and wherein the molar ratio of the radical to ozone (O3) is in the range of 0.08: 1 to 0.1:1.

The process for degradation of chemical contaminants in wastewater comprising the steps of maintaining the flow of O3 in the range of 0.15 L/min to 0.50 L/min to obtain an O3 microbubble (MB); and coating the O3 microbubble (MB) with a metal nanoparticle (NP) to obtain a catalytic metal coated-O3 microbubble (MB) for radical generation. The metal coated-O3 catalytic microbubble (MB) is contacted with a predetermined amount of waste water having at least one chemical contaminants to obtain a mixture. The mixture is reacted for a time period in the range of 2 to 6 minutes at a predetermined reaction conditions to obtain water free from the chemical contaminants.

The predetermined amount of the metal NP coated ozone (O3) microbubble (MB) for radical generation is in the range of 0.1-0.50 g/L. The predetermined reaction conditions are optimized pH in the range of 5-9, pressure of 1 atm, and room temperature. A FeNP coated ozone (O3) microbubble (MB), characterized by having molar ratio of radical: ozone of 0.08:1; and paramagnetic property of 55.4 emu/gm magnetism.

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWING
The catalytic composition and a process of the present disclosure will now be described with the help of the accompanying drawing, in which:
Figure 1 (a) illustrates the % degradation of Ciprofloxacin (CP) in a drug mixture in accordance with the present disclosure.
Figure 1 (b) illustrates the % degradation of Salicylic acid (SA) in a drug mixture in accordance with the present disclosure;
Figure 1 (c) illustrates the % degradation of Ibuprofen (IBU) in a drug mixture in accordance with the present disclosure;
In reference to Figure 1(a)-1(c), the experiments are performed using Ozone MB, and Metal NP coated Ozone MB (Fe-O3-MB) at a variable flow rate of 0.15L/min, 0.25L/min and 0.5L/min. The % degradation was comparatively higher with Fe-O3-MB, in accordance with the present disclosure,
Figure 2 (a) illustrates effect of pH on the % degradation of CP in accordance with the present disclosure;
Figure 2 (b) illustrates effect of pH on the % degradation of SA in accordance with the present disclosure;
Figure 2 (c) illustrates effect of pH on the % degradation of IBU in accordance with the present disclosure;
In reference to Figure 2(a)-2(c), the experiments are performed using Ozone MB, and Metal NP coated Ozone MB (Fe-O3-MB) at a pH of 5, 7 and 9,
Figure 3 (a) illustrates effect of the catalyst dose on the % degradation of CP in accordance with the present disclosure;
Figure 3 (b) illustrates effect of the catalyst dose on the % degradation of SA in accordance with the present disclosure;
Figure 3 (c) illustrates effect of the catalyst dose on the % degradation of IBU in accordance with the present disclosure;
In reference to Figure 3(a)-3(c), the experiments are performed using Ozone MB, and Metal NP coated Ozone MB (Fe-O3-MB) using the catalyst concentration of 0.1g/L, 0.25 g/L , and 0.50 g/L,
Figure 4 illustrates the effect of the % degradation of multiple drugs (CP, SA and IBU) simultaneously in the predetermined conditions at a pH in the range of 5-9, pressure of 1 atm, and room temperature using the catalyst conc. of 0.25 g/L;

Figure 5 (A) illustrates the LC-MS-MS study of Ciprofloxacin (CP), Salicylic acid (SA), Ibuprofen (IBU) in the waste water before the degradation;

Figure 5 (B) illustrates the LC-MS-MS study of the waste water post degradation of ciprofloxacin as contaminates using Fe-coated O3 ozone microbubble (MB) based on the process in accordance with the present disclosure,

Figure 6 illustrates the ESR spectrum of radicals formed in (a) O3MB and (b) O3 -FeNP O3 MB up to 5 minutes.
Figure 6(a) shows the formation of hydroxyl radicals from ozone microbubble (MB). Notably, the height of the DMPO-OH peaks increases continuously after 1 minute, suggesting that a significantly greater number of hydroxyl radicals are produced during the collapse of ozone microbubble (MB). In contrast, Figure 6(b) depicts the formation of hydroxyl radicals from catalyst-coated microbubble (MB)s (i.e. FeNP O3 MB). In this case, DMPO-OH peaks form within just 5 seconds, highlighting the effectiveness of metal NP coating on ozone microbubble.

