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Article

Graphene Oxide Decorated Ce2S3 Nanocomposite for Efficient Photocatalytic Degradation of Tetracycline

by
Zengguang Liu
,
Zeyu Zuo
,
Kai Yang
and
Kangqiang Lu
*
Jiangxi Provincial Key Laboratory of Functional Crystalline Materials Chemistry, School of Chemistry and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China
*
Author to whom correspondence should be addressed.
Catalysts 2025, 15(1), 21; https://doi.org/10.3390/catal15010021
Submission received: 26 November 2024 / Revised: 18 December 2024 / Accepted: 27 December 2024 / Published: 29 December 2024
(This article belongs to the Special Issue Recent Advances in Photocatalytic Degradation of Tetracycline Antibiotics)
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Abstract

Photocatalysis technology has been shown to be a promising and effective method for solving the growing energy and environmental challenges through the use of solar energy. In this work, Ce2S3 semiconductor photocatalysts decorated with small amounts of reduced graphene oxides are successfully synthesized by hydrothermal and calcination methods. The synthesized Ce2S3-RGO nanocomposite shows outstanding photocatalytic performance on the degradation of tetracycline (TC). The combination of Ce2S3 and RGO significantly promotes the separation of photon-generated carriers. The degradation rate of TC achieves 76% under visible light, which is 2.5 times over the pure Ce2S3 sample. In addition, a series of characterizations demonstrate that the introduction of RGO expands the visible light absorption range and increases the number of active sites. This work introduces the pivotal role of graphene oxide in the field of photocatalytic degradation and offers novel insights for the reasonable construction of effective composite photocatalysts.

1. Introduction

Tetracycline antibiotics, widely used for treating bacterial infections in both human medicine and veterinary practice, are also extensively applied in agriculture and livestock management [1,2,3,4]. However, tetracyclines possess a highly stable and robust aromatic ring structure, making them resistant to environmental degradation. This characteristic results in their persistence in water and rivers, contributing significantly to water pollution. To mitigate the highly detrimental effects of tetracycline, especially in water sources, it is of utmost importance to develop effective strategies for its elimination [5,6,7,8]. For the past several years, researchers from around the world have dedicated a great deal of effort to conducting a large volume of research on tetracycline degradation and some removal processes have been developed, such as physical adsorption and membrane treatment [9,10,11]. Physical adsorption involves the attachment of tetracycline molecules to the surface of a suitable adsorbent material, while membrane treatment utilizes membranes with specific pore sizes to separate tetracycline from water. While these methods do demonstrate significant efficacy in removing tetracycline to a certain extent, they also come with their own set of limitations [12,13,14,15]. For instance, physical adsorption and membrane treatment are costly and often require a substantial amount of energy consumption, which can limit their widespread application. Therefore, in light of these limitations, it is essential to develop a new degradation process that is not only highly efficient in removing tetracycline from water sources but is also environmentally friendly and requires low-energy consumption [16,17,18,19]. As photocatalytic technology continues to advance, photocatalytic degradation receives much attention from researchers and is identified as an excellent degradation method because of its advantages of being non-polluting, highly efficient, and cost-effective. However, it should be noted that the construction of an effective photocatalyst is one of the key factors that significantly affect the performance of photocatalysis. The properties of the photocatalyst, such as its composition, structure, and surface area, play a crucial role in determining how efficiently it can initiate and drive the photocatalytic degradation process.
Up to now, a great number of photocatalysts have been developed with the aim of degrading antibiotic residues present in the environment. These photocatalysts include but are not limited to, g-C3N4-based photocatalysts [20,21,22], TiO2-based photocatalysts [23,24,25], and Ce2S3-based photocatalysts [26,27,28]. Among the wide variety of photocatalysts that have been developed so far, Ce2S3 is particularly prominent. It is a narrow-band gap material that has found extensive use in both pigment-related applications and photocatalytic applications [29]. This is mainly due to the good visible light absorption capacity, which clearly shows that Ce2S3 has the potential to be an excellent photocatalyst under visible light conditions. In addition, Ce2S3 is non-toxic, which is a crucial factor when considering materials that will be used in environmental applications where safety and biocompatibility are paramount [30]. Nevertheless, there are certain limitations associated with single-component Ce2S3. The electron-hole pairs that are generated by light in Ce2S3 are prone to recombine. Additionally, unmodified Ce2S3 does not possess sufficient active sites, which ultimately results in a less-than-satisfactory performance. In order to overcome this problem, the rational introduction of a cocatalyst represents a viable approach to enhance the activity of Ce2S3.
Reduced graphene oxide (RGO) has gradually become a major focus in research because it has several distinctive properties [31]. For instance, it has a typical two-dimensional structure, which gives it certain unique physical and chemical properties. The outstanding electrical conductivity of RGO aids in the efficient transfer of electrons, which can help reduce the recombination of electron-hole pairs and improve the overall photocatalytic efficiency. Furthermore, this structure provides RGO with a large specific surface area, which is beneficial for increasing the contact area between the photocatalyst and the pollutants and can provide a large number of reaction active sites. When conductive RGO is combined with Ce2S3, it not only resolves the problem of the limited number of reaction sites on Ce2S3 but also plays an effective role in preventing the structural stacking of Ce2S3.
In this work, we compound ceria with RGO by facile hydrothermal method and calcination to synthesize Ce2S3-RGO composite with different RGO loading mass gradients. The results show that the obtained composite has tight interface contact. Moreover, the synergistic effect between RGO and Ce2S3 significantly enhances the transfer of photoinduced charge carriers and facilitates a more uniform and dispersed growth of Ce2S3 nanoparticles. Experimental results indicate that the Ce2S3-3%RGO composite demonstrates exceptional performance in degrading tetracycline (TC), achieving a degradation rate of 76% under visible light conditions, which is 2.5 times greater than blank Ce2S3. We believe this research provides valuable insights for synthesizing cocatalyst-modified semiconductor composites and advancing photocatalytic degradation systems.

