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Article

Facile Hydrothermal Synthesis of Cu2MoS4 and FeMoS4 for Efficient Adsorption of Chlortetracycline

by
Junhui Zhou
1,2,
Keyu Zhu
2,
Yong Wang
1,
Peng Cui
3,
Linhua Zhu
4,
Haofeng Wu
1,2,
Mingqing Hua
3,
Yan Huang
3,
Guiling Luo
3,
Yanhong Chao
1,2,* and
Wenshuai Zhu
2,3,*
1
School of Pharmacy, Jiangsu University, Zhenjiang 212013, China
2
College of Science, China University of Petroleum-Beijing, Beijing 102249, China
3
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China
4
Key Laboratory of Water Pollution Treatment and Resource Reuse of Hainan Province, College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, China
*
Authors to whom correspondence should be addressed.
Catalysts 2023, 13(1), 61; https://doi.org/10.3390/catal13010061
Submission received: 23 November 2022 / Revised: 15 December 2022 / Accepted: 25 December 2022 / Published: 28 December 2022
(This article belongs to the Special Issue Functional Materials for Application in Adsorption & Catalysis)
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Abstract

:
Contamination of antibiotics in an aqueous environment has attracted wide attention. Developing high-efficiency adsorbents for antibiotics removal is urgent. In this work, two kinds of ternary transition metal chalcogenides—Cu2MoS4 and FeMoS4 with superior adsorption performance were prepared by a facile hydrothermal synthesis method. The microstructure and physicochemical properties of the adsorbents were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscope (XPS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The as-prepared Cu2MoS4 and FeMoS4 were found to have dramatic potential for the adsorption of chlortetracycline (CTC) in an aqueous solution with an extremely high adsorption capacity. The Langmuir maximum adsorption capacity of Cu2MoS4 and FeMoS4 to CTC can reach 1203.81 and 2169.19 mg/g, respectively, which goes far beyond the common adsorbents as reported. Moreover, the adsorption kinetics, thermodynamics as well as adsorption mechanism were examined in detail by a batch of adsorption experiments.

1. Introduction

The scarcity of freshwater resources and the increase in global water consumption have put enormous pressure and an urgent need for strict control of pollutants. The development of efficient remediation technologies become particularly important. Recently, the discharge of drugs, especially antibiotics, has been recognized as one of the emerging environmental issues in the water environment. Due to their excellent bactericidal and anti-inflammatory effects, antibiotics have been widely used in the pharmaceutical industry, agriculture, aquaculture, and animal husbandry [1,2]. Antibiotics and their metabolites were frequently detected in various aqueous mediums, such as hospital, aquaculture, and livestock production wastewater, even in surface and drinking water. The continuous accumulation of antibiotics in natural water bodies may lead to the development of antibiotic-resistant pathogens and are detrimental to the health of ecology and human beings [3,4,5,6]. Chlortetracycline (CTC) is one of the most used antibiotics in human therapeutic history and animal husbandry. Human allergic reactions, bacterial resistance, and marked fluctuations in environmental microbiota have been associated with the overuse of chlortetracycline. Consequently, there is a need to develop more efficient ways to remove antibiotic contamination within water [7,8,9].
Nowadays, the methods of removing antibiotics from the aquatic environment are well established [10], including adsorption [11,12,13,14], membrane separation [15,16], photocatalysis degradation [17,18,19], biodegradation [20,21], electrochemistry [22] and oxidation [23,24,25]. Compared with other methods, adsorption has the advantages of being ecologically friendly, and economical, with no by-products, simple operation, and high efficiency in the treatment of antibiotics, which enable it a promising and valuable method of water pollution treatment for research [26]. With the widespread application of adsorption methods, a variety of adsorption materials have been developed, such as graphene [13,27], boron nitride [28,29], layered double hydroxide [30,31,32], and MoS2 [33,34].
MoS2 belongs to the family of transition metal chalcogenides (TMCs) and can be used as a favorable adsorbent material owing to its special layered structure, van der Waals interactions, and strong covalent bonds [35,36]. In recent years, ternary TMCs are of great interest on account of their intriguing structure and physicochemical properties. Ternary TMCs possess higher electron mobility, richer redox sites, and better adjustability of the interlayer distance compared to single-component metal chalcogenides, and can be applied in many fields [37,38]. Highly stable metallic CuFeS2 nanosheets with metallic-like conductivity and large accessible surface area were successfully prepared as an excellent noble-metal-free nanocatalyst for hydrogen evolution reaction by Li et al. The catalytic performance of CuFeS2 was higher than CuS and FeS2 [39]. Zhao et al. synthesized Cu2MoS4 with the best phase composition by precisely adjusting the reaction time, under visible light irradiation, it can rapidly degrade methyl orange in a short period of time [40]. However, the research on the adsorption performance of ternary TMCs is quite limited. In recent years, amorphous CoMoS4 nanostructure and flower-like Cu2MoS4/g-C3N4 composites were reported to be effective in adsorbing methylene blue (the maximum adsorption capacity of qm = 292.4 mg/g) and Rhodamine B dye (qm = 420.2 mg/g), respectively [41,42]. It confirms that ternary TMCs have the potential to adsorb pollutants from aquatic environments. Therefore, a more comprehensive, and deeper study on the adsorption performance of ternary TMCs is very important and strongly necessary for the development of efficient adsorbents.
In this work, we synthesized ternary TMCs of Cu2MoS4 and FeMoS4 by a simple hydrothermal method, and their adsorption properties on antibiotics were investigated. By optimizing the transition metals sources and hydrothermal synthesis condition, the as-prepared ternary TMCs exhibited extremely high adsorption performance to antibiotics. The maximum adsorption capacities of Cu2MoS4 and FeMoS4 were up to 1203.81 and 2169.19 mg/g to chlortetracycline, respectively, which were much higher than most of the reported adsorbents. Moreover, the adsorption mechanism during the adsorption process was also investigated systematically to explore the adsorption kinetics, isotherms, and thermodynamics.