Figure 7 illustrates the comparison of O3 MB and FeNP-O3MB within 5 seconds.

Figure 8 illustrates Hyperfine splitting diagram of DMPO-OH radical adduct involved in microbubble (MB) system.

Figure 9 illustrates ESR spectra of Fe nanoparticle at 297K wide range of magnetic
field (500mT).

DETAILED DESCRIPTION
Embodiments, of the present disclosure, will now be described with reference to the accompanying drawing.

Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and process, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.

The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms "a,” "an," and "the" may be intended to include the plural forms as well, unless the context clearly suggests otherwise. The terms "comprises," "comprising," “including,” and “having,” are open ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, modules, units and/or components, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the process and process of the present disclosure is not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed. When an element is referred to as being "mounted on," “engaged to,” "connected to," or "coupled to" another element, it may be directly on, engaged, connected or coupled to the other element. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed elements.

The terms first, second, third, etc.,should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure. Terms such as “inner,” “outer,” "beneath," "below," "lower," "above," "upper," and the like, may be used in the present disclosure to describe relationships between different elements as depicted from the figures.

There is an emerging global concern of wastewater contaminated with the pharmaceutical. The known processes for treating wastewater contaminated with pharmaceutical compounds are the electrochemical process, Membrane bioreactors, biological treatment, Bio filtration, oxidation, etc. These process have disadvantages, not limited to the incomplete removal of contaminants, energy-intensive process, chemical usage, high-cost resistance, and persistence. To address these drawbacks, there is a growing need for innovative and advanced wastewater treatment technologies that specifically target pharmaceutical contaminants.

Among the known process to treat wastewater contaminated with the pharmaceutical compounds, the advanced oxidation process (AOP) based on the ozone is effective in transforming the pharmaceutical contaminants into biodegradable compounds. The exemplified Fe magnetic NP (nanoparticles) as the catalyst for such oxidation reaction using the microbubble (MB)s of ozone has demonstrated the exceptional ability for effective treatment of the multiple pharmaceutical compounds in wastewater. Advanced oxidation processes (AOPs) create free radical species that function as oxidizing agents for the pharmaceuticals. The catalyst accelerates the dissociation of ozone (O3) and the formation of OH radicals that can effectively degrade various types of organic compounds.

The present disclosure relates to a metal coated catalytic composition, and a process for degradation of chemical contaminants in waste water.

The first aspect of the present disclosure is to provide a metal coated catalytic composition for degradation of chemical contaminants in waste water.

In an embodiment, the metal coated catalytic composition for degradation of chemical contaminants in waste water comprising of:
• Ozone (O3) microbubble (MB) having a predetermined size; and
• At least one metal nanoparticle selected from cobalt (Co), iron (Fe) and magnesium (Mg) nanoparticles (NP),
wherein the metal NP coated ozone (O3) microbubble (MB) generates radical for catalysis.

In an embodiment, the size of ozone (O3) microbubble is in the range of 40 to 60 µm.

In an embodiment, the ozone (O3) microbubble is formed at the ozone (O3) flow rate in the range of 0.15 L/min to 0.50 L/min. In an exemplary embodiment, the ozone (O3) microbubble is formed at the ozone (O3) flow rate is 0.25 L/min.

In an embodiment, the metal for the metal NP is a transition metal selected from cobalt (Co), iron (Fe) and magnesium (Mg). The transition metal is a substrate having high stability to ozone (O3); and activates ozone (O3) surface for radical generation.

In an embodiment, the radical generation from the metal coated ozone (O3) microbubble is up to 15% of molar mass of ozone (O3). The molar ratio of the radical to ozone (O3) is in the range of 0.08: 1 to 0.1:1.

In an embodiment, the metals are selected from Fe, Co and Mg.

In an embodiment, the metal coated ozone MB are selected from iron (Fe) coated nanoparticle O3MB.

In an embodiment, the Metal coated nanoparticle O3MB can have a particle size in the range of 10 µm to 80 µm.

In an embodiment, the metal coated ozone MB can be used for oxidative degradation of the contaminants.

In an embodiment, the Fe3O4 could be a catalyst to enhance ozone based degradation.

The second aspect of the disclosure is to provide a process for the catalytic degradation of the contaminants.

In an embodiment, the present disclosure provides a process for the degradation of contaminants based on metal coated ozone (03) MB.

