In this study, silver oxide nanoparticles (Ag2O NPs) were generated by synthesizing green leaf extract of Punica granatum and used as adsorbent and used as adsorbent to remove the antibiotic additive sulfamethoxazole (SMX) from an aqueous solution. The chemical composition, surface morphology, and textural properties of the Ag2O NPs were identified using XRD, FTIR, BET/BJH, SEM-EDX, and TEM analyses. For 100 mg L− 1 SMX antibiotic concentration, Ag2O NPs achieved almost complete removal of 98.93% within 90 min by using 0.8 g L− 1 of adsorbent dose and initial solution pH of 4 at a temperature of 308 K. Langmuir model efficiently elucidates the experimental data, which amounts to homogeneous nature of antibiotic adsorption onto the Ag2O NPs. The maximum uptake capacity was 277.85 mg g− 1. Kinetic studies promise a PSO model. The ΔGº and ΔHº values confirm the spontaneity and endothermicity of the adsorption process. The regeneration study shows that the Ag2O NPs can be efficiently reused for up to five cycles. The geometric structures have been optimized and quantum chemical parameters were calculated for the SMX unprotonated (SMX+/−) and protonated (SMX+) using density functional theory (DFT) calculation, indicating that the SMX+/− is reacting more favorably on the surface of Ag2O NPs compared to the SMX+. According to this study, the Ag2O NPs as an excellent potential the adsorbent will be able to have remarkable effects in the treatment of pharmaceutical wastewater.
Research Article
Green synthesis of Ag2O nanoparticles using Punica granatum leaf extract for sulfamethoxazole antibiotic adsorption: characterization, experimental study, modeling, and DFT calculation
https://doi.org/10.21203/rs.3.rs-1642752/v1
This work is licensed under a CC BY 4.0 License
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Sulfamethoxazole removal
green synthesis
Ag2O nanoparticles
kinetics and isotherm
DFT calculation
The main source of water pollution is the direct discharge of wastewater into water bodies without any prior treatment (El Messaoudi et al. 2021a). Among the water pollutants, antibiotics, when released, pose serious threats even in small quantities. Antibiotics are chemical compounds that have the ability to inhibit the life processes of selected microorganisms (Khameneh et al. 2019). Antibiotics can be classified based on several factors such as chemical structure, method, etc. mode of action, the spectrum of action, and route of administration (injection, oral and topical). One of the best-known, perhaps simplest, classifications of antibiotics is based on the presence of distinct functional groups, such as macrolides, tetracyclines, quinolones, sulfonamides, oxazolidinones, etc. (Suzuki and Hoa 2012; Berges et al. 2021; Grenni 2022). Sulfonamides have been widely approved and used to treat a wide range of different clinical infections. They have been used for decades due to their high potency, broad-spectrum activity, and high serum concentrations (Fair and Tor 2014; Wang et al. 2019). Sulfamethoxazole (SMX) is a synthetic veterinary drug with a para-aminobenzene sulfonamide structure (Cheong et al. 2020). As a bacteriostatic sulfonamide antibiotic, SMX is used for the treatment and prevention of diseases in animals and humans (Zhang et al. 2011; Chen et al. 2017; Gao et al. 2019). Exposure of SMX to the environment can cause severe toxicity to be aquatic and nearby systems, bacteria, animals, and human health (Straub et al. 2016; Hwang et al. 2016; Xu et al. 2022). Therefore, the presence of antibiotics in water is unacceptable and there are currently several techniques to remove them, such as biodegradation, membrane separation, hydrolysis, and photodegradation (Mitchell et al. 2014; Reis et al. 2020; Wu et al. 2021; Yin et al. 2021). However, most of these techniques are still expensive, especially when applied to large quantities of industrial wastewater. Adsorption is one of the widely used and cost-effective techniques to remove pollutants from wastewater (El Khomri et al. 2021).
Multiple adsorbents such as graphene oxide (Chen et al. 2015), CuZnFe2O4/biochar (Heo et al. 2019), high silica zeolite Y (Braschi et al. 2016), waste-based activated carbon (Jaria et al. 2021), calcined layered double hydroxide (Mourid et al. 2019), zeolite (Liu et al. 2020a), sediment (Wang et al. 2017), and magnetic activated carbon (Lv et al. 2021), have been used for sulfamethoxazole (SMX) liquid phase remediation.
In recent years, green nanoparticles (ZnO, MgO, Fe2O3, Ag2O, CuO, Si2O, etc.) synthesized from extracts of lignocellulosic biomass have emerged as a cost alternative and are attractively low for cost-prohibited commercial NPs to reduce pollution as they promise effective adsorption due to their high efficiency, surface chemistry, porosity, selectivity, and surface chemistry (Ehrampoush et al. 2015; Stan et al. 2017; Asghar et al. 2018; Khani et al. 2018; SI et al. 2020; Pai et al. 2021). Compared with other synthesis methods (sol-gel, hydrothermal, precipitation, ultrasound, etc.), green synthesis of silver oxide nanoparticles (Ag2O NPs) is simple, inexpensive, non-toxic, and environmentally friendly (Shamaila et al. 2016; Marouzi et al. 2021).
