In this study, we report a facile hydrothermal synthesis of strontium-doped SnS nanoflowers that were used as a catalyst for the degradation of antibiotic molecules in water. The prepared sample was characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet–visible absorption spectroscopy (UV–Vis). The photocatalytic ability of the strontium-doped SnS nanoflowers was evaluated by studying the degradation of metronidazole in an aqueous solution under photocatalytic conditions. The degradation study was conducted for a reaction period of 300 min at neutral pH, and it was found that the degradation of metronidazole reached 91%, indicating the excellent photocatalytic performance of the catalyst. The influence of experimental parameters such as catalyst dosage, initial metronidazole concentration, initial reaction pH, and light source nature was optimized with respect to metronidazole degradation over time. The reusability of the strontium-doped SnS nanoflowers catalyst was investigated, and its photocatalytic efficiency remained unchanged even after four cycles of use.

  • Sr-doped SnS is synthesized by the hydrothermal process.

  • Sr-doped SnS nanoflowers were selected to remove dyes from water.

  • The removal percentage of Sr-doped SnS could reach 91%.

  • The reusability of our catalyst Sr-doped SnS was also explored.

Water pollution is a serious environmental problem that occurs when harmful substances, such as chemicals, waste materials, and sewage, contaminate bodies of water like oceans, rivers, and lakes. Human activities such as industrialization, agricultural practices, and improper waste disposal are major contributors to water pollution (Bashir et al. 2020; Qadri et al. 2020; Akhtar et al. 2021; Karri et al. 2021; Sarker et al. 2021). The consequences of water pollution can be devastating for both aquatic life and humans who rely on these water sources for drinking, irrigation, and recreational purposes. It can lead to the depletion of fish populations, the spread of waterborne diseases, and the contamination of food sources. Addressing water pollution requires a concerted effort from individuals, governments, and industries to adopt sustainable practices and reduce harmful pollutants in our water sources (Weldeslassie et al. 2018; Chowdhary et al. 2020; Kiliç 2021; Morin-Crini et al. 2022).

Water pollution caused by antibiotics, including metronidazole (MNZ), is a growing concern worldwide. When antibiotics are used in human or animal medicine, a portion of the drug is excreted from the body and ends up in wastewater. Treatment plants are not designed to remove antibiotics from wastewater, so they are discharged into rivers, lakes, and oceans. This discharge of antibiotics into water bodies can lead to the development of antibiotic-resistant bacteria, which can pose a serious threat to public health (Polianciuc et al. 2020; Baaloudj et al. 2021; Jovanovic et al. 2021; Tian et al. 2021). MNZ, in particular, is an antibiotic used to treat infections such as bacterial vaginosis and periodontitis. It has been found to persist in the environment for long periods and can be toxic to aquatic organisms, even at low concentrations. The accumulation of MNZ in the environment can have detrimental effects on aquatic ecosystems and pose a risk to human health (Bashiri et al. 2020; Ighalo et al. 2020; Wang et al. 2022a; Aoudjit et al. 2023).