2. Results

2.1. Characterization and Analysis

X-ray diffraction (XRD) resorted to investigating the crystalline properties of as-prepared Cu2MoS4 and FeMoS4, and the results are recorded in Figure 1. As shown in the XRD pattern of Cu2MoS4, the diffraction peaks appeared at 2θ = 17.22°, 18.66°, 29.27°, 31.85°, 33.02°, 37.69°, 46.67°, 47.98°, 48.69°, and 51.03° correspond to the (002), (011), (112), (013), (020), (004), (123), (220), (015) and (024) crystal planes of Cu2MoS4 as previously reported [43]. All of the XRD peaks can be attributed to Cu2MoS4 with I-phase [40]. Meanwhile, impurity peaks like Cu2O, Cu2S, and MoO3 are not detected. On the XRD pattern of as-prepared FeMoS4, it doesn’t show obvious diffraction peaks, which may be attributed to the low crystallinity of FeMoS4.
The morphological and microstructural aspects of the prepared samples investigated by SEM and TEM were shown in Figure 2. In Figure 2a,c, the SEM images of Cu2MoS4 reveal a structure of messy stacked layered plates and rectangular tubes with better crystallinity. Meanwhile, the SEM images of FeMoS4 (Figure 2b,d) present an obvious thick layered structure of hierarchical stacked lamination form. The difference in the morphological appearance of these two samples is consistent with their different XRD patterns illustrated above. The TEM images of Cu2MoS4 and FeMoS4 are shown in Figure 2e,f, respectively. Cu2MoS4 displays a messy layered nanosheet micromorphology, and FeMoS4 reveals a stacked lamelliform microstructure. In addition, the elemental mapping images have been carried out, the related results are presented in Figure 2g,h. The elements of Cu, Mo, and S can be observed and are distributed evenly in Cu2MoS4. Meanwhile, uniformly distributed Fe, Mo, and S elements also can be observed in FeMoS4.
Furthermore, elemental composition in detail of Cu2MoS4 and FeMoS4 was performed via XPS, and the obtained results are shown in Figure 3.
The XPS survey spectra of Cu2MoS4 and FeMoS4 indicate the peaks corresponding to the occurrence of the Cu 2p, Fe 2p, O 1s, N 1s, C 1s, S 2p, Mo 3d states. Exposure to air or originating from raw materials led to the presence of C, N, and O in the spectrum [42]. In Figure 3c, the peaks located at 951.93 and 931.76 eV represent Cu 2p1/2 and Cu+ 2p3/2, the 932.54 eV peak indicates that Cu has a divalent oxidation state [33]. The peaks located at 710.55 and 723.69 eV (Figure 3d) can be associated with the characteristic signals of Fe 2p3/2 and Fe 2p1/2, respectively. Meanwhile, the two peaks at 707.58 and 720.26 eV are attributed to Fe2+ 2p3/2 and Fe2+ 2p1/2 [43,44]. The spectra of Mo 3d for Cu2MoS4 and FeMoS4 (Figure 3e,f) are similar, the Mo6+ 3d3/2 and Mo6+ 3d5/2 peaks are respectively observed at 235.3 and 229.8 eV, as a result of the reduction of Mo, Mo4+ 3d3/2 and Mo4+ 3d5/2 correspond to the presence of peaks at 232.3 and 228.5 eV, and a minor peak around 226.07 eV due to the presence of the S 2s state [33,45]. In the spectra of S 2p (Figure 3g,h), the diffraction peak of S 2p3/2 is located at 161.8 eV, and the peaks of 162.9 and 163.7 eV are both attributed to S 2p1/2. Furthermore, the peaks of 168.2 and 169.4 eV can correspond to the SOx group on the S 2p XPS spectrum of FeMoS4 [46].