The present study is regarding the green synthesis of Ag2O nanoparticles extracted from Punica granatum leaves and their evaluation by the adsorption of the sulfamethoxazole antibiotic from an aqueous solution. Additionally, the developed adsorbent was characterized using scanning electron microscopy/energy-dispersive X-ray (SEM/EDX), N2 adsorption-desorption, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and transition electron microscopy (TEM) analyses. The effects of five independent active variables (pH, adsorbent dose, contact time, antibiotic concentration, and temperature) and their interactions on the adsorption capacity to remove SMX were examined. Kinetics (PFO, PSO, and IDP), equilibrium (Langmuir, Freundlich, Temkin, and D-R), and thermodynamics parameters (ΔGº, ΔHº, and ΔSº) were also carried out to identify the adsorption properties of the adsorbent. Ag2O nanoparticles were regenerated and reused to remove SMX. The optimized geometries, highest occupied and lowest unoccupied molecular orbitals (HOMO-LUMO), and electrostatic potential (ESP) maps corresponding to the and quantum chemical parameters (EHOMO, EHOMO, ∆Egap, µ, χ, ղ, and σ) of the SMX unprotonated (SMX+/−) and protonated (SMX+) were investigated using calculations based on DFT/B3LYP 6–31 + G (d,p) under the solvation conditions. Finally, a possible mechanism of SMX adsorption on Ag2O NPs was proposed.
2.1 Chemicals and instrumentations
Hydrochloric acid (HCl), acetone, methanol, sodium hydroxide (NaOH), potassium nitrate (KNO3), ethanol, and SMX antibiotic have been purchased from Sigma-Aldrich and have analytical quality. Distilled water was used in all experiments. The characteristics of SMX are summarized in Table 1.
Table 1. Physicochemical characteristics of SMX.
| Characteristic |
Value |
| Class |
Sulfonamid antibiotic |
| IUPAC name |
4-amino-N-(5-methyl-1,2-oxazol-3-yl)benzenesulfonamide |
| Moleular structure |
 |
| Formula |
C10H11N3O3S |
| λmax (nm) |
263 |
| Molecular weight (g mol–1 ) |
253.279 |
| pka1 |
1.97 |
| pka2 |
6.16 |
| Polarisability |
24.16 |
| Diffusion coefficient (10–1 m2 s–1) 2 |
6.25 |
The surface properties of GP-C and GPAC
Experiments of X-ray diffraction (XRD) are performed on a Bruker D8 Advance Twin diffractometer to determine the nature of the crystals of Ag2O nanoparticles. The FTIR spectrum of Ag2O NPs has been obtained using ATR technique on IR JASCO 4100 spectrophotometer and scanned on a wavelength range from 500 to 4000 cm− 1. The surface properties of Ag2O NPs were determined by Brunauer-Emmett-Teller analysis (BET, Belsorp Mini II). The morphology characteristics of Ag2O NPs was identified using Scanning Electron microscopy with energy dispersive X-ray analysis (SEM-EDX, JEOL, JSMIT200) and transmission electron microscope (TEM, JEOL Ltd, Tokyo, Japan). The point of zero charge (PZC) of Ag2O NPs has been determined according to the process reported by El Messaoudi et al. (El Messaoudi et al. 2022b).
2.2 Green synthesis of Ag2O NPs
The Punica granatum leaves (PGL) were obtained from an area of Tinghir (Morocco). The PGL were cleaned thoroughly using distilled water to eliminate dirt, dust, and other surface contaminants before sun drying. The cleaned PGL then were soaked in methanol for 24 h to remove the pigments and fat, and then washed with distilled water several times dried in the dryer for 12 h. The dry biomaterial was ground by a mechanical grinder and screened at 50 µm. 10 g PGL powder was added to 50 mL of distilled water for 2 h at 70°C. After that, the mixture was filtered and centrifuged to separate the water extract and the residue of the PGL powder. 20 mL of the obtained extract was added to 40 mL of a solution consisting of AgNO3 (0.2 M) and 5 mL of NaOH (0.1 M), stirring continuously for 5 h at 65°C. After precipitation, the sample was rinsed with distilled water multiple times and then dried in 16 the dryer for 12 h at 70°C, and then calcined in an oven at 450°C for 3 h. The green synthesis process of Ag2O nanoparticles from Punica granatum leaf extract is detailed in Fig. 1.