2. Results and Discussion

Scheme 1 gives a schematic diagram of the preparation process of Ce2S3-RGO. Firstly, the CeO2-RGO precursor is produced by the hydrothermal method. Subsequently, oxygen atoms are replaced by sulfur atoms by calcination using thiourea as raw material to form a cerium sulfide graphene oxide hybrid. The crystal structures of both Ce2S3 and the Ce2S3-3%RGO composite are analyzed utilizing X-ray diffraction (XRD). As shown in Figure 1, the primary diffraction peaks observed at 26.9° and 43.8° for Ce2S3 can be attributed to the (121) and (321) planes of Ce2S3 (PDF#43-0799). Moreover, the diffraction pattern for the Ce2S3-3%RGO composite closely resembles that of pure Ce2S3, suggesting that adding RGO does not significantly alter the structure or lead to new crystalline phases within Ce2S3. Additionally, no peaks from graphene oxide are observed, indicating that incorporating RGO into Ce2S3 does not affect its crystallinity.
The morphology and microstructure of photocatalysts have an important effect on the performance of photocatalysis [32]. In order to examine the surface morphology and microstructural characteristics of the Ce2S3-3%RGO hybrid, a scanning electron microscope (SEM) is carried out [33,34]. As shown in Figure 2a,b, pure Ce2S3 presents stacked and irregular nanoparticle morphology, which is detrimental to the light absorption of pure Ce2S3 and the full exposure of the reaction active site. In addition, it can be observed that RGO is essentially composed of thin, wrinkled sheets in Figure 2c, which allows RGO to better bind to other materials and provide a larger surface area. So as displayed in Figure 2d,e, after the addition of the RGO cocatalyst, Ce2S3 can grow uniformly on the surface of the RGO nanosheet, which can effectively prevent the stacking of Ce2S3 nanoparticles. In addition, it can be seen that the intimate contact between RGO and Ce2S3 is constituted in the hybrid photocatalyst.
To accurately assess the photocatalytic activity of the sample, the TC solution is degraded under visible light exposure [35]. Figure 3 illustrates the TC degradation efficiency of Ce2S3 composites with different RGO mass fractions (1 wt%, 3 wt%, and 5 wt%). After a 150-min irradiation period with a 300 W Xenon lamp, the unmodified Ce2S3 sample exhibited only a 30% degradation efficiency for TC. This limited performance is primarily due to the low utilization of visible light by unmodified Ce2S3. In contrast, significant improvements in degradation rates are noted when RGO is incorporated with Ce2S3. Specifically, at an RGO content of 3 wt% relative to Ce2S3, the photodegradation efficiency for TC significantly increased to 76%, which is a rise of 2.5 times compared to pure Ce2S3. In addition, as presented in Table 1, the photocatalytic performance of Ce2S3-3%RGO composite is better than that of most reported catalysts. This enhancement can be attributed to the optimal amount of RGO added to Ce2S3, promoting the separation of photogenerated carriers. However, increasing the RGO content beyond this point resulted in reduced photodegradation activity; this decline may be linked to excessive load, causing particle agglomeration that limits active site availability and negatively impacts charge transfer rates. Therefore, these results indicate that judicious incorporation of RGO can enhance solar light absorption and subsequently improve the photocatalytic efficacy of Ce2S3.
The effect of reduced graphene oxide (RGO) on the properties of Ce2S3 is further explored through a series of electrochemical tests. As shown in Figure 4, the composite material consisting of Ce2S3 and 3% RGO exhibits a significantly smaller arc radius in its Nyquist plot when compared to pure Ce2S3. This smaller arc radius is a clear indication of a lower charge transfer resistance, suggesting that the addition of RGO improves the electrochemical performance of Ce2S3. More specifically, the reduced interfacial resistance in the Ce2S3-3%RGO composite facilitates more efficient electron and hole transport and separation. This enhancement in charge carrier mobility is likely due to the conductive nature of the RGO, which provides additional pathways for charge transfer, thereby improving the overall electrochemical behavior and efficiency of the composite material. These findings suggest that the incorporation of a small amount of RGO into Ce2S3 significantly enhances its electrochemical properties [42].
