In this paper, a novel efficient photo-catalyst have been fabricated by hybridizing ZnIn2S4 and S-C3N4 through hydrothermal method. The SEM and HRTEM images, together with XPS analysis revealed that the combination of ZnIn2S4 and S-C3N4 was successful and the structure of ZnIn2S4 was well preserved, which played a crucial role for improving the photocatalytic performance. The optimum 18% ZnIn2S4/S-C3N4 nanocomposites exhibit dramatically enhanced photocatalytic performance for degradation of tetracycline with 86.3% removal rate within 120 minute, higher than 50% degradation efficiency of pure S-C3N4. The corresponding enhanced mechanism for 18% ZnIn2S4/S-C3N4 can be attributed to the effective interfacial electron-hole pairs separation and migration between ZnIn2S4 and S-C3N4. And in the process of photodegradation for tetracycline, the largest contribution rate is the photo-excited cavity (h+), followed by ∙O2− and ·OH. Herein, we have provided a good example for removing antibiotic residues by using S-C3N4 based heterojunction towards environmental remediation.
Research Article
Constructed a novel of Znln2S4/S-C3N4 heterogeneous catalyst for efficient photodegradation of tetracycline
https://doi.org/10.21203/rs.3.rs-2951958/v1
This work is licensed under a CC BY 4.0 License
Journal Publication
published 07 Oct, 2023
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ZnIn2S4
S-C3N4
heterojunction
photodegradation
environmental remediation
With the global scale increasing quantity of antibiotics in the last two decades, many antibiotic residues have been found in our surroundings, liking in groundwater, surface water and even in daily fruits and milk, which has raised seriously threaten to human health (Elmolla and Chaudhuri 2009; Khan et al. 2010; Murphy et al. 2012). Even though various traditional strategies including physical or chemical absorption, biological treatment, etc. have been employed to eliminate antibiotic contamination for many years. However, the absorption method can only separate antibiotics from the polluted environment rather than thoroughly decomposed them (Chen et al. 2021). And the biological treatment cannot be an efficiently way to completely remove the antibiotic residues owing to their antimicrobial properties (Guo et al. 2017). In contrast, photocatalytical degradation is an attractive option because of its high efficiency, low-cost and friendly environment (Long et al. 2020; Wang et al. 2023).
Among the photocatalysts explored so far, g-C3N4, a non-metal semiconductor photocatalyst have been extensively investigated due to its significant advantages like less toxic, cost-free, narrow bandgap and stability (Kuldeep et al. 2021). Nevertheless, some inherent vice of g-C3N4, like small specific surface area, quick recombination of electric charge and low absorption in visible region, have significantly limited its practical utilization (Chen et al. 2009). To overcoming these obstacles, various of efforts have been tried. Among various previously reported strategies, heterojunction can guarantee the effective detachment of e−-h+ and generate great redox potential (Cai et al. 2022). Therefore the construction of heterojunction has been ranked as an efficient method to enhance its photolysis efficiency. For instance, BiOI/C3N4 (Liu et al. 2022), ZnS/C3N4 (Kim et al. 2017) and CdS/C3N4 (Cao et al. 2022) and Bi2O3/biochar/C3N4/ (Huang et al. 2023), have been exhibited high photocatalytic activity and drove the photodegradation efficiency of tetracycline to reach 86.7%. Another efficient method is the element doping strategy, such as Fe/C3N4 (Tonda et al. 2014), Co/C3N4 (Zhang et al. 2014)d C3N4 (Li et al. 2012), can be regarded as a simple and feasible way to enhance catalytic efficiency. Among the doped elements, S-doping is also a significant method, which can result in the charge density redistribution and improve the light absorption property of C3N4 (Zhang et al. 2019; Jiang et al. 2016). In 2010, Liu et al. synthesized S doped C3N4 using hydrothermal method, which showed high efficient photo-reactivity in the field of photocatalysis (2010). Since then, many excellent researches have been reported. For instance, Shcherban et al. (2016) discovered that the sulfur-doped C3N4 by pyrolysis of melamine and sulfuric acid exhibited high photo-catalytic activity towards reduction of CO2 with water vapor. Long et al. (2020) prepared cavernous S-C3N4 nanoparticles with a narrow band gap 2.57 eV through polymerizing urea and 2-thiobarbituric acid. The obtained photocatalyst has a superior photocatalytic H2 evolution from water splitting. Very recently, a novel core-shell constructive catalyst S-g-C3N4@P123 has been developed, which showed good oxygen reduction reaction (ORR ) persistence, dramatic tolerance to methanol, and large-capability as the cathode of Zn-air cell (Ding et al. 2022).