2.2. Adsorption Performance of Cu2MoS4 and FeMoS4

2.2.1. Effect of Synthesis Conditions for Adsorption Performance

The adsorption performance of Cu2MoS4 and FeMoS4 which were synthesized under different conditions (the synthesis temperature, the source, and the number of copper salts) for CTC were assessed and compared. As illustrated in Figure 4a, the temperature and copper source had a noticeable effect on the adsorption properties of Cu2MoS4. Cu2MoS4 synthesized with CuBr at 170 °C showed the highest removal efficiency to CTC. The optimization of CuBr amount is shown in Figure 4b, when the increment of CuBr amount from 0.1 to 0.6 g, the removal efficiency of CTC was enhanced; but decreased with further increasing the amount. Cu2MoS4 synthesized using 0.6 g CuBr at 170 °C had the best removal efficiency to CTC, which was applied for the further investigation of the adsorption performance, mechanism, and characterization.
Figure 4c,d reveals the effect of synthesis temperature and the amount of FeCl2·4H2O on the removal efficiency of CTC by FeMoS4. As the increase of the temperature and the iron amount, the adsorption performance showed an increase and then a decreasing trend. The removal efficiency of CTC reached 98% by FeMoS4 as the temperature is 170 °C and the amount is 0.2 g. Consequently, FeMoS4 synthesized using 0.2 g FeCl2·4H2O at 170 °C is chosen for further investigation.
In addition, the UV-vis absorption spectra of CTC before and after adsorption by Cu2MoS4 and FeMoS4 are shown in Figure S1. It is noticed that the characteristic peaks of CTC decreased significantly to almost disappearance and no other new peaks appeared after the adsorption, indicating that the CTC was adsorbed almost entirely by Cu2MoS4 and FeMoS4 under the experiment conditions, and no detectable degradation byproducts were produced.