Eliminating organic pollutants from water is a complex process that requires the use of various techniques. One of the most effective methods is activated carbon filtration, which involves passing water through a bed of activated carbon to remove organic contaminants (Castiglioni et al. 2022; Zioui et al. 2022; Huang et al. 2023; Yang et al. 2023). Another technique is reverse osmosis, which uses a semi-permeable membrane to filter out pollutants (Hu et al. 2023; Liao et al. 2023; Pezeshki et al. 2023; Shen et al. 2023). Biological treatment, which uses bacteria or other microorganisms to breakdown organic compounds, is also an effective method for eliminating pollutants (Yang et al. 2022; Rokkarukala et al. 2023; Tian et al. 2023). Membrane process represent an efficient, straightforward, and low-cost alternative as a pretreatment step for continuous treatment processes for simultaneous organic and inorganic contaminants' remediation in real industrial effluent sources as reported by Zioui et al. (2023). Additionally, advanced oxidation processes (AOPs) such as UV oxidation or ozonation can be used to breakdown organic contaminants into less harmful substances. Overall, a combination of these techniques may be necessary to completely eliminate organic pollutants from water (Liu et al. 2022; Li et al. 2023; Saoud et al. 2023; Wardighi et al. 2023). Photocatalysis is a powerful technique used to eliminate organic pollutants from water and air. It involves the use of a catalyst that can convert light energy into chemical energy to breakdown organic molecules into harmless substances such as water and carbon dioxide. This technique is highly effective and environmentally friendly as it does not produce any toxic byproducts or require any additional chemicals. Photocatalysis is becoming an increasingly popular technique of choice for eliminating organic pollutants due to its high efficiency, low cost, and versatility in treating a wide range of contaminants (Sun et al. 2023; Yin et al. 2023; Yu et al. 2023; Wang et al. 2023a, 2023b). The decontamination of wastewater (degradation of oil in wastewater) using AOP photocatalysts and solar wastewater treatment (SOWAT) has been reported as possible techniques for wastewater purification using solar radiation for reuse in agriculture and industry (Igoud et al. 2019, 2021, 2022; Zioui et al. 2019; Martins et al. 2021).

Semiconductor photocatalysts, particularly those based on sulfur, have gained significant attention in recent years due to their unique properties and potential applications in various fields. Sulfur-based photocatalysts have a narrow bandgap, allowing them to absorb light in the visible range and generate charge carriers that can facilitate chemical reactions. This property makes them particularly useful in photocatalytic applications, such as environmental remediation, hydrogen production, and organic synthesis. Additionally, sulfur-based photocatalysts are cost-effective and environmentally friendly, making them a promising alternative to traditional photocatalytic materials. Ongoing research in this area aims to optimize the performance of sulfur-based photocatalysts and explore new applications for these versatile materials (Lincho et al. 2023; Liu et al. 2023; Saoud et al. 2023; Zhang et al. 2023).

SnS (tin sulfide) is a semiconductor material with a tunable bandgap energy that makes it suitable for various optoelectronic and photovoltaic applications, including photocatalysis. The bandgap energy of SnS ranges from 0.9 to 1.3 eV, which corresponds to the visible to near-infrared light spectrum, making it an efficient absorber of solar radiation. In photocatalysis, SnS-based materials have been used for the degradation of organic pollutants, water splitting, and CO2 reduction. The unique electronic and optical properties of SnS, such as its high absorption coefficient, long carrier lifetime, and high quantum efficiency, make it a promising candidate for photocatalytic applications. Additionally, the abundance, low toxicity, and earth-abundant constituent elements of SnS make it a sustainable and environmentally friendly alternative to other photocatalytic materials. Further research is needed to optimize the photocatalytic performance of SnS and to develop efficient and stable SnS-based photocatalysts for practical applications (Nengzi et al. 2020; Hegde et al. 2021; Zhang et al. 2021; Alikarami et al. 2022; He et al. 2023; Katoch et al. 2023).

The process of doping photocatalysts involves adding impurities to improve their photocatalytic properties by altering their electronic structure and enhancing their ability to absorb light and generate charge carriers. Metals like silver, gold, and platinum and nonmetals like nitrogen and sulfur are common dopants used. Doping with strontium (Sr) has shown to significantly enhance photocatalytic activity by improving visible light absorption and charge carrier separation, leading to applications in water splitting, pollutant degradation, and hydrogen production. Sr doping also improves stability and durability, making it a promising strategy for developing high-performance photocatalysts (Tran et al. 2020; Iqbal et al. 2021; Yarahmadi et al. 2021; Uma et al. 2022; Sharma et al. 2023).

In this work, we have successfully synthesized nanoflowers of SnS and Sr-doped SnS, which demonstrate excellent performance for the degradation of MNZ. The unique morphology of the nanoflowers provides a large surface area for the active sites to interact with the target pollutant, while the Sr doping enhances the catalytic activity and stability of the material. Our results suggest that the synthesized nanoflowers have great potential for the treatment of MNZ -contaminated wastewater, and may also inspire the development of new nanomaterials for environmental remediation.