Znln2S4, as an important ternary chalcogenide catalyst, has been drawn extensive attention due to its superior optical characteristics, excellent chemical stability and appropriate redox potentials (Pascale et al. 1989). However, Znln2S4 itself also has two major deficiencies. One is the rapid integration of photo-induced carriers, and another is the narrow response range of light absorption (Chao et al. 2019; Bo et al. 2017; Li et al. 2020).
At present, building a heterojunction between Znln2S4 and other semiconductors has been considered as a promising solution. Many heterojunctions with excellent photocatalytic activity, such as WO3/Znln2S4 (Tang et al. 2020), Znln2S4/rGO (Dang and Zhao 2021), ZnO/Znln2S4 (Xu et al. 2022) and Sb2S3/Znln2S4 (Xiao et al. 2022) have been prepared. Compared with the pure Znln2S4, the luminous absorption and separating capacity of photo-induced carriers can be improved significantly. According to previous literature, few research has been reported on Znln2S4/S-C3N4 heterojunction, especially on photocatalytic degradation.
Based on the above discuss, we have supposed that if S doped g-C3N4 and Znln2S4 are hybridized together, might be a wonderful strategy to overcome the inherent defects of C3N4 and Znln2S4 described above (Jourshabani et al. 2018). Hence, we have designed and synthesized an amount of Znln2S4/S-C3N4 p-n heterojunction photocatalysts by hydrothermal method, which display a remarkable photo-degradation ability for tetracycline. This work may offer some ideas for constructing the other highly efficient heterojunction photocatalysts towards antibiotic residues contaminant.
2.1. Materials
2-thiobarbituric acid (98%), urine (99%), InCl3·4H2O (98%), ZnCl2 (98%), Thioacetamide (99%) and all other materials used in this work were supplied by Aladdin Chemical Co. Ltd.
2.2 Sample manufacture
2.2.1 Synthesis of S doped g-C3N4
The S doped g-C3N4 (S-C3N4) was synthesized through polycondensation method by using urea and 2-thiobarbituric acid as precursor (Long et al. 2020). First, 10 g urine and 0.03 g 2-thiobarbituric acid were dispersed in 10 mL 50% ethanol, stirring 20 min. Then, evaporating the solution to obtain the white complex which was calcinated at 550°C for 2 h under N2 protected to obtain S-C3N4. After that, the product was collected for further using.
2.2.2 Synthesis of Znln2S4/S-C3N4 catalysts
A series of Znln2S4/S-C3N4 (donated as ZSC) catalysts with various mass proportion were synthesized according to the rout shown in Scheme 1. As 36 wt.% Znln2S4/S-C3N4 (36% ZSC) for example, firstly, 0.3 g S-C3N4 was inputted into 40 mL non-ion water and sonicated 30 min. Second, ZnCl2 (0.16g), InCl3·4H2O (0.35g) and thioacetamide (0.18g) were resolved in a beaker with 100 mL non-ion water, adjusting the pH to 2.5 by hydrochloric acid. Then, the S-C3N4 suspension was drop-wisely instilled into the later mixture and vigorously agitated about 1 h. Subsequently, the composition was heated to 160 °C for 16 h to obtain 36% ZSC, which was rinsed three times by EtOH and H2O, and finally desiccated in an oven at 60 °C for about 6 h. According to the same steps, different amount of ZnIn2S4 (3 ~ 18wt.%) was loaded with S-C3N4 to obtained 3% ZSC, 9% ZSC and 18% ZSC. The raw Znln2S4 was prepared under the same process without adding S-C3N4.
2.3 Samples characterizations
XRD: Shimadzu corporation (Japan), the range of 2θ = 20–80°C. SEM: JSM-6700F, JEOL FE-SEM instrument. TEM: FEI Tecnai G2 F20 with 200KV operating voltage. XPS: Thermo ESCALAB 250 using Al Kα X-ray (E = 1486.2 eV). FR-IR Spectrometer: Nicollet 170SX with KBr pellets. The photoluminescence (PL) spectra: Fluorolog-TCSPC Luminescence spectrometer. UV/Vis absorption spectrometer: UV-1800 PC (SHIMADZU). Diffused reflectance spectra (DRS): Varian cary 500 UV-vis spectrometer. Electrochemical analysis: CHI 660b workstation with three-electrode quartz cells. Electron spin resonance (ESR): JES FA200 (JEOL) spectrometer, using DMPO as the trapping molecular for radical.
2.4 Photolysis performance
The photolysis performances of ZSC photocatalyst for tetracycline (TC) were evaluated in a quartz photo-reactor under a high-pressure Xe lamp (300 W) at room temperature. Firstly, 30 mg ZSC was dispersed in TC aqueous solution (20 mg/L). Pre irradiation, the suspension was mixed for 30 min to reach an absorption-desorption equilibrium. Then, at each 20 min intervals, 3 mL aliquots were extracted and monitored on a UV spectrophotometer to detect the degradation rates of TC.