2.3 Adsorption experiments
The batch adsorption experiments were performed in an aqueous solution. The adsorption performance of Ag2O NPs was evaluated for the removal of SMX to identify the effect of operating conditions, including adsorbent dosage (0.2–1.4 g L− 1), initial SMX concentration (50–400 mg L− 1), initial pH of antibiotic solution (2–10) and contact time (5–180 min) at temperature (298–318 K). Evaluation of adsorption capacity was analyzed using the isotherm studies carried out at 298 K, 308 K, and 318 K by equilibrating Ag2O NPs (40 mg) with 50 mL of SMX solution (50–400 mg L− 1) for 90 min at solution pH = 4, while kinetics and thermodynamic experiments were conducted in a similar way at three different initial SMX concentrations 100 mg L− 1, 150 mg L− 1, and 200 mg L− 1 for 5–180 min, and at the above three temperatures, respectively. After each adsorption experiment, the antibiotic solution was filtered using a syringe filter (0.45 µm), and the concentration of the final solution was determined using a UV-visible spectrophotometer (UV/Vis 2300) at a maximum absorbance wavelength of 263 nm. The removal percentage (%) of the SMX solution was determined using Eq. (1):
$$\% Removal=\frac{\left({C}_{i}-{C}_{f}\right)}{{C}_{i}}\times 100 \left(1\right)$$
C i (mg L− 1) and Cf (mg L− 1) refer to the initial and final concentrations of SMX, respectively.
The amount of SMX adsorption at equilibrium, qe (mg L− 1) was determined from Eq. (2):
$${q}_{e}=\frac{\left({C}_{i}-{C}_{f}\right)\times V}{m} \left(2\right)$$
V/m (g L− 1) denotes the adsorbent dosage.
2.4 DFT computational
The electronic structure calculations were performed with Gaussian 9 software packages. The equilibrium structure of the unprotonoted (SMX+/−) and protonoted (SMX+), as well the parameters, EHOMO, ELUMO, energy gap (∆Egap), ESP maps, dipole moment (µ), and parameters that give valuable information on the reactive behavior such as the electronegativity (χ) ionization, hardness (ղ), softness (σ) were determined using density functional theory (DFT) combined with the Lee-Yang-Parr correlation function (B3LYP) (Becke 1993; Stephens et al. 1994) and the 6–31 + G (d,p) basis set (Kendall et al. 1992). All calculations were performed in the aqueous phase. The quantum parameters are presented by mathematical formulas as follows:
$$\varDelta {E}_{gap}={E}_{LUMO}-{E}_{HOMO} \left(3\right)$$
$$\chi =\frac{-\left({E}_{LUMO}+{E}_{HOMO}\right)}{2} \left(4\right)$$
$$\eta =\frac{\left({E}_{LUMO}-{E}_{HOMO}\right)}{2} \left(5\right)$$
$$\sigma =\frac{1}{n} \left(6\right)$$
3.1 Ag2O NPs characterization
XRD is one of the most widely used methods for characterizing the structure of an Ag2O nanoparticle. XRD graph gives the most direct results such as crystallinity. The XRD results obtained (Fig. 2a) show almost identical plots and exhibit the same intense diffraction peaks at 38.6°, 45°, 65°, 75.4°, and 81.6° with (111), (200), (220), (311), and (222) planes (JCPDS 00-041-1106), respectively that are attributed to Ag2O (Bian et al. 2020). From Fig. 2a, it is clear that the crystallinity of Ag2O NPs and maintained at a face-centered cubic crystal structure (Rashmi et al. 2020; Zamanpour et al. 2021).
Figure 2b exhibits the infrared spectrum of Ag2O NPs. The analysis was performed over a range of wavelengths from 500 to 4000 cm− 1. The peaks at 3407 cm− 1 and 1623 cm− 1 may arise due to O‒H stretching mode of absorbed water molecules (Xu et al. 2013b). The bonds observed around 546 cm− 1 and 718 cm− 1 are corresponds to the stretching vibration of the Ag-O group (Ananth and Mok 2016; Bhogal et al. 2020).
The surface properties of Ag2O NPs were identified by using BET analysis (Fig. 2c). The BET surface area of Ag2O NPs was found to be 107.09 m2 g− 1, and the result obtained revealed that Ag2O NPs has a higher porosity with a total pore volume and average pore diameter was 0.38 m3 g− 1, and 31 nm, respectively.
The morphology of the adsorbent was analyzed by using SEM analysis. Figure 3a shows the micrograph of Ag2O NPs. The spherical shapes of the particles are clearly evident from the SEM image, and irregular structure with pores of different shapes and sizes, provide enough surface area for interaction with SMX molecules (Xu et al. 2013a; Abdalameer et al. 2021). The EDX spectra (Fig. 3b) showed the major elements detected as O (25.80%), and Ag (74.20%) similar to that reported by Mohammadi et al. (Mohammadi et al. 2019) and Haq et al. (Haq et al. 2018).
The TEM image of Ag2O NPs obtained, as shown in Fig. 3c. This image presents the highly ordered porous structure of Ag2O NPs, and spherical in the shape of the particles (Ahmad and Majid 2018). The bioactive compounds trapped on the surface of Ag2O NPs can be attributed to the Ag2O NPs surrounding the thin layer (Camacho-Escobar et al. 2020). The size and average of nanoparticles ranged from 24 to 36 nm confirming that the Ag2O NPs synthesized were in the nano-scale range.