Catalyst preparation

In this study, a hydrothermal technique was employed to synthesize SnS and Sr-SnS NPs. Initially, SnS NPs were prepared by dissolving 2.25 g of SnCl2 2H2O in 20 mL of distilled water (625 mM) and 4.5 g of SC(NH2)2 in 40 mL of distilled water (1.5M) separately. Each solution was stirred for 30 min. Next, the SnCl2 2H2O solution was added to the SC (NH2)2 solutions, and the resulting mixture was stirred for a duration of 2 h, while introducing 20 mL of distilled water. The mixed solution is then transferred to a 100-mL Teflon-lined stainless steel autoclave and maintained at 180 °C for 12 h. The Sn0.9Sr0.1S samples were synthesized using 62.5 mM of SrCl2 6H2O. After the reaction was completed, the autoclave was allowed to cool down to room temperature. To eliminate any remaining impurities, the resulting powder underwent multiple washes with ethanol and distilled water. Finally, the powder was air-dried for duration of 2 h at 50 °C.

Catalyst characterization

The X-ray diffraction (XRD) patterns and scanning electron microscope (SEM) micrographs of the samples prepared as mentioned above were recorded. The XRD patterns were recorded on a Siemens D-5000 diffractometer with Cu-Kα radiation (λ = 1.5418 Å) and surface morphology was studied using SEM (Thermo Fisher Scientific). The UV–Vis absorption spectra were measured by UV–Vis spectrophotometer (Shimadzu UV-2401).

Photocatalytic removal studies

The photocatalytic process was conducted in batch mode at room temperature. MNZ solutions containing the desired concentrations (10, 20, and 30 mg/L) were prepared by dissolving the corresponding amount of MNZ in distilled water. The solution was transferred to a triple-walled Pyrex batch reactor and an appropriate amount of SnS and Sr-doped SnS (1 g/L) catalyst was determined to be the optimal dose, and was added. The pH of the solution was adjusted using NaOH or HCl. All mixtures were magnetically stirred. Each sample was kept in the dark for 30 min in order to reach adsorption-equilibrium, the reactor was then exposed to natural sunlight irradiation for 5 h. Sampling for analysis was affected by taking 3 mL aliquots from the reaction mixture at regular time intervals (30 min), subjected to vigorous centrifugation (6,000 rpm, 20 min) to remove the catalyst particles, and filtered through 0.45-mm millipore filters. Finally, the absorbance of the solution was measured at 320 nm. The percentage of degradation was estimated using the following equation:
formula
(1)
where C0 is the initial MNZ concentration and Ct is the MNZ concentration at certain reaction time t (min).

Characterization of the catalyst

XRD analysis

The XRD patterns of SnS and Sr-doped SnS are depicted in Figure 1, with diffraction peaks located at 22.03°, 26.03°, 27.41°, 30.48°, 31.53°, 31.94°, 39.04°, 44.73°, 48.6°, 51.28°, 54.22°, and 64.20°. According to the JCPDS card (96-900-8786), these peaks have been identified as the orthorhombic structure's Bragg's planes (101), (201), (210), (011), (111), (400), (410), (411), (211), (151), (061), and (512), respectively (Baby et al. 2021; Dar et al. 2022). Furthermore, no additional strontium-related peaks showed up, proving that no new impurity phases have developed. An in-depth analysis of the XRD peaks (111) (400) (see supplementary material) of both SnS and Sr-SnS patterns showed a slight shift toward high diffraction angles (Figure 1), demonstrating the incorporation of Sr2+ in SnS substitutional sites. In addition, structural parameters such as average crystallite size, dislocation density, microstrain, and lattice parameters were calculated using the following equations, with the results shown in Table 1.
Table 1