2.5 Active species capturing
For better understanding the photocatalytic degradation mechanism of ZSC, tetracycline was used as an example to conduct the active radicals trapping experiments. 1mmol/L scavenger like EDTA (disodium ethylenediaminetetraacetate), IPA (isopropanol) and BQ (1,4-benzoquinone) were used severally to catch light-induced h+, ·OH and ⋅O2− (He et al. 2019). In addition, the electron spin resonance (ESR) was applied to further assay the existence of h+ and ⋅O2− radicals in the photodegradation system. 1mg photocatalyst was dispersed to 0.1mol/L DMPO solvent to determine the exist of superoxide radicals (DMPO-⋅O2−) and free h+ respectively.
Firstly, the Infrared spectrum of S-C3N4, ZnIn2S4 and ZSC are described in Fig. 1a. The main characteristic absorption bands of 9% ZSC and 18% ZSC are similar with those of S-C3N4. The angular peak at 812 cm− 1 is attributed to the out-of-plane bending vibration of C-H, which is related to the triazine structure in S-C3N4. And 1628 and 1244 cm− 1 are the characteristic stretching vibrations of C = C double bonds in aromatic rings (Wang et al. 2009). However, due to the ZnIn2S4 is an inorganic compound with no significant infrared characteristic peaks, herein, the absorption bands of ZSC cannot reveal the existence of ZnIn2S4. Therefore, further analysis and detection are needed.
The elemental composition and valence conditions of 18% ZSC was disclosed by X-ray photoelectron spectroscopy (XPS). As shown in the XPS survey spectrum (Fig. 2a), the main element are C, N, S, In and Zn, which explains the hybrid of ZnIn2S4 with S-C3N4 was successful. For C 1s Fig. 2b, two main signals centered at 281.0 and 284.1 eV were related to = C of graphite and C = N units in triazine skeleton, respectively (Jiang et al. 2015). The N 1s Fig. 2c (394.8, 399.9 and 403.0 eV) was fitted with N-C, N-Hx and N = C, respectively (Zhang et al. 2016). Correspondingly, 166.0 eV in Fig. 2d (S 2p) were ascribed to S 2p1/2. 449.7 and 457.2 eV in Fig. 2e (In 3d) were associated with In 3d5/2 and In 3d3/2. For Zn 2p spectra, main peaks located at 1027.2 and 1050.3 eV (Fig. 2f) corresponds to Zn 2p3/2 and 2p1/2. Noteworthy, the bonding power of each element in ZnIn2S4 were consistent with those reported in the references, which demonstrated ZnIn2S4 is hybridized with S-C3N4 successfully (Shi et al. 2015).
For better analyzing the microstructure of ZSC sample, the TEM and HRTEM were employed in Fig. 4a and 4b. As shown in Fig. 4a, the darker nanosheets can be attributed to ZnIn2S4, while the lighter part correlated to S-C3N4 (Guo et al. 2017). The HRTEM in Fig. 4b revealed the crystal-line with an planar spacing of 0.32 and 0.40 nm, corresponding to the (006) and (102) peak of ZnIn2S4 (Guo et al. 2017). In addition, the boundary conjugated by Znln2S4 and S-C3N4 can also be seen clearly from Fig. 4b. In Fig. 4c, the EDS elemental mapping clearly verifies that the element composition of ZSC are unanimous with the result of XPS, including C, N, Zn, In and S respectively. Moreover, form Fig. 4d-h, it can be seen that distribution of all the elements are homogeneous and the position of each unit conforms to the composite. All these phenomena illustrated that the combination of ZnIn2S4 and S-C3N4 was successful and the structure of ZnIn2S4 was well preserved, which played a crucial role for improving the photocatalytic performance of ZSC.
3.2. Photocatalytic performance
The photocatalytic efficiency of different ratio of ZSC heterojunctions were evaluated by using tetracycline hydrochloride (TC, 20 mg/L, 30 mL) as pharmaceutical residue and irradiating with visible light (Fig. 5a). Firstly, the blank control trial showed that TC solvent is stable under the visible light. Without photocatalyst ZSC, only 12.6% self-degradation rate can be neglected. Secondly, compared with pure S-C3N4 samples, the ZSC composites show remarkably increased photocatalytic activities to degrading the tetracycline, indicating the formation of ZSC heterojunction is an efficient solution to upgrade the photo-catalysis level of S-C3N4. The highest photocatalytic efficiency is belongs to the 18% ZSC, which can remove 86.3% TC within 120 minute, higher than 50% degradation efficiency of pure S-C3N4. Furthermore, the ln(C/C0) curve exhibits a good linear relationship (Fig. 5b), illustrating that the photoinduced degradation of TC solution catalyzed by ZSC conforms to the first-order dynamic model. In addition, the time variation of tetracycline concentration (Fig. 5c) can directly prove that TC molecules were decomposed irradiating by visible light in the presence of 18% ZSC. With the extension of light irradiation, the absorption intensity of tetracycline hydrochloride at 370 nm drastically decreased and blue shift occurred. For further survey the application prospect of ZSC, the stability of this heterojunction under the photolysis of TC was also evaluated. As illustrated in Fig. 5d, after three successive runs, the degradation efficiency of TC with 18% ZSC can still be remained above 80%. Even recycle five times, the degradability of TC was still remained at 73.4%. These experimental data show that the as-constructed 18% ZSC possesses fine stability and potential utilization for eliminating antibiotics contaminants.