In an embodiment, the process for degradation of chemical contaminants in the wastewater comprising the steps of:
• maintaining the flow of O3 in the range of 0.15 L/min to 0.50 L/min to obtain an O3 microbubble (MB);
• coating the O3 microbubble (MB) with a metal nanoparticle (NP) to obtain a catalytic metal coated-O3 microbubble for radical generation;
• contacting a predetermined amount of the metal coated-O3 catalytic microbubble with the waste water having at least one chemical contaminants to obtain a mixture: and
• reacting a mixture for a time period in the range of 2 to 6 minutes at a predetermined reaction conditions to obtain water free from the chemical contaminants.

In an embodiment, the predetermined reaction conditions are the optimized pH in the range of 5-9, pressure of 1 atm, and room temperature.

In an embodiment, the predetermined amount of the catalyst i.e. metal NP coated ozone (O3) microbubble (MB)s for radical generation is in the range of 0.1-0.50 g/L, In an exemplary embodiment, the amount of metal NP coated ozone (O3) microbubble (MB) is 0.25 g/L.

In an embodiment, the chemical contaminants are selected from Ciprofloxacin (CP), Salicylic acid (SA), and Ibuprofen (IBU).

Flow rate of ozone:
In the heterogeneous catalytic process which involves ozone, the ozone flow rate plays an important role. The increase in the flow rate of ozone can enhance the rate of ozone mass transfer, thereby promoting the generation of highly reactive oxygen species. The ozone flow rate is regulated to achieve optimal production of hydroxyl radicals and minimize ozone loss due to decomposition. In the case of an ozone microbubble high ozone flow rate gives macro bubbles instead of microbubble (MB)s. Increasing air flow rate increases the probability of collision and coalesce which leads to large microbubble (MB)s. Therefore 0.25 LPM ozone flow rate has been selected for experiments.

Effect of pH:
The pH value increased the % degradation significantly. This influence of pH on the degradation rate is attributed to the presence of • OH radicals. It is known that at acidic pH, O3 remains in water in molecular form. But at alkaline pH, OH - initiated the chain reactions of ozone decomposition to • OH radicals.

Fe3O4 is a catalyst to enhance ozone decomposition to • OH radicals, and the • OH radicals were a powerful, effective, no selective oxidizing agent. Thus, pollutant removal was significantly improved. Although the optimum pH for the process was 9, in the case of catalyst-coated ozone microbubble a near complete degradation of contaminants (? 100%) was achieved within 6 minutes at pH 7. Maintaining a working pH of 7 in the wastewater aligns with industrial parameters, making it useful from an industrial viewpoint.

Catalyst Conc.
The Fe coated-O3 microbubble is enabling the rapid generation of • OH radicals in neutral pH conditions. The production of a higher number of • OH radicals at the optimum pH level is crucial for the rapid degradation of multiple drug pollutants. One way to increase the number of radicals is to adjust the catalyst dosage and O3 flow rate. The catalyst dosage was varied in the range of 0.1-0.50 g/L. It was found that the complete degradation of pollutants occurs within 6 minutes and goes below the detection limit of the instrument.

Therefore, the performances of the change in catalyst doses over 6-minute duration were compared, as shown in Figures 3(a), 3(b), and 3(c).

To briefly compare the degree % degradation observed at 6 min, the catalyst dose of 0.1, 0.25, and 0.50 g/L resulted in degradation percentages of 100%.

These findings suggest that the minimum amount of catalyst dose facilitates the generation of • OH radicals, resulting in a higher % degradation of the pollutant. It might be possible that further increasing the catalyst dose will lead to more rapid degradation of pollutants, but that would also create more usage and loss of the synthesized catalyst. The 0.25 g/L catalyst dose degrades the pollutant within 6 minutes completely, which is considered as optimal catalyst dose.

The present disclosure is further described in light of the following experiments which are set forth for illustration purpose only and not to be construed for limiting the scope of the disclosure. The following experiments can be scaled up to industrial/commercial scale and the results obtained can be extrapolated to industrial scale.

EXPERIMENTS
Chemicals and Equipment Materials
The chemicals used for the experiments were procured from the standard commercial establishments and were of LR/AR grade. All other solvents were of analytical grade. All the equipments, materials used were procured from the standard commercial establishments and were properly calibrated before use to minimize errors. Ozone (O3) generator purchased from Eltech Ozone, Mumbai, India. The Metal salts including Fe, Co, Mg are purchased from Merk, India.