Structural parameters of SnS and Sr-SnS nanoflowers

SamplesDiffraction anglesCrystallite size (nm)Microstrain 10−3Dislocation density 10−3 (nm2)Lattice parameters (Å)
abc
SnS 31.54 44 0.2151 0.5593 11.20 3.99 4.31 
Sr-SnS 31.57 40 0.2309 0.6594 11.19 3.99 4.30 
SamplesDiffraction anglesCrystallite size (nm)Microstrain 10−3Dislocation density 10−3 (nm2)Lattice parameters (Å)
abc
SnS 31.54 44 0.2151 0.5593 11.20 3.99 4.31 
Sr-SnS 31.57 40 0.2309 0.6594 11.19 3.99 4.30 
Figure 1

XRD spectra of SnS and Sr-SnS nanoflowers.

Figure 1

XRD spectra of SnS and Sr-SnS nanoflowers.

Close modal
The mean crystallite size D of the synthesized nanoparticles was estimated from the full width half maximum FWHM (β) of all peaks, using the Debye–Scherer's formula (Salima et al. 2023):
formula
(2)
where λ is the used wavelength (λ = 1.5406 Å) and θ is the Bragg's diffraction angle.
The crystallite mean size was estimated to 44 and 40 nm for both SnS and Sr-SnS, respectively. Moreover, the orthorhombic lattice parameters (a, b, and c) were determined using the following formula (Arefi-Rad & Kafashan 2020):
formula
(3)
where ‘dhkl’ represents the interplanar spacing, ‘hkl’ is the Miller indices. The planes (400), (011) and (101) were used for the calculation of lattice parameters a, b, and c, respectively. The dislocation density and microstrain were calculated using the following relations, respectively (Messai et al. 2023):
formula
(4)
and
formula
(5)
Table 1 shows that the diffraction peaks shift slightly toward the higher diffraction angles and the lattice parameters (a, c) are slightly decreased with increasing Sr2+ concentrations, despite the fact that the value of parameter b remains constant. These observations revealed that Sr2+ was successfully substituted into the SnS host. Additionally, we can see that Sr doping results in an increase in microstrain and dislocation density. These results being comparable with those observed on Sr-incorporated ZnS (Boulkroune et al. 2019).

Optical properties and band gap estimation

Figure 2 presents the optical properties of both undoped SnS and Sr-SnS NPs in the range of 200–700 nm. Upon Sr doping, a remarkable alteration in absorbance was evident, notably showcasing a shift toward higher longer wavelengths. This shift can be attributed to the incorporation of additional electrons during the Sr doping process, leading to a redistribution of energy levels within the crystal structure of the nanoparticles. The observed change in absorbance suggests a modification in the electronic band structure of the SnS nanoparticles due to Sr doping.
Figure 2

UV–Visible spectra for SnS and doped Sr-SnS nanoflowers. The inset shows a shift toward longer wavelengths.

Figure 2

UV–Visible spectra for SnS and doped Sr-SnS nanoflowers. The inset shows a shift toward longer wavelengths.

Close modal

The doping also led to a change in the gap energy of SnS NPs. Gap energy is an essential characteristic that directly influences the electronic and optical properties of semiconductor materials. Commonly, the direct bandgap energy (Eg) is estimated via Tauc's relation (F(R))2=A (Eg), which and A are incident photon energy and ‘A’ constant, respectively (Arefi-Rad & Kafashan 2020). The interception of the linear fit of (F(R) hν)2 plot with axis shows the Eg (Salima et al. 2023).

Figure 3 displays the Tauc's plots for SnS and Sr-SnS NPs. The bandgap of SnS was measured to be 1.42 eV, whereas for Sr-SnS, it was found to be 1.48 eV. The same results have been documented (Hegde et al. 2020; Baby et al. 2021). The increase in the gap energy observed here can be attributed to the introduction of additional levels into the conduction band, effectively lowering the energy required to excite electrons in the material.
Figure 3

Estimation of band gap for SnS and doped Sr-SnS nanoflowers using the Kubelka–Munk approach.