3.2 Adsorption studies
3.2.1 Effect of solution pH
Figure 4a displays the SMX speciation diagram as a function of the solution pH. The SMX displays a pKa couple of 1.97 (pKa1) and 6.16 (pKa2), between these values the SMX has the unprotonated form (SMX+/−), while charged positively (SMX+) at pH < pKa1 and negatively (SMX−) at pH > pKa2 (De Oliveira et al. 2018). The effect of pH on SMX adsorption onto Ag2O NPs was investigated at different pH values ranging from 2 to 10 (Fig. 4b) at the kept factorial values (time = 180 min, temperature = 298 K, concentration = 100 mg L− 1, and Ag2O NPs dose = 1 g L− 1). Acidic pH promotes protonation of the Ag-O group (Ag-OH2+) resulting in acidic adsorption sites. Excess of H+ ions battle against the positive groups of antibiotic (SMX+) for adsorption surface, resulting in repulsion among the Ag-O group (Ag-OH2+) of adsorbent and SMX+ and antibiotic adsorption is disfavored. Whereas basic pH causes deprotonating of Ag-O group (Ag-O−) of adsorbent, more hydroxide ions render adsorption of SMX−, making the surface negatively charged of Ag2O NPS and antibiotic adsorption is also disfavored. The pH range 2–10 was selected for the sequestration of the SMX antibiotic. SMX adsorption depends upon charge and surface characteristics. The PZC of Ag2O NPs was found to be 5.3. At pH < PZC, the adsorbent is positively charged (Ag-OH2+) while it is negative at pH > PZC (Taher et al. 2021), the repulsive forces resulting between the Ag-OH2+ and Ag-O− groups and SMX+ and SMX−, respectively, therefore, the SMX adsorption is unfavorable. At pH near PZC (zwitterionic), the attractive forces result between the Ag-OH2+ and Ag-O− groups of adsorbent and SMX+/− antibiotic, thus antibiotic adsorption is favored. The result obtained is similar to that reported by Zhang et al. (2010) (Zhang et al. 2010). The highest uptake quantity of SMX was 122.45 mg g − 1 at pH = 4.
3.2.2 Effect of adsorbent dose
The effect of Ag2O dosage on the SMX adsorption was examined in the range 0.2–1.4 g L− 1 (Fig. 4c), while the other conditions are kept at the central value (time = 180 min, temperature = 298 K, concentration = 100 mg L− 1, and pH = 4). The SMX removal increased from 60.29 to 98.19% by increasing the adsorbent dose from 0.2 to 0.8 g L− 1 because large nanoparticle production provides an outspread surface area of the adsorbent which provides numerous active adsorbent sites for the antibiotic to get adsorbed. Hence more active site accessibility for the SMX molecules to adsorb (El Messaoudi et al. 2022a). After reaching maximum adsorption efficiency (> 0.8 g L− 1), an increase in dosage does not have much antibiotic sequestration efficiency. This is due to the gradient distribution between the Ag2O NPs and antibiotic as well as active sites saturation (Ogunleye et al. 2020). Adsorption capacity decreased (301.49 − 70.46 mg g− 1) with adsorbent dose from 0.2 to 1.4 g L− 1 due to an increase in unsaturated sites with an increase in the adsorbent dose and a rise in SMX concentrations (Ahsan et al. 2018). Hence, 0.8 g L− 1 of the adsorbent dose was selected for further experiments as higher concentrations did not yield significant results.
3.2.3 Effect of contact time
SMX antibiotic sequestration by Ag2O NPs is determined by finding the least time required for achieving equilibrium of antibiotic with the adsorbent in the range 5–180 min for three concentrations (100, 150, and 200 mg L− 1) at experiment conditions (Ag2O NPs dose = 0.8 g L− 1, T = 298 K, and pH = 4) (Fig. 5a). Noting strong adsorption of the SMX on the Ag2O NPs from the first minutes of contact between the antibiotic and the adsorbent is due to the number of active sites available on the surface (Guo et al. 2019). The balance of adsorption is reached in 90 min, beyond this time, it was found that the amount adsorbed for 100 mg L− 1 is about 122.78 mg g− 1, 181.61 mg g− 1 for 150 mg L− 1, and 231.12 mg g− 1 for 200 mg L− 1. After 90 min, the SMX adsorption capacity became de-escalate due to the occupation of active sites of Ag2O NPs (Liu et al. 2017). Therefore, 90 min is considered the equilibrium time optimum.