The cyclic voltammetry (CV) curves of the sample at various scanning rates are displayed in Figure 5a,b, showcasing the electrochemical behavior of the materials at different scan rates. As observed in Figure 5c, the double-layer capacitance (Cdl) of the Ce2S3-3%RGO composite (15.30 µF·cm−2) is higher than that of the blank Ce2S3 (14.02 µF·cm−2), indicating that the incorporation of reduced graphene oxide (RGO) into the Ce2S3 structure enhances the electrochemically active surface area, leading to improved charge storage capacity [43,44]. In addition, the photoluminescence (PL) spectra shown in Figure 5d provide insights into the recombination behavior of photogenerated carriers. The results reveal that Ce2S3 alone exhibits a higher photogenerated carrier recombination efficiency compared to the Ce2S3-3%RGO composite, suggesting that the introduction of RGO significantly reduces the recombination of electrons and holes in Ce2S3 [45]. This observation is consistent with the electrochemical impedance spectroscopy (EIS) results, further confirming that RGO enhances charge carrier separation and transportation within the composite material.
The optical properties of a material, including its ability to absorb visible light and its band gap energy, are critical factors in determining its photocatalytic performance, as these properties directly influence the material’s efficiency in light-driven reactions [46,47,48]. In this context, Figure 6 presents a detailed analysis of the UV-visible diffuse reflection spectrum (DRS) for both the pure Ce2S3 photocatalyst and the Ce2S3-3%RGO composite. For the pure Ce2S3 material, the absorption range is observed to be limited to approximately 500 nm, with a corresponding band gap of around 2.47 eV. This characteristic indicates that Ce2S3 primarily absorbs light in the ultraviolet (UV) region of the electromagnetic spectrum, with less absorption in the visible light range. This relatively narrow absorption range may restrict its effectiveness in photocatalytic applications, particularly under visible light illumination. In contrast, the Ce2S3-3%RGO composite shows a significant enhancement in its optical properties, with an extended absorption range that reaches up to approximately 800 nm. This remarkable redshift in the absorption edge is attributed to the incorporation of reduced graphene oxide (RGO) into the Ce2S3 structure, which effectively broadens the material’s light absorption capacity into the visible region. The improvement in visible light absorption of Ce2S3-3%RGO composites suggests that the introduction of graphene enhances the ability of Ce2S3 to use light energy in photocatalytic applications.
Furthermore, the semiconductor properties and band structure of Ce2S3 are characterized utilizing Mott-Schottky (M-S) (Figure 7) [28]. Since the slope of the M-S curve is positive, this indicates that Ce2S3 is an N-type semiconductor [49]. Meanwhile, the flat-band potential (Efb) of Ce2S3 is calculated to be −0.55 eV in comparison to Ag/AgCl. The conduction potential (ECB) of N-type semiconductors is approximately 0.2 V negative than Efb, thereby the CB value of Ce2S3 is −0.35 eV (vs. Ag/AgCl). Through the calculation based on the formula ENHE = EAg/AgCl + Eg, it is found that the ECB of Ce2S3 is −0.55 eV (vs. NHE). Additionally, as the band gap of Ce2S3 is 2.47 eV, the valence band potential (EVB) for Ce2S3 is 1.92 eV (vs. NHE).
Based on the experimental findings and related literature reports, we reasonably speculated a refined mechanism illustrated in Figure 8 [50,51]. The electron and hole pairs in graphene (GR) and Ce2S3 undergo significant changes under visible light. The electrons (e−) in the conduction band (CB) of Ce2S3 are transferred and recombined with holes (h+) in the valence band (VB) of GR. This migration of charge carriers leads to the accumulation of electrons in the CB of GR, while holes are retained in Ce2S3. As a result, the electrons in the CB of GR can interact with O2, generating superoxide radicals (·O2−). Meanwhile, the holes in the VB of Ce2S3 oxidize H2O, producing hydroxyl radicals (·OH−). These reactive species subsequently interact with adsorbed tetracycline (TC) molecules, leading to the formation of various degradation products.
The primary reaction equations are as follows:
Ce2S3-RGO + hv → Ce2S3 (e− + h+) + RGO (e− + h+)
Ce2S3 (e−) + RGO (h+) → RGO (recombination)
RGO (e−) + O2 → ·O2−
Ce2S3 (h+) + H2O→ ·OH−
·O2− + ·OH− + h+ + TC → degradation products