2.2.2. Adsorption Kinetics of Cu2MoS4 and FeMoS4 to CTC

The adsorption capacity of CTC onto Cu2MoS4 and FeMoS4 at different times was illustrated. In this study, the pseudo-first-order model, the pseudo-second-order model, the intra-particle diffusion model, and the Elovich model were adopted to evaluate the kinetics of the CTC adsorption data on the Cu2MoS4 and FeMoS4. These four models were described in Equations (S3)–(S6).
The adsorption capacity of CTC on Cu2MoS4 and FeMoS4 at different times is presented in Figure 5a, it could be noticed that the adsorption capacity of CTC on Cu2MoS4 reaches 453.37 mg/g in 36 h, then the arrival of adsorption equilibrium was followed by the adsorption capacity of 470.81 mg/g when the adsorption time was greater than 48 h; meanwhile, the FeMoS4 reached equilibrium at 36 h and reached an adsorption capacity of 477.79 mg/g. The related results and the corresponding parameters are displayed in Figure 5b–e and Table 1. The calculated adsorption capacity (qe,cal = 467.29 and 490.19 mg/g) from the pseudo-second-order model was similar to the experimental value (qe,exp = 470.81 and 477.79 mg/g), simultaneously, the R2 fitted by the pseudo-second-order model was higher than 0.998, which verified that the pseudo-second-order model had a better fit for experimental data. This result indicated that chemisorption played a dominant role in the adsorption process, the chemisorption can be attributed to the complexation between Cu/Fe and CTC [6,44,45]. In addition, the piecewise linear regressions were observed by fitting the intra-particle diffusion model, representing the three steps of the adsorption process: (a) adsorbates transfer from solution to adsorbent surface; (b) adsorbates diffuse in the pores of adsorbent; (c) antibiotic adsorbs onto the active site of the adsorbent. Since the linear regression curve didn’t intersect with the origin, it meant that there are other factors controlling the adsorption process besides the intra-particle diffusion, the liquid-film diffusion, and the boundary layer diffusion may also be involved in the adsorption process [28,29].

2.2.3. Adsorption Isotherms of Cu2MoS4 and FeMoS4 to CTC

It is vital for further study of adsorption mechanisms by analysis of the adsorption isotherm result during the adsorption process of CTC on Cu2MoS4 and FeMoS4. In this study, the equilibrium adsorption data were analyzed using three isothermal equations, Langmuir, Freundlich, and Temkin. These three models were described in Equations (S7)–(S9).
The adsorption isotherm of CTC onto Cu2MoS4 and FeMoS4, the related fitting results, and corresponding constants are presented in Figure 6 and Table 2. It can be concluded that Langmuir and Temkin’s models fit experimental data well. The adsorption process of CTC onto Cu2MoS4 and FeMoS4 may be monolayer adsorption on the uniform surface due to the higher R2 and lower APE obtained from the Langmuir model. The theoretical maximum adsorption capacity (qm) of Cu2MoS4 and FeMoS4 calculated from the Langmuir model was 1203.81 and 2169.19 mg g−1, which exceeded the adsorption performance of the great majority of other reported adsorbent materials (Table 3). The constant separation factor RL is smaller than 1, which illustrated a favorable adsorption process [45]. Temkin’s model suggested the binding force decreased linearly as the coverage of antibiotic molecules on the surface increased. The Temkin model with the high correlation coefficient indicated that there may be uniformly distributed binding force (e.g., strong electrostatic interaction) between CTC and adsorbents. The result is consistent with the observation from the effect of pH [28,46]. In addition, when high concentrations of CTC solutions were adsorbed using FeMoS4, aggregates were observed at the bottom (Figure S2), presumably owing to CTC molecules forming complexes with the iron ions, inducing flocculation, leading to increased removal efficiency [44,47].

2.2.4. Adsorption Thermodynamics

The temperature-dependent adsorption behavior of adsorbents had also been investigated under four temperatures (298, 308, 318, and 328 K). The parameters of ΔG0 ΔH0, and ΔS0 derived from Gibbs-Helmholtz were further introduced to clarify the thermodynamic characteristics, they were calculated by Equations (S10) and (S11). As shown in Figure 7a, the adsorption capacity of CTC onto Cu2MoS4 and FeMoS4 both improved with rising temperature, indicating that the higher the temperature the more conducive the adsorption. The obtained thermodynamic parameters of adsorption are presented in Table 4. The negative ΔG0 values indicated that the adsorption process was spontaneous, and there was physical adsorption in the adsorption process (−20 kJ/mol < ΔG0 < 0). The endothermic feature of the adsorption process can be proved by the positive value of ΔH0, the reaction between adsorbents and CTC at higher temperatures was favorable. Moreover, the value of ΔS0 was positive, implying the increase of randomness at the solid-liquid interphase [28].