Figure 3

Estimation of band gap for SnS and doped Sr-SnS nanoflowers using the Kubelka–Munk approach.

Close modal
Figure 4

SEM images for SnS and doped Sr-SnS nanoflowers.

Figure 4

SEM images for SnS and doped Sr-SnS nanoflowers.

Close modal

SEM analysis

The morphological analysis of SnS and Sr-doped SnS nanoparticles reveals intriguing and heterogeneous structures that hold significant potential for various surface applications, particularly in the realm of photocatalysis. In the case of pristine SnS nanoparticles, a rich diversity of morphologies is evident from the images, showcasing distinct nanoflower formation, along with nano-triangles and nano-plates that intricately assemble into flower-like structures. Similarly, the Sr-doped SnS nanoparticles exhibit striking resemblances in their morphologies, featuring nanoflower arrangements and nano-plates organized in captivating flower-like configurations (Figure 4) (Vaughn et al. 2012; Bai et al. 2021). These intricate morphologies play a pivotal role in dictating the nanoparticles' surface properties, making them highly promising candidates for photocatalytic applications. The heterogeneity of these morphologies not only enhances the surface area, but also influences the light absorption and charge separation capabilities, ultimately boosting the photocatalytic efficiency. The EDX profile (Figure 5) also proves the coexistence of Sn, S, and Sr elements.
Figure 5

EDS spectrum for SnS and doped Sr-SnS nanoflowers.

Figure 5

EDS spectrum for SnS and doped Sr-SnS nanoflowers.

Close modal

Photodegradation of MNZ

Evaluation of the treatment strategy for MNZ degradation

In order to evaluate the effectiveness of photocatalysis, a series of preliminary tests were conducted. The objective was to study the degradation process of MNZ in polluted water using various experimental conditions. Three different approaches were considered, based on the use or absence of a catalyst (Sr-doped SnS) and a light source (sunlight). As a result, three distinct scenarios were analyzed: (1) without catalyst and without radiation, which corresponds to adsorption phenomena; (2) with catalyst and without radiation, which represents photolysis process, and (3) with catalyst and radiation, which corresponds to photocatalysis. Figure 6 illustrates the evolution of MNZ degradation under each of these three conditions.
Figure 6

Degradation of MNZ under different processes (CMNZ = 20 mg/L, Ccatalyst = 1 g/L and free pH = 6, 4).

Figure 6

Degradation of MNZ under different processes (CMNZ = 20 mg/L, Ccatalyst = 1 g/L and free pH = 6, 4).

Close modal

The results of the experimental tests clearly indicate that photocatalysis has a substantial impact on the photodegradation of MNZ, while the effects of adsorption and photolysis are relatively insignificant. This finding is consistent with prior research in the field, which has already demonstrated the effectiveness of photocatalytic methods in removing pollutants from water. The use of a catalyst in combination with sunlight leads to a significant increase in the degradation rate of MNZ, highlighting the potential of photocatalysis as an efficient and sustainable method for water treatment. These results provide valuable insights into future research in the field of environmental engineering and water treatment (Chekir et al. 2017; Aoudjit et al. 2018; Bouarroudj et al. 2021).

Furthermore, after 300 min of exposure to sunlight in the presence of Sr-doped SnS catalyst nanoflowers, 91% of MNZ was degraded. In this experiment, we also studied the photocatalytic activity of pure SnS and Sr-doped SnS nanoparticles under solar radiation. The results are presented in Figure 7. The study confirmed that Sr-doped SnS nanoparticles exhibit significantly higher photocatalytic activity than observed for pure SnS nanoparticles when exposed to sunlight. This remarkable improvement in photocatalytic activity is likely due to the decrease in the energy gap. UV–Vis analysis revealed this decrease, suggesting that the presence of Sr in the material's structure plays a key role in enhancing its ability to catalyze photochemical reactions. These results are promising and could have significant applications in the field of renewable energy production and environmental pollution remediation.
Figure 7

Comparison of SnS and Sr-doped SnS photocatalytic activities under sunlight irradiation (CMNZ = 20 mg/L, Ccatalyst = 1 g/L and free pH).