3.3. Photocatalytic mechanism analysis
To deeply understand the activity of composite photocatalyst 18% ZSC under visible light, some experiments like UV-vis/DRS, PL emission, photo-electrochemical, ESR properties are carried out to assess the charge carrier dissociation and transfer rate of the composites S-C3N4, ZnIn2S4 and 18% ZSC.
In Fig. 6a, it is obvious that the absorbed boundary of S-C3N4 is about 475 nm, slightly higher than 460 nm of pure C3N4, because of the doping effect of S (Long et al. 2020). Compared with S-C3N4, the ZnIn2S4 as a semiconductor with UV-visible light response offers a wide absorption (300–500 nm), with an absorption boundary around 570 nm, although the intensity of absorption peak is not as high as S-C3N4 in the ultraviolet region. Notably, when incorporation of ZnIn2S4 within S-C3N4, the obtained absorption spectra exhibit all the characteristics of ZnIn2S4 and S-C3N4. The optical absorption almost covers the entire spectral range. And although the intensity of absorption in 450–800 nm is not stronger than ZnIn2S4 and S-C3N4, the absorbed boundary of composite displays a significant red-shift to 650 nm, which is benefit to improve the utilization of visible light for photocatalysts.
Generally, the fluorescence intensity is related to the re-compounding of charge carriers. Therefore, photoluminescence (PL) spectrum of ZnIn2S4, S-C3N4 and 18% ZSC were investigated and displayed in Fig. 6b. Obviously, ZnIn2S4 has a strong absorption band in a broad spectral range from 400 to 600 nm. In case of S–C3N4, a weaker emission peak centered at 475 nm is observed, which is consistent with the previous literature reported (Shi et al. 2014). For 18% ZSC, the PL peak is much weaker than ZnIn2S4 and S-C3N4, which alludes that the synergetic effect is occurred between the two semiconductors. It suggests that the recombination rate of photogenerated carries has been inhibited significantly, which is a reasonable explanation for the improvement of photocatalytic efficiency of 18% ZSC. In addition, this result is further validated by photocurrent time curves in Fig. 6c. In comparison to ZnIn2S4 and S-C3N4, the 18% ZSC heterojunctions emerge a remarkable increased photocurrent, illustrating the 18% ZSC heterojunctions can act as the effective mediators for promoting photoinduced electron-hole pairs separation and diffusion. Simultaneously, the electrochemical impedance spectroscopy (EIS) of 18% ZSC, ZnIn2S4 and S-C3N4 are delineated in Fig. 6d. The much smaller arc size of 18% ZSC discloses the resistance of photoinduced electron-hole pairs migration within the 18% ZSC electrode is much lower than ZnIn2S4 and S-C3N4 electrodes. All these above experimental results are consistent with the most efficient photodegradation effect of 18% ZSC, originated from the more effective charge carrier partition and electron transport between S-C3N4 and ZnIn2S4.
To further expose the photocatalytic mechanism of 18% ZSC, radical trapping experiments are conducted to reveal the primary active components in photodegradation. In Fig. 7a, it can be illustrated that the degradability of TC is reduced obviously to 10.4% after adding EDTA-2Na, demonstrating that the photo-excited cavity (h+) plays a vital effect in the degradation of TC. In addition, adding BQ directly results the elimination to 50.9%, revealing that ⋅O2− also contribute greatly to photodegradation. After adding IPA, the eliminated efficiency of TC slightly decreases to 77.2%, indicating that ·OH species has slight affected on the photolysis of TC. In short, the order of contribution to degradation efficiency is h+ > ⋅O2− > ·OH. To further verify the contribution rate of ·OH to degradation, we designed the fluorescence experiment to detect ·OH, according to the principle that p-phthalic acid can react on ·OH to generate some strong fluorescent substances. In Fig. 7b, we find a weak fluorescence peak at 430 nm in absence of photocatalyst, illustrating that the content of ·OH was very small before photodegradation. After adding catalyst, as shown in Fig. 7c, although strong fluorescence absorption peaks appeared at 340 nm and 370 nm, there was no characteristic fluorescence absorption at 430 nm, possibly due to the appearance of another strong fluorescent substance in the reaction system. This is in agreement with the result of trapping test, suggesting that ·OH is not the primary active components for TC photolysis catalyzed by 18% ZSC.