2.2.5. Effect of Solution Coexisting Ions

The adsorption experiments at various ionic solutions were performed to assess the effect of solution coexisting ions solution on the adsorption of CTC on Cu2MoS4 and FeMoS4. The concentration of the solution that contains different cations like Na+, K+, Ca2+, and anions such as Cl−, and SO42− was maintained at 0.1 mol/L. As shown in Figure 7b, taken as a whole, the different degrees of inhibition on adsorption by the coexistence of ions in solution were observed, it is suggested that the important role in the adsorption process may be played by electrostatic interaction. By comparison, the cation Ca2+ had the greatest impediment to CTC removal, it was speculated that competition occurred between Ca2+ and CTC, which reduced the electrostatic attraction between CTC and adsorbents [29].

2.2.6. Effect of Solution pH

The effect of pH on the adsorption of CTC by Cu2MoS4 and FeMoS4 was investigated in the range of solution pH values from 3 to 9 and the results are shown in Figure 7c. The adsorption capacity initially increased with solution pH increasing, achieving an optimum at pH = 5, but decreased from 5 to 9. CTC was an amphiphilic molecule, in the pH range from 3.33 to 7.55, deprotonation occurs at CTC, and there is a zwitterion in the solution. Then, the second deprotonation of CTC occurs leading to a negatively charged CTC when 7.55 < pH < 9.33. In the pH range of 4–7, there was the unobvious effect of pH changes on the adsorption capacity and low electrostatic interactions (attraction or repulsion), due to the presence of CTC at pH 4–7 with almost no net electrical charge, predominantly in the form of amphiphilic ions. Nevertheless, when the pH value was 9, the negative charge on the CTC surface increased, thereby increasing the electrostatic repulsion between CTC and adsorbents [44,54].

2.2.7. Antibiotic Contamination and Regeneration Study

Due to the complexity of the actual wastewater environment, the adsorption performance of Cu2MoS4 and FeMoS4 for different antibiotics was examined and the results are shown in Figure 7d. Chlortetracycline (CTC), tetracycline (TC), doxycycline (DC), oxytetracycline (OTC), sulfamethazine (SMZ), ciprofloxacin (CIP) were used to explore the effects of adsorption selectivity on Cu2MoS4 and FeMoS4. The order of adsorption by Cu2MoS4 and FeMoS4 on different antibiotic contaminants was CTC > TC > DC > OTC > CIP > SMZ. Finally, to evaluate the stability of the adsorbents, the regeneration performance of Cu2MoS4 and FeMoS4 was studied by six cycles (Figure 8a). It can be seen that adsorption removal efficiency can maintain above 90% after the 6th regeneration, and the spectra of adsorbents before and after the regeneration (Figure 8b) did not change significantly and the peak shapes remained essentially identical, indicating that as-prepared adsorbents had excellent stability and may function as an effective and promising adsorbent for contaminants antibiotics. In addition, to avoid secondary contamination of water sources by leaching metals from the adsorbent, the solution after adsorption was collected and measured for metal ion concentrations by ICP-AES. The results are shown in Table S1, there were extremely low concentrations of metal ions detected, proving that the adsorbent does not cause secondary contamination of water resources.

3. Methods

3.1. Synthesis of Samples

3.1.1. Synthesis of (NH4)2MoS4

Firstly, 10 g of N6H24Mo7O24·4H2O was mixed with 40 mL of deionized water, then 90 mL (NH4)2S was added and heated at 70 °C for one hour. Afterward, the red-brown solution was cooled down and crystals of (NH4)2MoS4 were crystallized out. Finally, deionized water and anhydrous ethanol were used to wash the crystals several times and collected after drying and grinding.