3.2.4 Effect of SMX concentration and temperature
The influence of initial SMS concentration at three temperatures 298 K, 308 K, and 318 K on SMX adsorption using Ag2O NPs is shown in Fig. 5b. To investigate the effect of initial antibiotic concentration on SMX adsorption, the antibiotic concentration was varied from 50 to 400 mg L− 1. It is noted that the adsorption capacity of SMX increased from 60.96 to 250.26 mg g− 1 for 298K, from 61.57 to 260.14 mg g− 1 for 308 K, and from 61.98 to 276.48 mg g− 1 for 318 K with SMX concentration from 50 to 250 mg L− 1. This is because at a low concentration range the ratio between the Ag2O NPs surface and the SMX molecules in the solution are in abundance, therefore all of the antibiotic particles are easily imbibed over the surface of the active adsorbed and get eliminated from the media (Guo et al. 2019). After 250 mg L− 1 of SMX concentration, the adsorption capacity was achieved. This is because at higher concentrations the driving force is also higher due to the concentration gradient and the adsorbed amount of the antibiotic per unit mass of the Ag2O NPs is also high which leads to the saturation of active sites (Liu et al. 2017).
Figure 5b also shows the effect of temperature on the adsorption capacity of SMX. It is evident that qe increases with temperature from 298 to 318 K, which may probably be due to the high rate of mass transfer from the bulk solution to a solid phase, widening of pore size, and/or activation of adsorption sites (Fulazzaky 2011). Additionally, an enhancement in the quantity adsorbed with temperature is descriptive of the endothermic nature of adsorption (El Messaoudi et al. 2021b), this is confirmed by thermodynamic and equilibrium isotherm studies subsequently.
3.3 Adsorption modeling
3.3.1 Kinetics
The dynamics of the adsorption of SMX onto Ag2O NPs were investigated using Lagergren’s
pseudo-1st -order model (PFO) (Lagergren 1898), pseudo-2nd -order (PSO) model proposed by Ho and McKay (Ho and McKay 1998) and intraparticle diffusion model (IPD) (El Messaoudi et al. 2022b). The KPFO (PFO constant) was calculated from the plot of log (qe-qt) versus t (Fig. 6a), while the plot of t/qt versus t (Fig. 6b), and gives the value of KPSO (PSO constant), which are tabulated in Table 2 along with R2 values. Comparatively lower R2 values for PFO model along with the evident deviation from linearity suggest incongruity of the model with the kinetic data thus ruling out the possibility of interaction of the antibiotic molecule with a single active site. However, the linearity of the t/qt versus t plots and high R2 values (0.999) reflects that adsorption conforms better to the PSO kinetic model. Moreover, calculated equilibrium capacities qe,PSO are in complete agreement with that of experimental equilibrium capacities qe,exp. It is, therefore, concluded that the rate of adsorption of SMX onto Ag2O NPs for three concentrations (100, 150, and 200 mg L− 1) is related to the square of the number of available active sites and a single antibiotic molecule is capable of interacting with two adsorption sites simultaneously (Wang et al. 2015). This is similar to reports on the adsorption of SMX onto the Fe-impregnated graphited biochar (Zhang et al. 2020) and montmorillonite (Wu et al. 2019) adsorbents.
| Model | Parameter | SMX conc. (mg L− 1) | |||
|---|---|---|---|---|---|
| 100 | 150 | 200 | |||
| qe,exp (mg g− 1) | 123.87 | 182.23 | 233.87 | ||
| PFO \({ Log(q}_{e}-{q}_{t})={Log(q}_{e})-\frac{{K}_{PFO}}{2.303}t\) | qe,PFO (mg g− 1) | 39.79 | 92.44 | 147.40 | |
| KPFO (min− 1) | 0.030 | 0.033 | 0.035 | ||
| R2 | 0.926 | 0.923 | 0.954 | ||
| PSO \(\frac{t}{{q}_{t}}=\frac{1}{{K}_{PSO}{{q}_{e}}^{2}}+\frac{1}{{q}_{e}}t\) | qe,PSO (mg g− 1) | 126.58 | 192.30 | 238.09 | |
| KPSO (g mg− 1 min− 1) | 0.0017 | 0.0019 | 0.0024 | ||
| R2 | 0.999 | 0.998 | 0.998 | ||
| IPD \({q}_{t}={K}_{IDP}{t}^{1/2} + {C}_{i}\) | 1st linear portion | KIPD1 (mg g− 1 min− 1/2) | 14.303 | 16.215 | 21.198 |
| C1 (mg g− 1) | 41.31 | 58.04 | 60.42 | ||
| R2 | 0.958 | 0.978 | 0.975 | ||
| 2nd linear portion | KIPD2 (mg g− 1 min− 1/2) | 4.523 | 10.149 | 12.745 | |
| C2 (mg g− 1) | 83.28 | 78.22 | 115.06 | ||
| R2 | 0.997 | 0.996 | 0.966 | ||
| 3th linear portion | KIPD3 (mg g− 1 min− 1/2) | 0.237 | 0.368 | 0.641 | |
| C3 (mg g− 1) | 120.39 | 177.92 | 225.06 | ||
| R2 | 0.859 | 0.873 | 0.961 | ||
The intraparticle diffusion model controls the process when the three basic adsorption steps, that is, instant, gradual and equilibrium adsorptions become indistinguishable (El Messaoudi et al. 2022b). The slope and intercept of qt versus t1/2 plots give the values of KIPD (IPD constant ) and Ci (boundary layer thickness) at three different concentrations (Fig. 6c), which are tabulated in Table 2. From Fig. 6c, the SMX adsorption process on Ag2O NPs presents in three successive stages. The first stage describes the diffusion of SMX molecules from the aqueous phase to the external surface sites of Ag2O NPs (Ahmed et al. 2021). The second phase indicates the intraparticle diffusion of SMX species into the internal surface of Ag2O NPs with a rate-controlling step (Tavlieva et al. 2013). The values of C2 (83.28–115.06 mg g− 1) illustrate that liquid film diffusion plays a dominant contribution to the overall rate-controlling step for three concentrations (100, 150, and 200 mg L− 1). The third step corresponds to adsorption equilibrium because of the extremely low concentration of SMX (Yao and Chen 2017).