Moreover, the ESR trapping experiment were used to evaluate the efficiency of superoxide anion (⋅O2−) and photo-excited cavity (h+) in the TC degradation. In Fig. 7d, the characteristic absorption of DMPO-⋅O2− components appeared under visible light cannot be detected in the dark. By contrast, as in Fig. 7e, the peaks of h+ with same intensity can be seen either under visible light or in dark. This results further confirm that photo-excited cavity is the crucial active components in the TC photocatalysis, which is in concordance with the experiment data obtained from the radical capture experiments above.
To further estimate the photocatalytic degradation mechanism of ZSC, the band gaps and VB-XPS of catalysts were tested and exposed at Fig. 8. As shown in Fig. 8a and b, the bandgap width of the ZnIn2S4 and S-C3N4 were measured individually to be 2.46 and 2.68 eV. In Fig. 8c and d, the valence band potential of S-C3N4 and ZnIn2S4 were 1.85 and 1.37 V. Based on the band gap and valence band potential obtained above, the conduction band potential of ZnIn2S4 and S-C3N4 can be calculated as -1.09 and − 0.83 V, respectively.
According to the data required before, the possible photocatalysis principle of ZSC composites is proposed in Fig. 9. With the compact hetero-interface and well-matched band structure, a local field electric filed would be established between S-C3N4 and ZnIn2S4, which leading to the remarkably accelerating the segregation of charge (e−) -cavity (h+) pairs. When irradiated through visible spectrum, the electronics on the valence band of ZnIn2S4 is motivated to its conduction band, and then transferred to the conduction band of S-C3N4. In the meantime, the h+ is transferred from the valence band of S-C3N4 to ZnIn2S4. This process conforms to the charge transfer mechanism of type II heterojunction. Such rapid segregation of charge-cavity pairs would lead to the accumulation of h+ in VB of ZnIn2S4 and form the oxidation centers. Meanwhile, the electronics would be stored in conduction band of S-C3N4 to become reduction sites. All these would significantly decrease the reassociation of electronic charge-cavity pairs, and upgrade the photocatalysis effect. Because the conduction band potential of S-C3N4 is more negative than O2/∙O2− couple (-0.33 V), the electrons of S-C3N4 can better react with O2 to form ∙O2−, which can be partially converted to ∙OH (He et al. 2022), then degrade tetracycline. In addition, the oxidation voltage of ∙OH/OH− (1.99 V) and ∙OH/H2O (2.68 V) are more positive than the VB of S-C3N4 (1.87 V) and Znln2S4 (1.37 V). So the ∙OH radicals cannot be produced directly either from OH− or H2O by oxidation reaction. Considering the continuous accumulation of h+ at the heterointerface, which can directly oxide the pollutants, as well as partially consumed ∙O2−, it can be sure that the forming amount of these radicals in the photodegradation of tetracycline is: h+> ⋅O2− > ·OH. These was unanimous with the results of actives species detection experiments.
In conclusion, we have designed and synthesized the binary heterojunction ZSC. The photocatalysis efficiency was assessed by degrading TC. And the optimized 18% ZSC composites displays the most efficient photodegradation activity for the elimination of TC, which was 1.7 times than that of net S-C3N4 (50%). Most importantly, the 18% ZSC heterojunctions retains high stability and has 73.4% catalytic efficiency after five cycles, being critical for practical applications. We hope this work can offer some ideas for designing more efficient photocatalysts to remove the contaminant in wastewater.
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This manuscript does not contain studies with human or animal subjects. So ethical approval is not applicable for this manuscript.
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Author Contributions
All authors contributed to the study conception and design. Material preparation, data collection, and analysis were performed by Qian Yang, Xueting Wang, Jing Shi, Jia Qi, Yangqing He. The first draft of the manuscript was written by Qian Yang and Yangqing He, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.
Funding
This work was supported by “Key Industry Innovation Chain of Shaanxi” (Grant numbers: 2023-ZDLSF-06).
Competing Interests
All authors have no relevant financial interests or non-financial interests to disclose.
Availability of data and materials
The data that support the findings of this manuscript are available from the corresponding authors, [Qian Yang], upon reasonable request.