3.1.2. Synthesis of Cu2MoS4

0.4 g of (NH4)2MoS4 and a certain amount of copper salt (CuCl, CuBr, and CuI) were dispersed in 15 mL of deionized water and a homogeneous solution could be formed after stirring. Then, a Teflon-lined stainless steel autoclave was used to load the solution and heated at a certain temperature (T = 160, 170, 180, and 190 °C) for 24 h. Finally, the hydrothermal product was centrifuged, washed, and dried to yield the precipitate of Cu2MoS4.

3.1.3. Synthesis of FeMoS4

Firstly, 0.4 g (NH4)2MoS4 and a certain amount of FeCl2·4H2O were dispersed in 15 mL deionized water and a homogeneous solution could be formed after stirring. Then a Teflon-lined stainless steel autoclave was used to load the solution and heated at a certain temperature (T = 160, 170, 180, and 190 °C) for 24 h. Finally, the hydrothermal product was centrifuged, washed, and dried to yield the precipitate of the FeMoS4.

3.2. Adsorption Experiment Set-Up

The adsorption properties of the Cu2MoS4 and FeMoS4 to CTC were assessed according to the following procedure: 5 mg of absorbents and 25 mL of 100 mg/L CTC aqueous solution were added into a conical flask, followed by shaking at 130 rpm at 298 K under dark condition. Afterward, 1 mL supernatant was taken out from the conical flask, diluted, and passed through a 0.22 μm cellulose membrane to analyze the residual CTC concentration by UV–visible spectrometer. The removal efficiency (R) and the adsorption capacity (q) were calculated using Equations (S1) and (S2).
To evaluate the adsorption performance of Cu2MoS4 and FeMoS4 synthesized under different conditions, 10 mg of adsorbents and 25 mL CTC solution (concentration: 100 mg/L) were used. CTC solutions with initial concentrations of 100–500 mg/L and dosages of 0.2–1 g/L of adsorbent were employed in the adsorption isotherm studies. The pH of the solution was maintained at 3, 5, 7, and 9 respectively in the experiment on the effect of the solution pH. For the effect of the solution’s coexisting ions, certain amounts of different salts were dissolved before adding the samples to maintain the solution ionic strength at 0.1 mol/L of various ions. For thermodynamics analysis, the temperatures were maintained at 298, 308, 318, and 328 K respectively in the adsorption experiments. For the antibiotic contamination study, different antibiotic concentrations were maintained at 100 mg/L. For the regeneration study, the CTC-adsorbed Cu2MoS4 and FeMoS4 were washed with deionized water and ethanol to reach desorption equilibrium, then reused for adsorption again after drying.

4. Conclusions

In summary, a simple hydrothermal method was adopted to synthesize the ternary transition metal chalcogenides—Cu2MoS4 and FeMoS4 and they were effective in the adsorption of CTC. The theoretical maximum adsorption capacities of Cu2MoS4 and FeMoS4 for CTC were 1203.81 and 2169.19 mg/g, respectively, according to the Langmuir model, which exceeded the adsorption capacities of most other adsorbent materials reported. The findings of the adsorption experiments demonstrated a good correlation between the experimental data and the pseudo-second-order kinetic mode, indicating that chemisorption dominates. The equilibrium adsorption data were well fitted by the Langmuir model, demonstrating monolayer adsorption between CTC and the adsorbents. The relatively high correlation coefficient of the Temkin model indicated a stronger electrostatic interaction between CTC and the adsorbents, which was consistent with the observation from the effects of pH. Studies on thermodynamics revealed that the adsorption process was endothermic, spontaneous, and feasible. The Cu2MoS4 and FeMoS4 could effectively remove CTC in a wide range of pH 3–7, and the ionic strength presented an inhibition effect for the adsorption. After the 6th regeneration cycle, Cu2MoS4 and FeMoS4 still had an excellent removal percentage of 90% for CTC, indicating that the adsorbent has good renewable recycling performance. Hence, Cu2MoS4 and FeMoS4 synthesized by the facile single-step hydrothermal approach possess great potential as stable and high-efficient adsorbents for wastewater treatment applications.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/catal13010061/s1, Figure S1: UV-vis absorption spectra of CTC before and after adsorption; Figure S2: The flocculation of the complex; Table S1: Concentration of metal in solution after adsorption.