Example 1: Metal coated catalytic compositions in accordance with present disclosure.
The experiments for degradation of chemical contaminants in waste water were performed using the catalytic composition (Table 1). The metal NP was selected from cobalt (Co), iron (Fe) and magnesium (Mg) nanoparticles.
Table 1:
S.No Composition A Composition B Composition C
1. MB of Ozone (O3) MB of Ozone (O3) MB of Ozone (O3)
2. FeNP CoNP MgNP

Table 2: Comparative experiments for the radical generation of the metal coated O3MB in accordance with the disclosure
Table 2:
S.No Catalytic Composition Radical Generation (molar ratio with respect to O3)
1. Ozone (03) Nil
2. MB of Ozone (O3) 0.05:1
3. Composition A 0.08:1
4. Composition B 0.1:1
5. Composition C 0.1:1

The radical generation for degradation of the chemical contaminants was found to be highest using the catalyst composition in accordance with the present disclosure. The molar ratio for the radical generation with respect to O3 was found to be in the range of 0.08: 1 to 0.1:1.

Example 2: A process for degradation of chemical contaminants in wastewater
The flow of O3 was maintained at 0.25 L/min (LPM) to obtain O3 microbubble (MB) (MB). The O3 microbubble (MB) was coated with Fe nanoparticle (NP) to obtain a catalytic Fe coated NP O3 microbubble (MB) for the radical generation. 25 g/L of the metal coated-O3 catalytic microbubble (MB) was contacted with the waste water consisting of CP, SA and IBU as the chemical contaminants and for 6 minutes at a pH of 7, and room temperature to obtain water free from the chemical contaminants.

Optimized process parameters:
Catalyst Dose = 0.25 g/L, O3 flow rate= 0.25 LPM, pH =7.
Fe-O3-MB = magnetic nanoparticle-coated O3 microbubble (MB).

Example 3: Degradation studies based on the process parameters for degradation of chemical contaminants in wastewater.
A. The Effect of Flow rate of ozone
The effect of ozone flow rate was studied under a fixed initial concentration of contaminants at preliminary pH of 5 and a catalyst dose of 0.25 g/L.
Figure 1(a), 1(b), and 1(c) shows the percentage removal of contaminants increased with increasing the ozone flow rate.
B. Effect of pH
The degradation of multiple pharmaceutical compounds at initial pH of was examined with an initial concentration of contaminants (60 mg/ L), with ozone flow rate of 0.25 LPM, and a catalyst dose of 0.25 g/ L.
Figure 2(a), 2(b), and 2(c) schematic of %degradation with respect to time maximum degradation
C. Effect of Catalyst Concentration
The Fe coated-O3 microbubble (MB) catalyst dosage was varied in the range of 0.1-0.50 g/L. It was found that the complete degradation of pollutants occurs within 6 minutes and goes below the detection limit of the instrument.
A performance of the change in catalyst doses over a 6-minute duration were compared, as shown in Figures 3(a), 3(b), and 3(c).

Example 4: LC-MS analysis
The LC-MS analysis was conducted to characterize both the fragmented products and the fragmentation mechanisms. Mass spectra were acquired for the chromatographic peak eluting at 3.29 minutes. The observed m/z peaks aligned with the expected fragmentation pattern of ciprofloxacin, with the most prominent peak being M+1 at 332.10, matching the molecular weight of ciprofloxacin (331 Daltons). After the ozone microbubble (MB) treatment, the chromatographic peak at 3.29 minutes completely disappeared, and the mass spectra displayed a prominent peak at m/z 148.05. Similarly, after subjecting the sample to Fe-coated NP O3 microbubble (MB) treatment, the peak at 3.29 minutes in the chromatogram vanished, and the corresponding mass spectra revealed a strong peak at m/z 74.82.9. (Refer Figure 5(B)).
The results have validated the degradation of ciprofloxacin to the smaller compounds (lower mol.wt compounds) when treated using the Catalyst in accordance with the disclosure.

Example 5: ESR result of O3MB and FeNP Coated O3 MB

Method: To detect radicals, we used the spin-trapping agent DMPO (5, 5- dimethyl-1-pyrroline–N-oxide), purchased from TCI, India. The catalyst was synthesised in the lab, and Eltech ozone generators were used for ozone.