- Battula VR, Kumar S, Chauhan DK, Samanta S, Kailasam K (2019) A true oxygen-linked heptazine based polymer for efficient hydrogen evolution. Appl Catal B Environ 244:313–319. http://dx.doi.org/10.1016/j.apcatb.2018.11.027
- Bo L, He K, Tan N, Gao B, Feng Q, Liu J, Wang L (2017) Photocatalytic oxidation of trace carbamazepine in aqueous solution by visible-light-driven Znln2S4: performance and mechanism. J Environ Manag 190:259–265. https://doi.org/10.1016/j.jenvman.2016.12.050
- Cai MJ, Wang CC, Liu YP, Yan RY, Li SJ (2022) Boosted photocatalytic antibiotic degradation performance of Cd0.5Zn0.5S/carbon dots/Bi2WO6 S-scheme heterojunction with carbon dots as the electron bridge. Sep Purif Technol 300:121892. https://doi.org/10.1016/j.seppur.2022.121892
- Cao LG, Zheng ZS, Liu Y, Li ZQ, Li YL (2022) Special sea urchin-like CdS/g-C3N4 photocatalyst with high specific surface area and efficient charge separation. J Mater Sci 57:17609–17621. https://doi.org/10.1007/s10853-022-07752-1
- Chao Y, Li Q, Xia Y, Kangle Lv (2019) Enhanced visible-light photocatalytic CO2 reduction performance of Znln2S4 microspheres by using CeO2 as cocatalyst. Appl Surf Sci 464:388–395. https://doi.org/10.1016/j.apsusc.2018.09.099
- Chen G, Yu Y, Liang L, Duan X, Li R, Lu X, Yan B, Li N, Wang S (2021) Remediation of antibiotic wastewater by coupled photocatalytic and persulfate oxidation system: a critical review. J Hazard Mater 408:124461. https://doi.org/10.1016/j.jhazmat.2020.124461
- Chen X, Jun YS, Takanabe K, Maeda K, Domen K, Fu X, Antonietti M, Wang X (2009) Ordered mesoporous SBA-15 type graphitic carbon nitride: a semiconductor host structure for photocatalytic hydrogen evolution with visible light. Chem Mater 21:4093–4095. https://doi.org/10.1021/cm902130z
- Dang XM, Zhao HM (2021) Signal amplifified sandwich-type photoelectrochemical sensing assay based on rGO-Znln2S4 functionalized Au–WO3 IOPCs Z-scheme heterojunction. Electrochim Acta 365:137382. https://doi.org/10.1016/j.electacta.2020.137382
- Ding XB, Li F, Cao QC, Wu H, Qin YH, Yang L, Wang TL, Zheng XT, Wang CW (2022) Core-shell S-doped g-C3N4@P123 derived N and S co-doped carbon as metal-free electrocatalysts highly efficient for oxygen reduction reaction. Chem Eng J 429:132469. https://doi.org/10.1016/j.cej.2021.132469
- Elmolla E, Chaudhuri M (2009) Optimization of fenton process for treatment of amoxicillin, ampicillin and cloxacillin antibiotics in aqueous solution. J Hazard Mater 170:666–672. https://doi.org/10.1016/j.jhazmat.2009.05.013
- Guo F, Cai Y, Guan WS, Huang H, Liu Y (2017) Graphite carbon nitride/ZnIn2S4 heterojunction photocatalyst with enhanced photocatalytic performance for degradation of tetracycline under visible light irradiation. J Phys Chem Solids 110:370–378. https://doi.org/10.1016/j.jpcs.2017.07.001
- Guo F, Cai Y, Guan WS, Shi W (2017) Ag3PO4 nanoparticles decorated on sheet-on-sheet structured g-C3N4/ZnIn2S4 for enhanced photocatalytic activity. Mater Lett 201:62–65. https://doi.org/10.1016/j.matlet.2017.04.142
- He H, Cao J, Guo MN, Lin HL, Zhang JF, Chen Y, Chen SF (2019) Distinctive ternary CdS/Ni2P/g-C3N4 composite for overall water splitting: Ni2P accelerating separation of photocarriers. Appl Catal B Environ 249:246–256. https://doi.org/10.1016/j.apcatb.2019.02.055
- He YQ, Huang ZR, Ma ZY, Yao BH, Liu HY, Hu LL, Zhao Q, Yang Q, Liu DJ, Du DG (2019) Highly efficient photocatalytic performance and mechanism of α-ZnTcPc/g-C3N4 composites for methylene blue and tetracycline degradation under visible light irradiation. Appl Surf Sci 498:143834. https://doi:10.1016/j.apsusc.2019.143834
- He YQ, Ma B, Yang Q, Tong Y, Ma ZY, Junior LB, Yao BH (2022) Surface construction of a novel metal-free g-C3N4-based heterojunction photocatalyst for the efficient removal of bio-toxic antibiotic residues. Appl Surf Sci 571:151299. https://doi.org/10.1016/j.apsusc.2021.151299