Figure 7

Comparison of SnS and Sr-doped SnS photocatalytic activities under sunlight irradiation (CMNZ = 20 mg/L, Ccatalyst = 1 g/L and free pH).

Close modal

Radiation source

In a study on the photocatalytic degradation of MNZ using Sr-doped SnS photocatalyst; two different irradiation sources were employed. The first source was an artificial one, which emanated from a PHILPS PL-L 24 W/10/4P UV lamp with a maximum wavelength of 365 nm and an intensity of 18.6 W/m2. The second source was solar UV radiation, which was measured using a Kipp & Zonzn CMP11 global UV radiometer with an intensity of 853 W/m2. The results of the study, as shown in Figure 8, indicate that after 300 min of irradiation, the Sr-doped SnS Photocatalyst was able to degrade 91% of the MNZ under sunlight and 58% under UV lamp irradiation. The high level of MNZ degradation observed under natural sunlight using the Sr-doped SnS Photocatalyst suggests that it could be a promising material for the photocatalytic degradation of MNZ in wastewater treatment applications under natural sunlight.
Figure 8

Comparison of degradation of MNZ exposed to different sources of light (CMNZ = 20 mg/L, Ccatalyst = 1 g/L and free pH = 6, 4).

Figure 8

Comparison of degradation of MNZ exposed to different sources of light (CMNZ = 20 mg/L, Ccatalyst = 1 g/L and free pH = 6, 4).

Close modal

The photocatalyst's ability to breakdown MNZ can be explained by its reaction with light. When the photocatalyst is exposed to light, electrons from the valence band move to the conduction band and holes are created in the valence band. This process generates photons that can reduce oxygen to create superoxide radicals (O2). In addition, the holes in the valence band can oxidize water molecules or (OH) ions to create hydroxyl radicals (OH•). These superoxide and hydroxyl radicals are involved in the breakdown of MNZ drugs. The photogenerated electrons that move to the conduction band are typically unstable and quickly return to the valence band, as has been demonstrated previously (Bouarroudj et al. 2021, 2023).

Effect of pH

The pH of the solution is a crucial factor that affects the rate of degradation of organic compounds in the photocatalytic process, and it is also an important operational parameter in wastewater treatments (Wu et al. 2001; Saien & Soleymani 2007). Figure 9 illustrates the impact of pH on the photocatalytic degradation of MNZ. The results show that the degradation efficiency of MNZ remains relatively stable at pH values between 3 and 6.4. However, the degradation efficiency at a pH value of 10 is significantly lower than those observed at the appropriate pH values. This is likely due to the fact that at high pH values, the MNZ molecules dissociate into their respective ions, which can decrease the interaction between the photocatalyst and the MNZ molecules, thus reducing the degradation efficiency. Therefore, optimizing the pH of the solution is critical to achieving optimal photocatalytic degradation efficiency of MNZ in wastewater treatments. The photocatalytic degradation of MNZ is generally higher at an acidic pH than at a basic pH due to the limited solubility of MNZ in water at high pH. At a basic pH, MNZ can dissociate into ions that are less likely to interact with the photocatalyst. On the other hand, at an acidic pH, MNZ remains primarily in its molecular form, which increases its reactivity with the photocatalyst. Additionally, the production of hydroxyl radicals (OH•) is higher at an acidic pH due to the increased concentration of protons (H+) in the solution, which promotes the photocatalytic degradation of MNZ (Farzadkia et al. 2015; Ayanda et al. 2023).
Figure 9

Sunlight photodegradation of MNZ at different pH values (CMNZ = 20 mg/L and Ccatalyst = 1 g/L).

Figure 9

Sunlight photodegradation of MNZ at different pH values (CMNZ = 20 mg/L and Ccatalyst = 1 g/L).