The recordings were conducted under the following parameters: a scan range from 330 to 342 mT, a time constant of 0.2 ms, a scan duration of 20 seconds, a modulation amplitude of 0.2 mT, a microwave frequency of 9.44 GHz, and a microwave power setting of 10 mW, utilising a Magnettech ESR 5000 spectrometer (Bruker, Germany).
The spectra of FeNPs were recorded over a wide magnetic field sweep range of 600 mT, using an amplitude modulation of 0.2 mT and a microwave power of 10 mW.

DMPO is an effective spin-trapping agent in electron spin resonance (ESR) spectroscopy. Hydroxyl radicals are strong oxidants in aqueous solutions, reacting rapidly with a wide range of dissolved compounds. In contrast, ozone acts as a highly selective oxidant. Understanding the transformation process of ozone into hydroxyl radicals is crucial for effective wastewater treatment.

Using electron spin resonance spectroscopy, we demonstrated that the collapse of ozone microbubbles generates hydroxyl radicals, as illustrated in Figure 6.

Figure 6(a) shows the formation of hydroxyl radicals from ozone microbubbles. Notably, the height of the DMPO-OH peaks increases continuously after 1 minute, suggesting that a significantly greater number of hydroxyl radicals are produced during the collapse of ozone microbubbles.

In contrast, Figure 6(b) depicts the formation of hydroxyl radicals from catalyst-coated microbubbles. In this case, DMPO- OH peaks form within just 5 seconds, highlighting the effectiveness of the catalyst coated with metal NP.

The catalyst accelerates ozone conversion into hydroxyl radicals, enabling the rapid degradation of pharmaceutical compounds in the wastewater.

In catalyst-coated microbubbles, the formation of hydroxyl radicals occurs an order of magnitude faster than with ozone microbubbles without a catalyst. With the catalyst-Fe coated O3 microbubbles, DMPO-OH peaks appear within 5 seconds (Figure 7).

This speedy production showcases the improved effectiveness of the catalyst in facilitating the transformation of ozone into hydroxyl radicals. In contrast, ozone microbubbles (independently) are formed at a slow rate, and no peak was observed in 5 sec. Overall, the production of hydroxyl radicals is accelerated, resulting in faster degradation in wastewater treatment using FeNP-O3MB.

DMPO is an effective spin trap for radical intermediates in many Advanced Oxidation Processes (AOP) systems. Different radicals are identified based on their hyperfine coupling constants, A N and A H. In AOP systems for water treatment, the radicals generated are predominantly centred on oxygen (O) or carbon (C).

The DMPO-OH adduct can be a criterion for identifying DMPO-trapped radicals in Electron Spin Resonance (ESR) spectra. It exhibits a characteristic quartet with overlapping A N = A H, resulting in a total spectral width of approximately 4.5 mT (45 G), as shown in Fig. 8. This quartet is typically associated with non-C-centered radicals. Conversely, radicals with a spectral width greater than 45 G are identified as C- centered, while those with less than 45 G are O-centered. Furthermore, radicals with higher A N and A H values are linked to lower electronegativity, reflecting the key physicochemical properties of these species.

Figure 9 displays the ESR spectra of Fe3O4 nanoparticles. The ESR spectra can be influenced by the super-paramagnetic surface effects and the presence of unpaired electrons from the iron ions in their structure. FeNPs usually exhibit a wide resonance peak originating from the dipolar interactions between magnetic moments and the super paramagnetic nature. Based on our calculations, the g-factor is 2.04, which is
Characteristic of unpaired electrons in the d-orbital of Fe 3+ ions. This implies that smaller nanoparticles have a higher surface-to-volume ratio; hence, Surface effects become more significant and can modify the line width as well as the position of the resonance.

Example 6: Process of preparing Nanoparticle
A. FeNPs were synthesised via the co-precipitation method. For nanoparticle synthesis, a solution was prepared by dissolving ferric chloride (FeCl3•6H2O) 10.40 gram and ferrous chloride (FeCl2•6H2O) 4.0 gram in a 2:1 molar ratio in 200 mL of deionised (DI) water under a nitrogen atmosphere. While stirring, 1 M ammonia solution (7.48 mL NH 3 in 100 ml DI water) was added until a black precipitate formed, and the solution was heated for 2 hrs at 80 °C. The nanoparticles were separated using an external magnet, washed with distilled water three times, and air-dried.
B. Cobalt ferrite (CoFe2O4) nanoparticles were prepared using the co- precipitation method. 0.2M 0.1M CoCl2•6H2O (2.37 gram) and FeCl3•6H2O (5.41 gram) were dissolved in 100 mL of deionised water and stirred separately when the lucid solution was formed. 0.63M NaOH (2.52 g in 100 ml DI water) was then added drop wise to the mixed solution, and a black precipitate was obtained from continuous stirring. The mixture was then stirred for 3 hours at 80°C and collected after 3 cycles of centrifugation (15 min at 3000 rpm) with deionised water and two washes with propyl alcohol. The product was dried in an oven for 24 hrs at 80 °C and calcined for 5 hours at 500 °C to give CoFe 2O4 nanoparticles.