- Huang LJ, Liu H, Wang Y, Zhang TC, Yuan SJ (2023) Construction of ternary Bi2O3/biochar/g-C3N4 heterojunction to accelerate photoinduced carrier separation for enhanced tetracycline photodegradation. Appl Surf Sci 616:156509. https://doi.org/10.1016/j.apsusc.2023.156509
- Jiang D, Li J, Xing C, Zhang Z, Meng S, Chen M (2015) Two-dimensional CaIn2S4/g-C3N4 heterojunction nanocomposite with enhanced visible-light photocatalytic activities: interfacial engineering and mechanism insight. ACS Appl Mater Inter 7(34):19234–19242. https://doi.org/10.1021/acsami.5b05118
- Jiang T, Wang Y, Wang K, Liang Y, Wu D, Tsiakaras P, Song S (2016) A novel sulfur-nitrogen dual doped ordered mesoporous carbon electrocatalyst for efficient oxygen reduction reaction. Appl Catal B-Environ 189:1–11. https://doi.org/10.1016/j.apcatb.2016.02.009
- Jourshabani M, Shariatinia Z, Badiei A (2018) High efficiency visible-light-driven Fe2O3-xSx/S-doped g-C3N4 heterojunction photocatalysts: direct Z-scheme mechanism. J Mater Sci Technol 34:1511–1525. https://doi.org/10.1016/j.jmst.2017.12.020
- Khan MH, Bae H, Jung JY (2010) Tetracycline degradation by ozonation in the aqueous phase: proposed degradation intermediates and pathway. J Hazard Mater 181:659–665. https://doi.org/10.1016/j.jhazmat.2010.05.063
- Kim WJ, Jang EY, Park TJ (2017) Enhanced visible-light photocatalytic activity of ZnS/g-C3N4 type-II heterojunction nanocomposites synthesized with atomic layer deposition. Appl Surf Sci 419:159–164. https://doi.org/10.1016/j.apsusc.2017.05.012
- Kuldeep AR, Dhabbe RS, Garadkar KM (2021) Development of g-C3N4-TiO2 visible active hybrid photocatalyst for the photodegradation of methyl orange. Res Chem Intermediat 47:5155–5174. https://doi.org/10.1007/s11164-021-04561-0
- Li C, Che H, Huo P, Yan Y, Liu C (2020) Confinement of ultrasmall CoFe2O4 nanoparticles in hierarchical ZnIn2S4microspheres with enhanced interfacial charge separation for photocatalytic H2 evolution. J Colloid Interface Sci 581:764–773. https://doi.org/10.1016/j.jcis.2020.08.019
- Li J, Shen B, Hong Z, Lin B, Gao B, Chen Y (2012) A facile approach to synthesize novel oxygen-doped g-C3N4 with superior visible-light photoreactivity. Chem Commun 4:12017–12019. https://doi.org/10.1039/C2CC35862J
- Liu G, Niu P, Sun CH, Smith SC, Chen ZG, Lu GQ, Cheng HM (2010) Unique electronic structure induced high photoreactivity of sulfur-doped graphitic C3N4. J Am Chem 132:11642–11648. http://doi.org/10.1021/ja103798k
- Liu H, Hun WC, Zhang TC, Ouyang L, Yuan SJ (2022) Photocatalytic removal of tetracycline by a Z-scheme heterojunction of bismuth oxyiodide/exfoliated g-C3N4: performance, mechanism, and degradation pathway. Mater Toady Chem 23:100729. https://doi.org/10.1016/j.mtchem.2021.100729
- Liu XM, Yang SQ, Yang F, Zhang YC, Yan LS, Li KX, Guo HQ, Yan JJ, Lin J (2022) Construction of Au/g-C3N4/ZnIn2S4 plasma photocatalyst heterojunction composite with 3D hierarchical microarchitecture for visible-light-driven hydrogen production. Int. J. Hydrogy 2022, 47: 2900–2913.https://doi.org/10.1016/j.ijhydene.2021.10.203
- Long D, Wang L, Cai HY, Bao X, Zhang YP (2020) Sulfur doped carbon–rich g–C3N4 for enhanced photocatalytic H2 evolution: morphology and crystallinity effect. Catal Lett 150:2487–2496. https://doi.org/10.1007/s10562-020-03156-5
- Long ZQ, Li QG, Wei T, Zhang GG, Ren ZJ (2020) Historical development and prospects of photocatalysts for pollutant removal in water. J Hazard Mater 395:122599. https://doi.org/10.1016/j.jhazmat.2020.122599
- Murphy S, Saurel C, Morrissey A, Tobin J, OelgemÖller M, Nolan K (2012) Photocatalytic activity of a porphyrin/TiO2 composite in the degradation of pharmaceuticals. Appl Catal B Environ 120:156–165. https://doi.org/10.1016/j.apcatb.2012.02.027