Author Contributions

Y.C.; Data curation, Y.W.; Formal analysis, J.Z., K.Z. and H.W.; Investigation, P.C. and L.Z.; Methodology, Y.C.; Resources, P.C., L.Z., M.H., Y.H., Y.C. and W.Z.; Writing—original draft, J.Z.; Writing—review & editing, K.Z., H.W., G.L. and Y.C. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the National Natural Science Foundation of China (22278426, 21878133, and 21908082), the Natural Science Foundation of Jiangsu Province (BK20190854), China Postdoctoral Science Foundation (2021M701472), and the Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX22_3688), Science Foundation of China University of Petroleum, Beijing (ZX20220042, ZX20220044).

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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Catalysts 13 00061 g001 550
Figure 1. XRD patterns of as-prepared Cu2MoS4 and FeMoS4.
Figure 1. XRD patterns of as-prepared Cu2MoS4 and FeMoS4.
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Figure 2. (a,c) SEM, (e) TEM, and (g) elemental mapping images of Cu2MoS4; (b,d) SEM, (f) TEM, and (h) elemental mapping images of FeMoS4.
Figure 2. (a,c) SEM, (e) TEM, and (g) elemental mapping images of Cu2MoS4; (b,d) SEM, (f) TEM, and (h) elemental mapping images of FeMoS4.
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Figure 3. XPS spectra of as-prepared Cu2MoS4 nanostructures: (a) survey spectra; core level spectra of (c) Cu 2p, (e) Mo 3d, (g) S 2p and FeMoS4 nanostructures: (b) survey spectra; core level spectra of (d) Fe 2p, (f) Mo 3d, (h) S 2p.
Figure 3. XPS spectra of as-prepared Cu2MoS4 nanostructures: (a) survey spectra; core level spectra of (c) Cu 2p, (e) Mo 3d, (g) S 2p and FeMoS4 nanostructures: (b) survey spectra; core level spectra of (d) Fe 2p, (f) Mo 3d, (h) S 2p.
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Figure 4. Effect of different synthesis conditions for the adsorption of Cu2MoS4 ((a) the copper source and temperature, (b) the mass of CuBr) and FeMoS4 ((c) the temperature and (d) the mass of FeCl2·4H2O) to CTC. (Csorbent = 0.4 g/L, C0 = 100 mg/L, T = 298 K).
Figure 4. Effect of different synthesis conditions for the adsorption of Cu2MoS4 ((a) the copper source and temperature, (b) the mass of CuBr) and FeMoS4 ((c) the temperature and (d) the mass of FeCl2·4H2O) to CTC. (Csorbent = 0.4 g/L, C0 = 100 mg/L, T = 298 K).
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Figure 5. (a) Adsorption kinetics and fitting results of (b) pseudo-first-order model, (c) pseudo-second-order model, (d) intra-particle diffusion model, (e) Elovich model. (Csorbent = 0.2 g/L, C0 = 100 mg/L, T = 298 K).
Figure 5. (a) Adsorption kinetics and fitting results of (b) pseudo-first-order model, (c) pseudo-second-order model, (d) intra-particle diffusion model, (e) Elovich model. (Csorbent = 0.2 g/L, C0 = 100 mg/L, T = 298 K).
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Figure 6. Adsorption isotherms of CTC onto (a) Cu2MoS4 and (b) FeMoS4 (Csorbent = 0.2 g/L).
Figure 6. Adsorption isotherms of CTC onto (a) Cu2MoS4 and (b) FeMoS4 (Csorbent = 0.2 g/L).