Close modal

Effect of concentration

The study of the influence of the initial concentration of pollutants on the efficiency of photocatalysis is crucial in determining the optimal conditions for the degradation of pollutants. In this experiment, we investigated the effect of varying the initial concentration of MNZ on the degradation rate of the pollutant using photocatalysis. The experiment was carried out at a free pH of 6.4 and a dose of 1 g of Sr-doped SnS photocatalyst. We monitored the degradation rate of MNZ over a period of 300 min for initial concentrations ranging from 20 to 40 mg/L. The results were plotted on a curve shown in Figure 10, which clearly shows the degradation rate of MNZ decreasing as the initial concentration of the pollutant increases. The findings of the study demonstrate that the degradation of MNZ is significantly affected by the initial concentration of the substrate. The results reveal that the degradation rate of the pollutant is higher when the initial concentration is lower. Specifically, when the initial concentration is at 20 mg/L, the degradation rate is remarkably high and yields about 91% after 300 min of solar irradiation. However, when the initial concentration is increased to 30 and 40 mg/L, the degradation rate decreases from 82 to 76%, respectively. These results suggest that the efficiency of degradation decreases as the pollutant concentrations increase. These findings are consistent with those reported in previous studies, which reinforce the notion that the initial concentration of the pollutant plays a crucial role in the effectiveness of the degradation process (Aoudjit et al. 2021, 2020, 2022; Ghribi et al. 2020). One possible explanation for this phenomenon is that increasing the initial concentration of the pollutant can lead to saturation of the active sites on the photocatalyst, which limits the photocatalyst's ability to degrade the pollutant. In other words, when the initial concentration of the pollutant is too high, there is increased competition for the active sites on the photocatalyst surface, which reduces the efficiency of the photocatalytic degradation. Furthermore, at high pollutant concentrations, there may be formation of intermediate products that can inhibit the photocatalytic degradation reaction. These intermediate products can adsorb onto the photocatalyst surface and block the active sites, thereby reducing the degradation efficiency. Moreover, the inner filtration effect occurs when the concentration of MNZ increases in a photocatalytic system, leading to a higher likelihood of UV light being absorbed by the MNZ molecules before reaching the photocatalyst surface. This results in a reduction in the number of photons that can reach the photocatalyst, potentially decreasing the efficiency of the photocatalytic process (Chatzitakis et al. 2008; Palominos et al. 2009; Wang et al. 2010; Prados-Joya et al. 2011; Farzadkia et al. 2015).
Figure 10

Photodegradation of MNZ with time at, different concentrations of MNZ, under sunlight irradiation (Ccatalyst = 1 g/L and free pH = 6, 4).

Figure 10

Photodegradation of MNZ with time at, different concentrations of MNZ, under sunlight irradiation (Ccatalyst = 1 g/L and free pH = 6, 4).

Close modal

Effect of catalyst dose

In order to determine the ideal amount of catalyst for achieving maximum photocatalytic degradation, a range of catalyst amounts were tested, varying from 0.1 to 1 g/L. The concentration of MNZ used in the experiment was held constant at 20 mg/L. The results of this investigation are displayed in Figure 11.
Figure 11

Photodegradation of MNZ at different doses of Sr-doped SnS catalyst, under sunlight irradiation (CMNZ = 20 mg/L and free pH = 6.4).

Figure 11

Photodegradation of MNZ at different doses of Sr-doped SnS catalyst, under sunlight irradiation (CMNZ = 20 mg/L and free pH = 6.4).