- Pascale T, Marinelli M, Meloni F (1989) Structural and electronic properties of the layer semiconductor Znln2S4. J Chim Phys 86:847–852. https://doi.org/10.1051/jcp/1989860847
- Shcherban ND, Filonenko SM, Ovcharov ML, Mishura AM, Skoryk MA, Aho A, Murzin DY (2016) Simple method for preparing of sulfur–doped graphitic carbon nitride with superior activity in CO2 photoreduction. ChemistrySelect 1:4987–4993. https://doi.org/10.1002/slct.201601283
- Shi F, Chen L, Chen M, jiang D (2015) Ag-C3N4/nanocarbon/ZnIn2S4 nanocomposite: an artificial Z-scheme visible-light photocatalytic system using nanocarbon as the electron mediator. Chem Comm 51(96):17144–17147. https://doi.org/10.1039/C5CC05323D
- Shi W, Guo F, Chen J, Che G, Lin X (2014) Hydrothermal synthesis of InVO4/Graphitic carbon nitride heterojunctions and excellent visible-light-driven photocatalytic performance for rhodamine B. J Alloy Compd 612(5):143–148. https://doi.org/10.1016/j.jallcom.2014.05.207
- Tang ML, Ao YH, Wang PF, Wang C (2020) All-solid-state Z-scheme WO3 nanorod/ZnIn2S4 composite photocatalysts for the effective degradation of nitenpyram under visible light irradiation. J Hazard Mater 387:121713. https://doi.org/10.1016/j.jhazmat.2019.121713
- Tonda S, Kumar S, Kandula S, Shanker V (2014) Fe-doped and -mediated graphitic carbon nitride nanosheets for enhanced photocatalytic performance under natural sunlight. J. Mater. Chem. A 2014, 2: 6772–6780. https://doi.org/10.1039/C3TA15358D
- Wang CC, Yan RY, Cai MJ, Liu YP, Li SJ (2023) A novel organic/inorganic S-scheme heterostructure of TCPP/Bi12O17Cl2 for boosting photodegradation of tetracycline hydrochloride: kinetic, degradation mechanism, and toxic assessment. Appl Surf Sci 610:155346. https://doi.org/10.1016/j.apsusc.2022.155346
- Wang XC, Maeda K, Thomas A, Takanabe K, Xin G, Carlsson JM, Domen K, Antonietti M (2009) A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat Mater 8:76–80. https://doi.org/10.1038/nmat2317
- Xiao Y, Wang H, Jiang YH, Zhang WL, Zhang JM, Wu XY, Liu ZC, Deng W (2022) Hierarchical Sb2S3/ZnIn2S4 core–shell heterostructure for highly effificient photocatalytic hydrogen production and pollutant degradation. J Colloid Interface Sci 623:109–123. https://doi.org/10.1016/j.jcis.2022.04.137
- Xu YC, Liu Q, Zhu JH, Zhang HS, Liu JY, Chen RR, Yu J, Li Y, Wang J (2022) Electron localization of ZnO/Znln2S4 interface induced lattice relaxation for triggering photocatalytic uranium evolution. Chem Eng J 435:134958. https://doi.org/10.1016/j.cej.2022.134958
- Ye L, Fu J, Xu Z, Yuan R, Li Z (2014) Facile one-pot solvothermal method to synthesize sheet-on-sheet reduced graphene oxide (RGO)/ZnIn2S4 nanocomposites with superior photocatalytic performance. ACS Appl Mater Inter 6:3483–3490. https://doi.org/10.1021/am5004415
- Zhang SW, Li JX, Zeng MY, Li J, Xu JZ, Wang XK (2014) Bandgap engineering and mechanism study of nonmetal and metal ions Co doped carbon nitride: C + Fe as an example. Chem Eur J 20:9805–9812. https://doi.org/10.1002/chem.201400060
- Zhang X, Wang Y, Du Y, Qing M, Yu F, Tian ZQ, Shen PK (2019) Highly active N, S co-doped hierarchical porous carbon nanospheres from green and template-free method for super capacitors and oxygen reduction reaction. Electrochim Acta 318:272–280. https://doi.org/10.1016/j.electacta.2019.06.081
- Zhang Z, Liu K, Feng Z, Bao Y, Dong B (2016) Hierarchical sheet-on-sheet ZnIn2S4/g-C3N4 heterostructure with highly efficient photocatalytic H2 production based on photoinduced interfacial charge transfer. Sci Rep 6:19221. https://doi.org/10.1038/srep19221
Scheme 1 is available in the Supplementary Files section
- Scheme1.docx
Scheme 1. The preparation of Znln2S4/S-C3N4 ( ZSC ) photocatalyst.