3.3.2 Equilibrium
To understand the mechanisms involved in the adsorption of SMX on Ag2O NPs at three temperatures (298, 308, and 318 K), four isotherm models are use such as Langmuir, Freundlich, Temkin, and Dubinin‒Radushkevich (D-R). The Langmuir model is very useful for the monomolecular adsorption of a solute by forming a monolayer on the surface of the adsorbent (Langmuir 1918). The Freundlich model is based on adsorption on heterogeneous surfaces (Freundlich 1907). Temkin isotherm model contemplates a linear decline in the heat of adsorption of molecules in the layer with surface coverage as an indirect consequence of adsorbate-adsorbent interactions, and the homogeneous distribution of binding energies characterizes the adsorption process (Johnson and Arnold 1995). Dubinin‒Radushkevich (D-R) isotherm is associated with multilayer adsorption with a tendency of adsorbate molecules to fill the micropores (Çelebi et al. 2007; Ayawei et al. 2017). It is also generally utilized for the prediction of the adsorption mechanism (Chen and Yang 2002; Gallego-Gómez et al. 2020).
The values of Qm (maximum adsorption capacity) and KL (Langmuir constant) at three different temperatures (298–318 K) were obtained from the slope and intercept, respectively of Ce/qe versus Ce plots (Fig. 7a). The values of KF (Freundlich constant) and 1/nF (heterogeneity factor) were obtained from the slope and intercept respectively of the linear lnqe versus lnCe plots (Fig. 7b). A linear plot of qe versus lnCe (Fig. 7c) gives the values of Temkin constants, KT (Temkin constant) and bT from its slope and intercept, respectively. The linear curves of lnqe versus ε2 (D-R constant, ε = RTln(1 + 1/Ce)) (Fig. 7d) were used to determine the Qm and β from the slope and intercept, respectively. From Table 3, the values of KL, which denotes the binding affinity or strength of antibiotic molecules with Ag2O NPs surface show a gradual increment from 0.232 to 0.394 L mg− 1 with raise in solution temperature (298 to 318 K) indicating thereby an improved SMX-Ag2O NPs binding strength at elevated temperature. The higher Qm, which is often considered a measure of the efficacy of an adsorbent (277.85–312.59 mg g− 1) confirms the efficient adsorption performance of Ag2O NPs at all tested temperatures. An ascending trend in KF from 82.121 to 109.039 mg g− 1 with rising in operating temperature from 298 to 318 K is illustrative of the endothermic adsorption of SMX. The calculated values of 1/nF (0.248–0.259) are positive but less than one which advocates favorable adsorption in the studied temperature range. The correlation coefficient R2 values for the Langmuir model is higher (0.999) for three temperatures signifying a good fit of the equilibrium data at high temperatures. The constant KT increases from 6.903 to 16.014 L mg− 1 with temperature further confirms the endothermic nature of SMX adsorption. The adsorption energy value (E = 1/(2 β)1/2) is functional in describing the nature of the adsorption mechanism (E < 8 kJ mol− 1 physisorption; E > 16 kJ mol− 1 chemisorption; and 8 ≤ E ≤ 16 kJ/ mol− 1: ion exchange) (Isiuku et al. 2021). The E values in the 0.845–2.236 kJ mol− 1 range reflect the physical mode of the adsorption. The R2 values for the Langmuir model (0.999) are considerably close to unity relative to Freundlich (0.847–0.868), Temkin (0.942–0.957), and D–R (0.817–0.898) models, which describes that the equilibrium data is more appropriately explicated by the Langmuir model, suggesting that monolayer adsorption of SMX on Ag2O NPs (Wu et al. 2019). The performance appraisal of Ag2O NPs based on comparative Qm values of hitherto reported adsorbents for SMX removal (Table 4), reveals that the present adsorbent has shown superior uptake competence outperforming the existing adsorbents.