Close modal

The experimental results clearly demonstrate a positive correlation between the quantity of catalyst used and the rate of degradation of MNZ. The rate of degradation increased in proportion to the quantity of the catalyst used, with a yield of 91% after 300 min when a 1 g/L catalyst dose was utilized. This suggests that the yield of the photodegradation process is directly proportional to the amount of catalyst used. One possible explanation for this phenomenon is that the increase in active sites available for the production of OH free radicals is responsible for the degradation of MNZ. Thus, using higher quantities of catalyst could result in more efficient and effective degradation of MNZ in wastewater treatment. However, excessive formation of free radicals can occur if the dose of photocatalyst is too high. This excessive formation of free radicals can combine and react with other species present in the solution, thereby reducing their effectiveness in degrading MNZ (Kaur & Singhal 2014; Farzadkia et al. 2015; Kumar & Kumar 2019; Bouarroudj et al. 2023).

Reuse of photocatalyst

In order to ensure that a photocatalyst is economically feasible, it is important that it is stable and can be reused for multiple cycles. To test this, several experiments were conducted using the Sr-doped SnS catalyst for the degradation of MNZ. The recovered catalyst was used for four cycles, with an adsorption time of 300 min followed by photocatalysis at optimum conditions. The results, as shown in Figure 12, indicate that even after repeated cycles, the catalyst remained active with only a slight decrease in MNZ degradation, from 91 to 83% after a repeated cycle. This demonstrates the potential for the synthesized photocatalyst to be both effective and economically viable for use in environmental remediation processes.
Figure 12

Photodegradation of MNZ over four catalytic cycles in sunlight, (20 mg/L, free pH = 6.4, and Ccatalyst = 1 g/L).

Figure 12

Photodegradation of MNZ over four catalytic cycles in sunlight, (20 mg/L, free pH = 6.4, and Ccatalyst = 1 g/L).

Close modal

It is possible that the efficiency of photocatalytic degradation decreases at 82% after several cycles of use, particularly after the fourth cycle of reuse. This decrease can be caused by several factors, such as the accumulation of contaminants on the surface of the catalyst, the physical or chemical deterioration of the catalyst, and the loss of active surface area of the catalyst. Organic contaminants can accumulate on the surface of the catalyst, reducing its efficiency, despite cleaning between use cycles. Additionally, the catalyst can undergo physical or chemical degradation over time, which can also reduce its efficiency. Finally, the active surface area of the catalyst can decrease due to the formation of passive layers or a decrease in specific surface area, which can also reduce the efficiency of degradation (Chakrabarti & Dutta 2004; Yu et al. 2016; Anjum et al. 2017; Zhao et al. 2018).

In conclusion, the synthesis of strontium-doped SnS nanoflowers using the solvothermal method has been successfully achieved. The structural analysis confirmed the successful substitution of Sr2+ ions into the SnS host lattice, resulting in a decrease in lattice parameter and a slight shift in diffraction peaks. Furthermore, the UV–Vis investigations revealed an increased band gap of Sr-doped SnS, with an estimated value of 1.48 eV, indicating improved photocatalytic properties.

The photocatalytic abilities of Sr-doped SnS were assessed through the degradation of MNZ under natural sunlight. The results demonstrated that the optimal conditions for MNZ degradation were a free pH of 6.4, a dye concentration of 20 mg/L, and a catalyst dose of 1 g/L. Remarkably, the Sr-doped SnS catalyst exhibited an impressive degradation efficiency, with 91% degradation of MNZ achieved under natural sunlight irradiation. Importantly, the catalyst maintained its photodegradation capacity even after multiple treatment cycles, highlighting its stability and reusability.

These findings contribute to the growing body of knowledge on the synthesis and characterization of doped semiconductor nanomaterials for environmental applications. The successful synthesis of strontium-doped SnS nanoflowers with enhanced photocatalytic properties opens up possibilities for their use in various fields, including wastewater treatment and environmental remediation. Further research and optimization of the synthesis process can lead to the development of even more efficient and sustainable photocatalytic materials for addressing environmental challenges.

The authors of this manuscript would like to thank the General Directorate for Scientific Research and Technological Development (DGRSDT) and the Ministry of Higher Education and Scientific Research (MESRS), Algeria, for funding this project.

All relevant data are included in the paper or its Supplementary Information.

The authors declare there is no conflict.

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