3. Experimental

3.1. Materials and Reagents

Cerium nitrate hexahydrate (Ce(NO3)3·6H2O), ethanol (C2H5OH), thiourea (CH4N2S), hexamethylenetetramine (HMTA), N,N-dimethylformamide (C3H7NO). All the chemicals are analytically pure and used without any purification.

3.2. Preparation of Pure GO

Synthesis of graphene oxide: GO is synthesized by a modified Hummers’ method. In detail, 10 g graphite powder (supplied from Qingdao Zhong tian Company, Qingdao, China) is put into 230 mL concentrated H2SO4 under moderate stirring. Then, 30 g KMnO4 is added gradually under stirring and the solution is cold below 5 °C in an ice bath. After that, the solution is heated to 35 °C in a water bath and kept stirring for 2 h. Then, the mixture is diluted with 500 mL DI water in an ice bath to keep the temperature below 5 °C. Shortly after the further diluted with 1.5 L of DI water, 80 mL 30% H2O2 is then added into the mixture. The mixture is centrifuged and washed with 1:10 HCl aqueous solution to remove metal ions followed by DI water to remove the acid. After that, the mixture is dialyzed for one week and the final GO sample is obtained after full sonication.

3.3. Synthesis of Ce2S3-RGO Hybrid

The CeO2-RGO precursor is prepared via a simple hydrothermal synthesis process. Initially, 0.6 mmol of cerium nitrate hexahydrate (Ce(NO3)3·6H2O, 260 mg) and 1.2 mmol of hexamethylenetetramine (HMTA, 168 mg) are dissolved in a mixture of 30 mL of distilled water and 30 mL of ethanol. Subsequently, graphene oxide is introduced into this solution. The mixture is then transferred to a 100 mL Teflon-lined autoclave and kept at 75 °C for 12 h. After cooling to room temperature, the product is collected by filtration and washed several times with deionized water, followed by drying at 60 °C for 10 h. The dried product obtained is designated as CeO2-RGO. Next, in order to synthesize Ce2S3-RGO, a crucible containing 250 mg thiourea and 50 mg prepared CeO2-RGO is heated in a tube furnace at 300 °C for 3 h at a heating rate of 10 °C/min. After cooling to room temperature, the Ce2S3-RGO sample is obtained.