| Model | Parameter | Temperature (K) | ||
| 298 | 308 | 318 | ||
| Langmuir\(\)\(\frac{{C}_{e}}{{q}_{e}}=+\frac{{C}_{e}}{{Q}_{m}}+\frac{{C}_{e}}{{Q}_{m}}\) | Qm (mg g− 1) | 277.85 | 295.85 | 312.59 |
| KL (L mg− 1) | 0.232 | 0.262 | 0.394 | |
| R 2 | 0.999 | 0.999 | 0.999 | |
| Freundlich \(Ln{q}_{e}=Ln{K}_{F}+\frac{Ln{C}_{e}}{{n}_{F}}\) | KF (mg g− 1) | 82.121 | 92.489 | 109.039 |
| 1/nF | 0.259 | 0.252 | 0.248 | |
| R 2 | 0.847 | 0.870 | 0.868 | |
| Temkin \({q}_{e}=\frac{RT}{{b}_{T}}Ln{K}_{T}+\frac{RT}{{b}_{T}}Ln{C}_{e}\) | bT (kJ mol− 1) | 0.061 | 0.064 | 0.072 |
| KT (L mg− 1) | 6.903 | 9.130 | 16.014 | |
| R 2 | 0.942 | 0.959 | 0.957 | |
| D-R \(Ln{q}_{e}=Ln{Q}_{m}-\beta {\epsilon }^{2}\) | Qm (mg g− 1) | 232.64 | 242.79 | 250.46 |
| E (kJ mol− 1) | 0.845 | 1.290 | 2.236 | |
| R 2 | 0.898 | 0.851 | 0.817 | |
| Adsorbent | Qm (mg g− 1) | Reference |
|---|---|---|
| Fe-impregnated graphited biochar | 205.00 | (Zhang et al. 2020) |
| carbonnanotubes/CoFe2O4 | 248.91 | (Wang et al. 2015) |
| CuZnFe2O4/biochar | 213.00 | (Heo et al. 2019) |
| Magnetic activated carbon | 173.00 | (Lv et al. 2021) |
| Activated carbon | 113.00 | (Jaria et al. 2021) |
| AC functionalized with thiol groups | 140.00 | (Jaria et al. 2021) |
| Fe3O4 /pectin-waste biomass | 120.00 | (Kadam et al. 2020) |
| Tea waste-SO3H | 258.87 | (Ahsan et al. 2018) |
| Commercially available activated carbon | 118.00 | (Calisto et al. 2015) |
| Graphene oxide | 240.00 | (Chen et al. 2015) |
| Ag2O NPs | 277.85 | Current study |
3.4 Thermodynamic studies
The study of the thermodynamics of the adsorption process is useful in obtaining the information related to the feasibility/spontaneity, exothermic/endothermic and disorder at the solid-solution interface based on the evaluated values of changes in Gibbs free energy (ΔGº), enthalpy change (ΔHº) and entropy (ΔSº) change, respectively. The values of ΔHº and ΔSº were obtained from the slope and intercept of the linear plot of lnKd versus 1/T (Fig. 8a) according to Eq. 8, while ΔGº was computed using Eq. 7 (El Messaoudi et al. 2021c):
$$\varDelta G^\circ =-RTLn{K}_{d} \left(7\right)$$
$$Ln{K}_{d}=\frac{\varDelta S^\circ }{R}-\frac{\varDelta H^\circ }{RT} \left(8\right)$$
where, R (8.314 J mol− 1 K− 1) is the universal gas constant and T (K) is the absolute temperature, and Kd is the distribution coefficient defined as qe/Ce. The values of the thermodynamic parameters are given in Table 5. For the SMX adsorption onto the Ag2O NPs, the negative ΔGº at all studied temperatures infers the feasibility of the process for three concentrations (100, 150, and 200 mg L− 1). Further, the increase of ΔGº with temperature shows that SMX removal is spontaneous and more promising at higher temperatures (Ahmed et al. 2021). This is supported by the positive ΔHº, which affirms the endothermic adsorption (Serna-Carrizales et al. 2021). Entropy change is a measure of the change in randomness at the solid-liquid interface. The positive ΔSº values (108.523–132.484 J mol− 1 K− 1) indicate the increase in randomness of SMX adsorption (Fierro et al. 2007).
| SMX conc. (mg L− 1) | T (K) | ΔG° (kJ mol− 1) | ΔH° (kJ mol− 1) | ΔS° (J mol− 1 K− 1) |
|---|---|---|---|---|
| 100 | 298 | –08 .741 | 23.619 | 108.523 |
| 308 | –09.798 | |||
| 318 | –10.925 | |||
| 150 | 298 | –06.917 | 27.712 | 114.461 |
| 308 | –08.117 | |||
| 318 | –09.927 | |||
| 200 | 298 | –05.584 | 33.887 | 132.484 |
| 308 | –06.942 | |||
| 318 | –08.241 |
3.5 Recyclability of Ag2O NPs
The reusability experiment gives useful insights into the possibility of recovery and operational behavior of the adsorbent. The recyclability of Ag2O NPs for the removal of SMX was tested after acetone and ethanol washing. The results are summarized in Fig. 8b. The difference in percentage removal between the first and five uses of Ag2O NPs adsorbent for removal of SMX was 22% at optimal conditions: 0.8 g L− 1 of adsorbent dose, pH of 4, 100 mg L− 1 of SMX concentration at 308 ± 1 K for 90 min. Still, further research is required for the usage of Ag2O NPs for antibiotics removal from wastewaters.