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Figure 7. Effect of (a) temperature, (b) solution coexisting ions, (c) pH, and (d) antibiotic contaminants on adsorption capacity (Csorbent = 0.5 g/L, C0 = 100 mg/L).
Figure 7. Effect of (a) temperature, (b) solution coexisting ions, (c) pH, and (d) antibiotic contaminants on adsorption capacity (Csorbent = 0.5 g/L, C0 = 100 mg/L).
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Figure 8. (a) Adsorption of regeneration performance and (b) FTIR spectra of Cu2MoS4, FeMoS4, Cu2MoS4, and FeMoS4 after cycle.
Figure 8. (a) Adsorption of regeneration performance and (b) FTIR spectra of Cu2MoS4, FeMoS4, Cu2MoS4, and FeMoS4 after cycle.
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Table
Table 1. Adsorption kinetics models parameters.
Table 1. Adsorption kinetics models parameters.
ModelParameterCu2MoS4FeMoS4
qe,exp (mg/g)470.81477.79
Pseudo-first-orderqe,cal (mg/g)170.54293.82
R20.9470.980
k1 × 10−3 (min−1)1.112.27
Pseudo-second-orderqe,cal (mg/g)467.29490.19
R20.9980.998
k2 × 10−5 (g/mg/min)3.942.31
t1/2 (min)54.3288.47
h (mg/g/min)8.615.54
Intra-particle kd1 (mg/g/min)21.1616.17
diffusionI1163.9496.31
R20.7790.963
Elovichα (mg/g/min)72.06189.859
β (g/mg)0.006970.0147
R20.9710.966
Table
Table 2. Adsorption isotherm parameters for CTC onto Cu2MoS4 and FeMoS4.
Table 2. Adsorption isotherm parameters for CTC onto Cu2MoS4 and FeMoS4.
ModelsParametersSamples
Cu2MoS4FeMoS4
LangmuirKL (L/mg)0.2760.108
qm (mg/g)1203.812169.19
RL0.007–0.0340.018–0.084
R20.9920.993
APE%2.851.93
FreundlichKF (mg/g)499.79425.01
1/n0.1830.369
R20.9030.916
APE%8.089.16
TemkinKT (L/mg)11.3781.345
B167.33422.29
R20.9620.986
APE%5.574.36
Table
Table 3. Comparison of different adsorbents for optimal CTC adsorption capacity.
Table 3. Comparison of different adsorbents for optimal CTC adsorption capacity.
AdsorbentAdsorption Capacity (mg/g)Ref.
MWCNT/MIL-53(Fe)180.68[48]
Fe(III)@CNFs232.56[49]
Al-MOF/GO240.13[50]
APT/C@NiFe-LDHs308.21[51]
Fe3O4/ZIF-8-G608.06[52]
CoO-c/P-BNFs655.47[53]
Cu2MoS41203.81This work
FeMoS42169.19This work
Table
Table 4. Adsorption thermodynamic parameters.
Table 4. Adsorption thermodynamic parameters.
ΔH0 (kJ/mol)ΔS0 (kJ/mol/K)ΔG0 (kJ/mol)
298 K308 K318 K328 K
FeMoS419.450.101−10.44−11.81−12.97−13.38
Cu2MoS459.610.225−7.41−10.21−12.81−14.01
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Zhou, J.; Zhu, K.; Wang, Y.; Cui, P.; Zhu, L.; Wu, H.; Hua, M.; Huang, Y.; Luo, G.; Chao, Y.; et al. Facile Hydrothermal Synthesis of Cu2MoS4 and FeMoS4 for Efficient Adsorption of Chlortetracycline. Catalysts 2023, 13, 61. https://doi.org/10.3390/catal13010061

AMA Style

Zhou J, Zhu K, Wang Y, Cui P, Zhu L, Wu H, Hua M, Huang Y, Luo G, Chao Y, et al. Facile Hydrothermal Synthesis of Cu2MoS4 and FeMoS4 for Efficient Adsorption of Chlortetracycline. Catalysts. 2023; 13(1):61. https://doi.org/10.3390/catal13010061

Chicago/Turabian Style

Zhou, Junhui, Keyu Zhu, Yong Wang, Peng Cui, Linhua Zhu, Haofeng Wu, Mingqing Hua, Yan Huang, Guiling Luo, Yanhong Chao, and et al. 2023. "Facile Hydrothermal Synthesis of Cu2MoS4 and FeMoS4 for Efficient Adsorption of Chlortetracycline" Catalysts 13, no. 1: 61. https://doi.org/10.3390/catal13010061

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