3.4. Preparation of Tetracycline Antibiotics

Weigh precisely 10 mg of tetracycline (an antibiotic) and put it into a 250 mL beaker. Then, prepare 200 mL of distilled water and pour it into the beaker. Stir the mixture to dissolve the tetracycline in the distilled water. Next, transfer the dissolved solution to a 2000 mL volumetric flask, add distilled water until the volume reaches the scale mark, and shake well. Eventually, a tetracycline solution with a concentration of 5 ppm is obtained.

3.5. Characterizations

The phase composition of synthesized samples is determined by X-ray diffraction (XRD Bruker D8 Advance, Bruker Corporation, Saarbrucken, German). Scanning electron microscopy (SEM, FEI MLA650F, Hillsboro, OR, USA) and transmission electron microscopy (TEM, FEI Tecnai G2-20, Hillsboro, OR, USA) are used to reveal the samples’ surface morphology and internal microstructure. UV–vis diffuse reflectance spectra (UV-2500, Shimadzu, Kyoto, Japan) are used to determine the absorption of UV-visible light by samples. An electrochemical workstation (CHI-660E, Bee Cave, TX, USA) is carried out to measure the photocurrent density (I-t) and electrochemical impedance (EIS) of the samples to analyze the electrochemical state of the samples. Information about the other instruments can be seen in Table S1.

3.6. Photocatalytic Performance Test

The photocatalytic activity of the samples is evaluated by degrading a 5 ppm TC solution, utilizing a Perfect-light 350 W Xe lamp (PL-XQ350W, Perfectlight, Beijing, China) as the light source. Specifically, 10 mg of the photocatalyst is added to a reactor containing 50 mL of the 5 ppm TC solution. This mixture is stirred in darkness for one hour to establish adsorption–desorption equilibrium while being cooled with circulating water. Samples are taken every 20 min, centrifuged, and the resulting supernatant is analyzed using UV–vis spectroscopy.

4. Conclusions

All in all, we successfully prepared the Ce2S3-RGO composite, which exhibits remarkable photocatalytic performance. The degradation rate of tetracycline (TC) achieved an impressive 76% within 150 min under visible light irradiation, marking a 2.5-fold improvement compared to pure Ce2S3 samples. The enhancement in photocatalytic efficiency can be ascribed to two primary factors: the augmented transfer and separation efficiency of electron-hole pairs, as well as the extended range of visible light absorption. In addition, electrochemical experiments show that the introduction of RGO increases the number of active sites of Ce2S3. According to the research results and related literature reports, we reasonably speculated the reaction mechanism of the degradation process, in which the O2− and OH radicals play a major role. Overall, this research provides valuable insights and guidance for developing effective systems for the degradation of tetracycline and other pollutants, aligning with the increasing need for practical solutions in environmental applications.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/catal15010021/s1, Table S1: Instruments.

Author Contributions

Z.L.: Data curation, Investigation, Writing—original draft, Writing—review and editing. Z.Z.: Data curation, Investigation, Writing—original draft. K.Y.: Writing—review & editing. K.L.: Funding acquisition, Project administration, Resources, Supervision, Writing—review & editing. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by the Jiangxi Provincial Natural Science Foundation (No. 20212BAB213016, 20224BAB203018, 20224ACB213010), the Jiangxi Province “Double Thousand Plan” (No. jxsq2023102143, jxsq2023102142, jxsq2023201086, jxsq2023102141, jxsq2019102053), the National Natural Science Foundation of China (No. 22366018, 5236005, 22462010), the Program of Qingjiang Excellent Young Talents, JXUST (No. JXUSTQJBJ2020005), Jiangxi University of Science and Technology students’ innovation and entrepreneurship training program (Preparation of nickel-cobalt dual-active site cocatalyst and their light-driven CO2 reduction performance research, S202410407065).

Data Availability Statement

Data will be made available on request.

Acknowledgments

The authors would like to thank Hu Jinpu from Shiyanjia Lab (www.shiyanjia.com) for the XPS analysis on August 2024 and Jiangxi Qianvi New Materials Co., Ltd. For SEM analysis and TEM analysis provided by zkec (www.zkec.cc) on July 2024.