3.6 DFT results
The analysis of the HOMO and LUMO energy levels, as well as the gap energy, is very important in the study of the properties of organic molecules (Jodeh et al. 2022). The energies of the HOMO and LUMO frontier orbitals and the gap energy of the molecules calculated by the DFT/B3LYP 6–31 + G (d,p) method under different pH conditions from the optimized structures are given in Table 6, a unprotonated and protonated state. From this table, we notice that the SMX+ molecule has the highest energy gap ΔEgap=5.717 eV, therefore it is the most stable and the least chemically active (Zhuang et al. 2020). In the case of SMX+/−, it has the lowest energy gap ΔEgap=5.197 eV, so it is the least stable and the most chemically active (Liu et al. 2020b). The importance of η and σ is to evaluate both reactivity and stability. The neutral form of SMX has the lowest value of chemical hardness (η = 2.598 eV), which means high reactivity compared to the protonated form (Alivand et al. 2019). Global reactivity plays an important role to describe the ability of SMX to interact with the surface of Ag2O NPs under different pH conditions. Optimized geometries, HOMO, LUMO frontier orbitals, and ESP maps corresponding to the two forms of SMX are presented in Fig. 9. This figure shows that the backbone of the SMX molecule in both the proton and unproton forms is characterized by positive potential (i.e. the blue regions in Fig. 9d and g) (Obot and Obi-Egbedi 2010). According to these observations, the non-protonated molecule is reacting more favorably on the surface of Ag2O NPs. These results are in good agreement with those obtained experimentally.
| SMX | EHOMO (eV) | ELUMO (eV) | ΔEgap (eV) | η (eV) | χ (eV) | σ (eV− 1) | µ(D) |
|---|---|---|---|---|---|---|---|
| SMX+/− | –6.278 | –1.081 | 5.197 | 2.598 | 3.680 | 0.386 | 15.55 |
| SMX+ | –8.359 | –2.642 | 5.717 | 2.858 | 5.500 | 0.349 | 11.761 |
| Graphical abstract | |||||||
3.7 Proposed adsorption mechanism
The FTIR and PZC of Ag2O NPs, DFT calculation of SMX, and the influence of operational solution pH are mainly functional in understanding the type of interactions taking place between the surface of Ag2O NPs and SMX molecules. Since qe was relatively unaltered with change in the initial pH, the possibility of interactions is excluded, thus pointing towards the involvement of hydrogen-bonding, hydrophobic, and π-π interactions (Fig. 10) (Eniola et al. 2019; Ahmed et al. 2021). The interactions were of the physical kind, which is supported by the D-R isotherm model study which established the physical nature of adsorption.
Ag2O nanoparticle has been successfully prepared by the green synthesis method from Punica granatum leaf extract. The XRD, FTIR, BET, SEM-EDX, TEM, and PZC techniques were used to examine the structural, morphological, and chemical properties of the Ag2O NPs. At optimal operating conditions (time = 90 min, Ag2O NPs dose = 0.8 g L− 1, SMX concentration = 100 mg L− 1, T = 308 K, and pH = 4), the removal and adsorption capacity of SMX were 98.93% and 122.63 mg g− 1, respectively. The kinetics of SMX adsorption was best appropriated by the PSO model. The adsorption was best explained by the Langmuir isotherm model, thus defining monolayer SMX adsorption onto homogeneous Ag2O NPs surface. Thermodynamically, the adsorption process revealed an endothermic nature and confirmed the feasibility and spontaneity of the reaction. Langmuir adsorption capacity of 277.85 mg g− 1 was considerably higher than those reported previously. The experimental results are in good agreement with those obtained by DFT calculation. Hydrogen-bonding, hydrophobic, and π-π interactions were majorly involved in the SMX uptake by Ag2O NPs.
Data availability
The datasets used during the current study are available from the corresponding author on reasonable request.
Author Contributions
Noureddine El Messaoudi: Investigation and Writing-original draft; Abdelaziz El Mouden: Verification and Methodology; Yasmine Fernine: Software and Review editing; Mohammed El Khomri: Verification, Validation, and Methodology; Amal Bouich: Verification, Validation, and Methodology; Nadia Faska: Review editing; Zeynep Ciğeroğlu: Review editing, Conceptualization, and Visualization; Juliana Heloisa Pinê Américo-Pinheiro: Review editing; Amane Jada: Review editing, and Conceptualization; Abdellah Lacherai: Review editing, Conceptualization, and Supervision.
Compliance with ethical standards
Ethics approval and consent to participate
Not applicable.
Funding
No funding.
Consent for publication
Not applicable.
Competing interests
The authors declare that they have no competing interests.
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