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Break oily water emulsion during petroleum enhancing production processes using green approach for the synthesis of SnCuO@FeO nanocomposite from microorganisms – Scientific Reports

Bacterial strains isolation

Eight distinct bacterial strains (MHB1-MHB8) have been isolated in the current investigation from a variety of samples collected. Their morphological characterizations were mentioned in Table 2. Bacterial isolates (MHB5) is considered as predominant isolate. The different bacterial isolates were screening for FeO nanoparticles production.

Table 2 The various bacterial isolates’ morphological characteristics.

Screening the production of Fe-nanoparticle

Screening of bacterial isolates for the ability to produce nanoparticles and the selection of the greatest nanoparticle producer were examined in the current work. The findings of the data collection for dynamic light scattering (DLS) were displayed in Table 3. The DLS results demonstrate that MHB5 (78.7 nm), employing FeCl3 as a nanoparticle precursor, produced the FeO nanoparticles with the minimal particles of those created. The results demonstrated that MHB5, which stands out from other researched bacterial isolates synthesizing nanoparticles not only by how efficiently it can make nanometals but also by creating the lowest particle size, produced iron nanoparticles with the smallest size nanoparticles. According to dynamic light scattering (DLS) study, Pseudomonas aeruginosa ATCC 10145 formed magnetic nanoparticles that were 71.21 nm in size.

Table 3 Fe2O3 nanoparticle size synthesized by different bacterial isolates using DLS analysis.

Characterization data

Identification of the selected bacterial strain molecularly

The selected isolate (MHB5) was identified by amplification and sequencing of 16S rRNA gene as Bacillus paramycoides strain OQ878685 with a similarity of 99.34%. Figure 2 illustrates how Phylogenetic study using the MEGA software validated the recovered bacteria’s molecular identity as members of the Bacillus paramycoides.

Figure 2
figure 2

A phylogenetic tree of Bacillus paramycoides strain OQ878685 evolutionary relationships to other strains, taken from the NCBI database.

FTIR spectrum

Figure 3 shows the FTIR spectrum of FeO, SnCuO, and SnCuO@FeO nanoparticles. The peak at around 560–580 cm−1, which corresponds to the Fe–O stretching vibration, indicates the presence of FeO. The spectrum for SnCuO shows peaks at around 600–700 cm−1 and 800–900 cm−1, which correspond to the Sn–O and Cu–O stretching vibrations, respectively. These peaks indicate the presence of Sn–O and Cu–O bonds. The spectrum for SnCuO@FeO shows peaks at around 600–700 cm−1 and 800–900 cm−1, that correspond to the Sn–O and Cu–O stretching vibrations indicating the presence of Sn–O and Cu–O bonds. In addition, there is a peak at around 400–450 cm−1, which corresponds to the Fe-Sn stretching vibration, indicating the presence of Fe-Sn bonds. There is also a peak at around 1500–1700 cm−1, which corresponds to the C=O stretching vibration, indicating the presence of a carbonyl group in the sample. In addition to, there is a peak at around 3400–3600 cm−1, which corresponds to the O–H stretching vibration, indicating the presence of hydroxyl groups in the sample. Table 4 presented the peaks of the FTIR.

Figure 3
figure 3

FTIR spectrum of the FeO, SnCuO, and SnCuO@FeO.

Table 4 FTIR peaks of the FeO, SnCuO, and SnCuO@FeO.

The effect of FeO modification with Sn or CuO can be seen in the SnCuO@FeO. The presence of Fe–Sn bonds in the SnCuO@FeO sample indicates that the FeO was modified with Sn. Similarly, the presence of Sn–O and Cu–O bonds in the SnCuO@FeO sample proposes that the FeO was also modified with CuO. These modifications may have been made in order to improve the properties of the FeO nanoparticles, such as their catalytic activity or stability.

The FTIR analysis results for SnCuO@FeO nanoparticles with different ratios of SnCuO and FeO were presented in the Fig. 4 and Table 5. The FTIR spectrum of all samples exhibits similar peaks, indicating the presence of Sn–O, Cu–O, Fe–O, Fe–Sn, C=O, and O–H groups in all samples. The peaks observed at 600–700 cm−1 correspond to the Sn–O stretching vibrations, indicating the presence of Sn–O bonds in all samples. Similarly, the peaks observed at 800–900 cm−1 correspond to the Cu–O stretching vibrations, indicating the presence of Cu–O bonds in all samples. The peaks observed at 560–580 cm−1 correspond to the Fe–O stretching vibrations, indicating the presence of Fe–O bonds in all samples.