The foregoing description of the embodiments has been provided for purposes of illustration and not intended to limit the scope of the present disclosure. Individual components of a particular embodiment are generally not limited to that particular embodiment, but, are interchangeable. Such variations are not to be regarded as a departure from the present disclosure, and all such modifications are considered to be within the scope of the present disclosure.

TECHNICAL ADVANCEMENTS
The present disclosure described herein above has several technical advantages including, but not limited to, the realization of:
The embodiments herein and the various features and advantageous details thereof are explained with reference to the non-limiting embodiments in the following description. Descriptions of well-known components and processing techniques are omitted so as to not unnecessarily obscure the embodiments herein. The examples used herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.

The present disclosure provides a composition and a process thereof, having technical advantages not limited to, having:
• a radical generation ability;
• Ozone stability;
• recover the catalyst for potential reuse;
• treatment of multiple pharmaceutical compounds simultaneously;
• fast and provides complete degradation of pharmaceuticals; and
• Is environmentally safe.
,CLAIMS:WE CLAIM:
1. A metal coated catalytic composition for degradation of chemical contaminants in waste water comprising of :
• Ozone (O3) microbubble having a predetermined size; and
• At least one metal nanoparticle selected from cobalt (Co), iron (Fe) and magnesium (Mg) nanoparticles (NP),
wherein the metal NP coated ozone (O3) microbubbles generates radical for catalysis.
2. The metal coated catalytic composition for degradation of chemical contaminants in waste water as claimed in claim 1 wherein the size of ozone (O3) microbubble is in the range of 40 to 60 µm.
3. The metal coated catalytic composition for degradation of chemical contaminants in waste water as claimed in claim 1 wherein the ozone (O3) microbubble is formed at the ozone (O3) flow rate in the range of 0.15 L/min to 0.50 L/min, in particular 0.25 L/min.
4. The metal coated catalytic composition for degradation of chemical contaminants in waste water as claimed in claim 1 wherein the metal for the metal NP is a transition metal selected from cobalt (Co), iron (Fe) and magnesium (Mg), wherein the transition metal is a substrate having high stability to ozone (O3); and activates ozone (O3) surface for radical generation.
5. The metal coated catalytic composition for degradation of chemical contaminants in waste water as claimed in claim 1 wherein the radical generation from the metal coated ozone (O3) microbubble is up to 15% of molar mass of ozone (O3), and wherein the molar ratio of the radical to ozone (O3) is in the range of 0.08: 1 to 0.1:1.
6. A process for degradation of chemical contaminants in wastewater comprising the steps of:
• maintaining the flow of O3 in the range of 0.15 L/min to 0.50 L/min to obtain an O3 microbubble (MB);
• coating the O3 microbubble (MB) with a metal nanoparticle (NP) to obtain a catalytic metal coated-O3 microbubble for radical generation;
• contacting a predetermined amount of the metal coated-O3 catalytic microbubble with the waste water having at least one chemical contaminants to obtain a mixture: and
• reacting a mixture for a time period in the range of 2 to 6 minutes at a predetermined reaction conditions to obtain water free from the chemical contaminants.
7. The process for degradation of chemical contaminants in wastewater as claimed in claim 6 wherein the predetermined amount of the metal NP coated ozone (O3) microbubbles for radical generation is in the range of 0.1-0.50 g/L.

8. The process for degradation of chemical contaminants in wastewater as claimed in claim 6 wherein the predetermined reaction conditions is an optimized pH in the range of 5-9, pressure of 1 atm, and room temperature.

9. The process for degradation of chemical contaminants in wastewater as claimed in claim 6 wherein the chemical contaminants are selected from Ciprofloxacin (CP), Salicylic acid (SA), and Ibuprofen (IBU).
10. A Fe NP coated ozone (O3) microbubble, characterized by having
• molar ratio of radical: ozone of 0.08:1; and
• Paramagnetic property of 55.4 emu/gm magnetism.