Conflicts of Interest

The authors declare no conflict of interest.

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Catalysts 15 00021 sch001
Scheme 1. The flowchart of Ce2S3-RGO composite preparation.
Scheme 1. The flowchart of Ce2S3-RGO composite preparation.
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Figure 1. The XRD map of the Ce2S3, Ce2S3-3%RGO composites.
Figure 1. The XRD map of the Ce2S3, Ce2S3-3%RGO composites.
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Figure 2. SEM image of Ce2S3 (a,b), RGO (c), Ce2S3-3%RGO (d,e) composite.
Figure 2. SEM image of Ce2S3 (a,b), RGO (c), Ce2S3-3%RGO (d,e) composite.
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Figure 3. Graph of photocatalytic degradation efficiency.
Figure 3. Graph of photocatalytic degradation efficiency.
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Figure 4. Electrochemical impedance spectrum of Ce2S3 and Ce2S3-3%RGO composite.
Figure 4. Electrochemical impedance spectrum of Ce2S3 and Ce2S3-3%RGO composite.
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Figure 5. The CV curves of (a) Ce2S3 and (b) Ce2S3-3%RGO. (c) Current versus density scan rate plots of Ce2S3 and Ce2S3-3%RGO. (d) Photoluminescence spectra.
Figure 5. The CV curves of (a) Ce2S3 and (b) Ce2S3-3%RGO. (c) Current versus density scan rate plots of Ce2S3 and Ce2S3-3%RGO. (d) Photoluminescence spectra.
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Figure 6. (a) DRS of Ce2S3, Ce2S3-3%RGO (b) estimated bandgap spectra of Ce2S3.
Figure 6. (a) DRS of Ce2S3, Ce2S3-3%RGO (b) estimated bandgap spectra of Ce2S3.
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Figure 7. Mott-Schottky curves of Ce2S3.
Figure 7. Mott-Schottky curves of Ce2S3.
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Figure 8. Schematic diagram of photocatalytic mechanism for Ce2S3-3%RGO.
Figure 8. Schematic diagram of photocatalytic mechanism for Ce2S3-3%RGO.
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Table 1. Compared the TC degradation activity of different reported materials.
Table 1. Compared the TC degradation activity of different reported materials.
PhotocatalystsTC
Degradation		Concentration
(mg/L)		Light SourcesReference
10%BiOIO3/BiOBr74.91%2012 W LED lamp[36]
PO43−-Bi2WO6/PI65.1%20150 W Xe lamp[37]
BiOI/Bi2S3/PAN84.49%10300 W Xe lamp
(λ ≥ 420 nm)		[38]
FeCo2O4/Co3O487.85%50300 W Xe lamp
(λ ≥ 420 nm)		[39]
ZnFe1.2Co0.8O470%20300 W Xe lamp
(λ ≥ 420 nm)		[40]
Ag/α-Fe2O3-573.9%10300 W Xe lamp[41]
Ce2S3-5%RGO76%5350 W Xe lampThis work
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Liu, Z.; Zuo, Z.; Yang, K.; Lu, K. Graphene Oxide Decorated Ce2S3 Nanocomposite for Efficient Photocatalytic Degradation of Tetracycline. Catalysts 2025, 15, 21. https://doi.org/10.3390/catal15010021

AMA Style

Liu Z, Zuo Z, Yang K, Lu K. Graphene Oxide Decorated Ce2S3 Nanocomposite for Efficient Photocatalytic Degradation of Tetracycline. Catalysts. 2025; 15(1):21. https://doi.org/10.3390/catal15010021

Chicago/Turabian Style

Liu, Zengguang, Zeyu Zuo, Kai Yang, and Kangqiang Lu. 2025. "Graphene Oxide Decorated Ce2S3 Nanocomposite for Efficient Photocatalytic Degradation of Tetracycline" Catalysts 15, no. 1: 21. https://doi.org/10.3390/catal15010021

APA Style

Liu, Z., Zuo, Z., Yang, K., & Lu, K. (2025). Graphene Oxide Decorated Ce2S3 Nanocomposite for Efficient Photocatalytic Degradation of Tetracycline. Catalysts, 15(1), 21. https://doi.org/10.3390/catal15010021

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