Figure 4
figure 4

FTIR spectrum of the SnCuO@FeO (1:1), SnCuO@FeO (1:2), ans SnCuO@FeO (1:3) nanocomposites.

Table 5 The FTIR analysis results for SnCuO@FeO nanoparticles with different ratios of SnCuO and FeO.

The presence of Fe-Sn bonds is indicated by the peak at 400–450 cm−1, which is present in all samples. This peak indicates that some of the FeO is modified by Sn to form Fe–Sn bonds.

The peaks observed at 1500–1700 cm−1 correspond to the C=O stretching vibrations, indicating the presence of a carbonyl group in all samples. This group may be present due to the use of certain organic compounds during the synthesis of the nanoparticles. The peaks observed at 3400–3600 cm−1 correspond to the O–H stretching vibrations, indicating the presence of hydroxyl groups in all samples. These groups may be present due to the use of certain solvents or surfactants during the synthesis of the nanoparticles. From the FTIR analysis results the nanoparticles are well-mixed and homogeneous, as all samples exhibit similar peaks. The differences in peak intensity may be due to slight variations in the composition or morphology of the nanoparticles.

XRD

Figure 5 shows the XRD pattern of FeO, SnCuO and SnCuO@FeO nanocomposite. The XRD pattern typically shows strong diffraction peaks at 2θ angles of around 33.2°, 35.6°, 43.0°, 53.6°, 57.2°, and 62.8°, which correspond to the (220), (311), (400), (422), (511), and (440) planes of the FeO crystal structure, respectively51. These peaks are sharp and well-defined, indicating that the nanoparticles have a crystalline structure with a high degree of order. The presence of these peaks confirms the formation of FeO nanoparticles and provides information about their crystal structure, which can be important for understanding their properties and potential applications.

Figure 5
figure 5

XRD spectrums of the FeO, SnCuO, and SnCuO@FeO.

For SnCuO composite typically exhibits characteristic peaks in the XRD pattern that can be used to identify the crystal structure and estimate the particle size. The SnCuO composite typically shows diffraction peaks corresponding to the crystal structures of SnO2, CuO, and SnCuO. The SnO2 peaks were commonly observed at around 26.7°, 33.9°, and 51.6°, corresponding to the (110), (101), and (211) planes, respectively52. The CuO peaks were usually located at around 35.5°, 38.7°, 48.2°, and 61.4°, corresponding to the (002), (111), (020), and (202) planes, respectively. The SnCuO peaks can be observed between the SnO2 and CuO peaks, indicating the formation of a new phase.

When SnCuO is combined with FeO to form SnCuO@FeO nanocomposites, new peaks may appear in the XRD pattern, inicating the formation of a new phase or the presence of impurities. In addition to the peaks observed for SnCuO, the XRD pattern of SnCuO@FeO nanocomposites may show peaks corresponding to the crystal structure of FeO. The characteristic peaks of FeO were typically observed at around 30.1°, 35.5°, 43.3°, and 62.7°, corresponding to the (104), (110), (113), and (214) planes, respectively. The XRD pattern of SnCuO@FeO nanocomposites typically shows the same diffraction peaks as the SnCuO composite, as well as additional peaks at around 35.4°, 43.6°, 53.5°, and 62.7°, which correspond to the (220), (311), (400), and (422) planes of the FeO crystal structure, respectively. The presence of these peaks indicates that FeO nanoparticles have been incorporated into the SnCuO composite to form a nanocomposite material. The particle size of the nanocomposite can also be estimated using XRD, and any changes in the peak positions or intensities may provide information about changes in the crystal structure or morphology of the nanoparticles.

TEM

Figure 6 shows the TEM images of the FeO, SnCuO, and SnCuO@FeO. FeO TEM imaging shows that the nanoparticles were spherical in shape with a relatively uniform size. High resolution TEM images show lattice fringes with interplanar spacing corresponding to the (220), (311) and (400) planes of magnetite/maghemite, indicating the crystalline nature of the nanoparticles. The TEM characterization reveals that the FeO nanoparticles produced by the microorganisms were relatively monodisperse spherical nanoparticles in the 5–20 nm size range, with crystallite sizes matching the particles sizes. The crystal structure and phase correspond to magnetite or maghemite iron oxides, and the nanoparticles show good dispersion and stability with little aggregation Fig. 6a.

Figure 6
figure 6

TEM of the FeO (a), SnCuO (b), and SnCuO@FeO (c).

The SnCuO nanoparticles were found to have a spherical shape with an average size of 70 nm Fig. 6b), while the SnCuO@FeO nanoparticles had a core–shell structure with a SnCuO core and a FeO shell, and an average size of 10 nm (Fig. 6c). The TEM images showed that the SnCuO nanoparticles were well dispersed and had a uniform size distribution, indicating a successful synthesis process. The SnCu@FeO nanoparticles also appeared well dispersed, with a clear core–shell structure observed in the images. The FeO shell was found to be approximately 10 nm thick, and appeared to be uniformly coating the SnCuO core Fig. 6c. Also, the images of SnCuO@FeO nanoparticles were appeared as bright spots on a dark background, and the size and shape of the particles could be measured from the images.

Jar experimental

Oil concentration

The Fig. 7 presents the results of an experiment aimed at removing oil from oily water emulsions under visible light using different nanocomposites. The concentration of oil in water (in mg/L), along with the corresponding separation efficiency (%) for each nanocomposite and the control sample (SE). The nanocomposites used in the experiment were SnCuO@FeO with different ratios of Sn to CuO (1:1, 2:1, and 3:1).

Figure 7
figure 7

Effect of oil concentrations on the removal efficiency of SnCuO@FeO nanocomposites.

From this figure, it is clear that all three nanocomposites exhibit superior separation efficiency compared to the control sample (SE). The best performance is achieved by the 1:1 ratio of Sn to CuO, with a separation efficiency of 85% at an oil concentration of 5 mg/L. As the concentration of oil increases, the separation efficiency of this nanocomposite remains relatively constant, with values around 82–83% at higher concentrations (10–30 mg/L). The other two nanocomposites (2:1 and 3:1 ratios) also show good separation efficiency, but their performances were not as consistent as the 1:1 ratio. The 2:1 ratio has a separation efficiency of 80% at 5 mg/L, which decreases to around 76% at higher concentrations (10–30 mg/L). Similarly, the 3:1 ratio starts at 75% at 5 mg/L and decreases to around 70% at higher concentrations. It is worth noting that the control sample (SE) has much lower separation efficiency than the nanocomposites, ranging from 1.8% at 5 mg/L to 22.5% at 30 mg/L. This highlights the significant improvement in separation efficiency offered by the use of nanocomposites. Consequently, it was clear that the synthesized nanocomposites have great potential for applications in oil removal from oily water emulsions under visible light. Specifically, the 1:1 ratio of Sn to CuO appears to be the most effective composition, offering high separation efficiency over a range of oil concentrations.

Retention time

Figure 8 shows the effect of retention time (min) on the removal efficiency of SnCuO@FeO nanocomposite. The results shown above demonstrate the effectiveness of using different nanocomposites for removing oil from oily water emulsions under visible light. The data indicates that increasing the concentration of Sn and CuO nanoparticles supported on FeO (1:1) surface leads to improved separation efficiency.

Figure 8
figure 8

Effect of retention time on the removal efficiency of SnCuO@FeO nanocomposites.

The 1:1 concentration of Sn and CuO nanoparticles showed the highest separation efficiency, with a retention time of 5 min and oil in water emulsion concentration of 12.18 mg/L. This regards to the presence of both Sn and CuO nanoparticles enhances the photocatalytic activity of the FeO (1:1) surface, leading to better degradation of the oil droplets and subsequent separation. The 2:1 and 3:1 concentrations of Sn and CuO nanoparticles also showed improved separation efficiencies compared to the control sample (SE), but to a lesser extent than the 1:1 concentration. The retention times for these concentrations were 10.94 min and 9.53 min, respectively, which correspond to oil in water emulsion concentrations of 63.5 mg/L and 68.2 mg/L.

Remarkably, the 3:1 concentration of Sn and CuO nanoparticles showed a slight decrease in separation efficiency compared to the 2:1 concentration, despite having a higher concentration of Sn and CuO nanoparticles. This may advocate that there is an optimal ratio of Sn to CuO nanoparticles that maximizes the photocatalytic activity of the FeO (1:1) surface, and that excessive amounts of either nanoparticle may actually hinder the separation process.

Temperature

Figure 9 shows the effectiveness of using different nanocomposites for removing oil from oily water emulsions at various temperatures between 283 and 373 K. At a temperature of 283 K, the SE (control sample without any nanoparticles) had a relatively low separation efficiency of 1.508494. In contrast, the addition of Sn and CuO nanoparticles significantly enhanced the separation efficiency, with the 1:1 concentration showing the highest efficiency of 60%. This indicates that the presence of both Sn and CuO nanoparticles improves the photocatalytic activity of the FeO (1:1) surface, leading to better degradation of the oil droplets and subsequent separation.

Figure 9
figure 9

Effect of temperature on the removal efficiency of SnCuO@FeO nanocomposites.

As the temperature increased to 298 K, the separation efficiency of the SE decreased slightly to 0.329983. However, the addition of Sn and CuO nanoparticles continued to improve the separation efficiency, with the 1:1 concentration showing a notable increase to 74%. This confirms that the nanocomposites were effective at higher temperatures as well, where the increased thermal energy can facilitate the degradation of the oil droplets. Further increases in temperature led to a marginal decrease in separation efficiency for all samples, including the SE. However, the 1:1 concentration of Sn and CuO nanoparticles remained the most effective, with a separation efficiency of 85% at 348 K and 93% at 373 K. These findings the optimized concentration of Sn and CuO nanoparticles can maintain their photocatalytic activity even at higher temperatures, resulting in consistent separation efficiencies.

Notably, the 2:1 and 3:1 concentrations of Sn and CuO nanoparticles showed varying degrees of separation efficiency across the different temperatures. While the 2:1 concentration exhibited generally high separation efficiency, the 3:1 concentration showed a slight decrease in efficiency at certain temperatures. This may indicate that the optimal ratio of Sn to CuO nanoparticles varies depending on the specific conditions of the experiment, such as temperature, reaction time, and initial oil concentration. Consequently, the potential of using nanocomposites consisting of Sn and CuO nanoparticles supported on FeO (1:1) surface for removing oil from oily water emulsions under visible light. The optimized concentration of 1:1 shows the highest separation efficiency across various temperatures, indicating that the combination of both Sn and CuO nanoparticles enhances the photocatalytic activity of the FeO (1:1) surface.

Figure 10 illustrates that as temperatures rise; there is an increase in sorption, as evidenced by higher q values for the same Ce. At elevated temperatures such as 323 K and 333 K, the maximum q value reaches the range of 90–92 mg/g. The selected Ce values encompass a broad range, spanning from very low to moderately high residual oil concentrations post-adsorption, providing comprehensive coverage for analysis.

Figure 10
figure 10

Plot the q-Ce at different temperatures (°K).

Kinetics models

Table 6 describe the adsorption kinetics models used to describe the adsorption of oil on SnCuO@FeO nanocomposite that were the pseudo first-order model, pseudo-second order model, and intraparticle diffusion model. The results were presented in the form of linear and nonlinear plots, and the parameters for each model were reported.

Table 6 The kinetics models of oil adsorption on SnCuO@FeO nanocomposite.

The pseudo-first order model assumes that the rate of adsorption was proportional to the difference between the equilibrium concentration and the concentration at any given time53. The linear and nonlinear plots show that the model fits the data well, with R2 values of 0.986 and 0.821, respectively. The calculated rate constant (k1) for the pseudo first-order model is 0.016 and 0.055 for linear and nonlinear plots, respectively, indicating that the adsorption rate is relatively slow.

The adsorption rate was assumed to be proportional to the square of the difference between the concentration at any given time and the equilibrium concentration in the pseudo-second order model. The linear and nonlinear plots show that this model also fits the data well, with R2 values of 0.986 and 0.821, respectively. The calculated rate constant (k2) for the pseudo-second order model was not reported, but the value of qe (the amount of oil adsorbed at equilibrium) is similar to that obtained from the pseudo-first order model.

The intraparticle diffusion model assumes that the rate of adsorption was controlled by the diffusion of oil molecules within the pores of the adsorbent. The linear and nonlinear plots show that this model fits the data moderately well, with an R2 value of 0.972. The calculated diffusion coefficient (D) from the intraparticle diffusion model is 2.7 and 5.8, for linear and nonlinear plots, respectively.

From the kinetic results, the adsorption of oil on SnCuO@FeO nanocomposite was best described by the pseudo first-order and pseudo-second order models, indicating that both film diffusion and intraparticle diffusion may be involved in the adsorption process. The relatively slow rate of adsorption suggests that the process may be limited by the availability of active sites on the surface of the nanocomposite.

Adsorption isotherm models

Table 7 describes the adsorption isotherm models that can be used to understand the adsorption behavior of oil on SnCuO@FeO nanocomposite and to predict the possible mechanisms involved in the adsorption process. The Ce values in the table represent the initial concentration of oil, while the Exp. values represent the equilibrium concentration of oil after adsorption. The Langmuir and Freundlich models were commonly employed to explain how solutes behave when they adsorb on solid surfaces. The Langmuir model postulates that there were a set number of active sites on a homogenous surface where adsorption takes place, and the adsorbed molecules do not interact with each other54. The Langmuir model can be represented by Eq. (1):

$${mathbf{Ce/qe = 1/}}left( {{mathbf{b*Qmax}}} right){mathbf{ + Ce/Qmax}}$$

(1)

where qe is the amount of oil adsorbed per unit weight of SnCuO@FeO nanocomposite, Ce is the equilibrium concentration of oil, b is the Langmuir constant related to the affinity of the adsorbent for the solute, and Qmax is the maximum adsorption capacity of the adsorbent.

Table 7 Adsorption isotherm models of adsorption of oil on SnCuO@FeO nanocomposite.

According to the Freundlich model, adsorption takes place on a heterogeneous surface with a variety of active sites55, and the adsorbed molecules interact with each other. The Freundlich model can be represented by Eq. (2):

$${mathbf{qe}};{mathbf{ = }};{mathbf{Kf*Ce}}^{{{mathbf{(1/n)}}}}$$

(2)

where Kf is the Freundlich constant related to the adsorption capacity, and n is the Freundlich exponent related to the intensity of adsorption.

The Dubinin-Radushkevich (D-R) model was used to predict the adsorption mechanism based on the free energy of adsorption56. The D-R model can be represented by Eq. (3):

$${mathbf{ln}} , {mathbf{qe}} , = , {mathbf{ln}} , {mathbf{qm}} – {mathbf{beta varepsilon }}^{{mathbf{2}}}$$

(3)

where qm is the maximum adsorption capacity, β is a constant related to the adsorption energy, and ε is the Polanyi potential given by Eq. (4):

$${{varvec{upvarepsilon}}} , = , {mathbf{RT}} , {mathbf{ln}}left( {{mathbf{1}} , + , {mathbf{1}}/{mathbf{Ce}}} right)$$

(4)

where R is the gas constant, T is the temperature, and Ce is the equilibrium concentration of oil.

From Table 7 of values, it can be observed that the Langmuir model provided the best fit for the experimental data, as indicated by the higher R2 value compared to the Freundlich model. This suggests that the adsorption of oil on SnCuO@FeO nanocomposite takes place on a homogeneous surface with a set number of active sites. Langmuir constant (b) and the maximum adsorption capacity (Qmax) increased with increasing initial concentration of oil, indicating that the adsorption capacity of the nanocomposite increases with increasing oil concentration. The D-R model provided very small values for the free energy of adsorption (β), indicating that the adsorption mechanism is physical rather than chemical. This suggests that the adsorption of oil on SnCuO@FeO nanocomposite is primarily due to van der Waals forces and other weak interactions between the oil molecules and the surface of the nanocomposite.

Thermodynamic model

Table 8 reported the adsorption thermodynamics parameters of oil on SnCuO@FeO nanocomposite as enthalpy change (∆H), entropy change (∆S), and the coefficient of determination (R2) for each model. The thermodynamic model used to analyze the data is not specified.

Table 8 Thermodynamic model for oil adsorption on SnCuO@FeO nanocomposite.

The enthalpy change (∆H) represents the amount of heat released or absorbed during the adsorption process. The linear and nonlinear plots show that ∆H was 18.62 kJ/mol indicating that the adsorption process exothermic Fig. 11. This illustrated that the adsorption of oil on SnCuO@FeO nanocomposite is a favorable process, as energy is released during the adsorption. The entropy change (∆S) represents the increase or decrease in disorder during the adsorption process. The linear and nonlinear plots show that ∆S is 0.0695 kJ/(mol K) for both plots, indicating that the adsorption process leads to an increase in order. This implies that the adsorbed oil droplets were more ordered on the surface of the nanocomposite compared to their bulk state. The coefficient of determination (R2) is a measure of how well the data fits the model. The linear and nonlinear plots show that the models fit the data well, with R2 values of 0.962 and 0.949, respectively. Consequently, the adsorption of oil on SnCuO@FeO nanocomposite was a process that increases order through exothermy. These findings were consistent with a physical adsorption mechanism, in which the oil molecules are attracted to the surface of the nanocomposite through weak van der Waals forces. The relatively high R2 values for both models suggest that the models were appropriate for describing the adsorption process, and can be used to predict the adsorption behavior under different conditions.

Figure 11
figure 11

Thermodynamic model of the oil adsorption on SnCuO@FeO nanocomposite.