A multifunctional magnetic nanomaterial CuS / Fe3O4@C, its preparation method and application
By synthesizing CuS/Fe3O4@C nanomaterials on biomass charcoal sponge, the problems of rapid detection and efficient removal of Hg(II) and degradation of organic dyes were solved, realizing the application of low-cost, multifunctional nanoenzyme materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- LIAONING UNIVERSITY
- Filing Date
- 2024-04-07
- Publication Date
- 2026-05-15
AI Technical Summary
Existing technologies are insufficient for the rapid and cost-effective detection and removal of heavy metal ions (Hg(II)) and degradation of organic dyes in industrial wastewater, and traditional nanozyme materials have limited applications in degradation.
Using biomass charcoal fiber sponge as a substrate, a multifunctional magnetic nanomaterial CuS/Fe3O4@C was synthesized. Utilizing its abundant active sites and specific surface area, Hg(II) was detected by colorimetry and organic dyes were degraded under light conditions.
It achieves efficient removal of Hg(II) and efficient degradation of organic dyes by portable colorimetric detection, with a degradation efficiency of over 95%. The synergistic effect of CuS and Fe3O4 enhances the activity of nanozymes.
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Figure CN118287034B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of nanomaterials technology, specifically relating to a multifunctional magnetic nanomaterial CuS / Fe3O4@C, its preparation method, and its application in the detection / removal of Hg(II) and degradation of organic dyes. Background Technology
[0002] Organic pigments are insoluble organic compounds, typically added to substrates in a highly dispersed state to color them. Current figures indicate that the textile, leather, paint, food, and consumer electronics industries generate millions of tons of organic dyes and inorganic waste annually. Organic dye pollutants, such as methylene blue, methyl orange, and rhodamine B, have been found in industrial wastewater in today's environment. In addition, heavy metal ions are also a major cause of environmental pollution. Heavy metal ions can enter the human body through water and food, leading to permanent chronic poisoning. Therefore, the detection of heavy metal ions is crucial for protecting ecosystems and human health. However, most platforms for heavy metal ion analysis (such as atomic absorption spectroscopy, chromatography, chemiluminescence, electrochemical analysis, fluorescence spectroscopy, and inductively coupled plasma mass spectrometry) rely on expensive instruments and complex experimental techniques. Therefore, there is an urgent need for a rapid, accurate, and low-cost method to detect trace amounts of heavy metal ions. However, current nanozyme materials focus on colorimetric detection, with limited applications in degradation. Therefore, there is a need to design a multifunctional nanozyme material that can simultaneously perform detection, adsorption, and degradation for efficient analytical applications.
[0003] Biochar, a material with numerous pore sizes and a large specific surface area, has garnered significant attention for its adsorption properties. Meanwhile, metal nanoparticles possess inherent advantages, including multifunctional components, abundant redox active sites, and open coordination structures. The emergence of bimetallic nanoparticles has revealed their unique enzymatic activity, offering potential applications in colorimetric sensing. Therefore, there is an urgent need for the rational design and research of biochar and metal nanoparticles, aiming to create a low-cost, multifunctional material for colorimetry, adsorption, and degradation. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention synthesizes a multifunctional magnetic nanomaterial, CuS / Fe3O4@C, using biomass charcoal sponge as a substrate. This material possesses abundant active sites and a large specific surface area. It can be used for portable colorimetry, Hg(II) removal, and the degradation of organic dyes.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: a multifunctional magnetic nanomaterial CuS / Fe3O4@C, the preparation method of which includes the following steps:
[0006] 1) Preparation of Fe3O4@C: The pretreated loofah sponge was completely immersed in an aqueous solution of Fe(NO3)3·9H2O and magnetically stirred at 75-85℃ for 3-4 hours to allow Fe to form a soluble compound. 3+ Adsorb as much material as possible onto the loofah sponge, then add KOH solution and stir at 95-105℃ until the water is completely evaporated. Carbonize the obtained material at 600℃ under N2 atmosphere for 2-3 hours. Wash the resulting material with water to remove K. + After drying, the composite material Fe3O4@C is obtained;
[0007] 2) Preparation of CuS / Fe3O4@C: Copper chloride was dissolved in ethylene glycol solution, thiourea was added, and the mixture was stirred at room temperature for 4-5 h. Fe3O4@C was then added, and the mixture was stirred at room temperature for another 3-4 h. The resulting product was subjected to a hydrothermal reaction. After the reaction was completed, the product was washed and dried to obtain CuS / Fe3O4@C.
[0008] Further, in step 1), the pretreatment of the loofah sponge involves adding sodium hydroxide solution to the chopped loofah sponge, soaking for 1-2 hours, rinsing with deionized water, and then drying at 100-120°C for 20-24 hours.
[0009] Furthermore, the concentration of the sodium hydroxide solution is 3-5 wt%.
[0010] Furthermore, in step 1), the concentration ratio of Fe(NO3)3·9H2O to KOH is 1:10.
[0011] Furthermore, in step 2), the molar ratio of copper chloride to thiourea is 1:4.
[0012] Furthermore, in step 2), the hydrothermal reaction is carried out at a temperature of 120°C for a heating time of 12 hours.
[0013] Furthermore, in step 2), the mass ratio of copper chloride:Fe3O4@C is 1:1.0-1.5.
[0014] This invention provides the application of a multifunctional magnetic nanomaterial CuS / Fe3O4@C in the detection of Hg(II).
[0015] This invention provides the application of a multifunctional magnetic nanomaterial CuS / Fe3O4@C in the adsorption of Hg(II).
[0016] This invention provides the application of a multifunctional magnetic nanomaterial CuS / Fe3O4@C in the degradation of organic dyes.
[0017] The beneficial effects of this invention are as follows: The multifunctional magnetic nanomaterial CuS / Fe3O4@C provided by this invention has abundant active sites and a large specific surface area. It can be used for portable colorimetry, removal of Hg(II), and degradation of organic dyes. Moreover, the inherent synergistic effect of CuS and Fe3O4 greatly enhances the peroxidase-like activity of the nanozyme, catalyzing the generation of more reactive oxygen species. In the presence of Hg(II), the enzyme-like activity is significantly inhibited, thus establishing a method for colorimetric removal of Hg(II). These reactive oxygen species can be used to degrade organic dyes under light conditions, with a degradation efficiency of over 95%. Attached Figure Description
[0018] Figure 1 This is a scanning electron microscope image of the CuS / Fe3O4@C morphology;
[0019] Among them, (a) is a scanning electron microscope image of loofah sponge; (b) is a scanning electron microscope image of CuS / Fe3O4@C.
[0020] Figure 2 These are the full XPS spectra (a) and electron binding energy spectra of Cu 2p (b) and Fe 2p (c) of CuS / Fe3O4@C materials.
[0021] Figure 3 This is the condition optimization diagram for the material CuS / Fe3O4@C;
[0022] (a) represents pH optimization; (b) represents temperature optimization.
[0023] Figure 4 This is a free radical trapping diagram of the material CuS / Fe3O4@C.
[0024] Figure 5 This is a linear relationship graph of CuS / Fe3O4@C and Hg(II) in Example 2.
[0025] Figure 6 This is a graph showing the removal efficiency of Hg(II) by the material CuS / Fe3O4@C in Example 3.
[0026] Figure 7 This is a graph showing the degradation efficiency of organic dyes by the material CuS / Fe3O4@C in Example 4.
[0027] Figure 8 This is a diagram illustrating the synthesis process of the material CuS / Fe3O4@C.
[0028] Figure 9 This is a schematic diagram illustrating the multifunctional application principle of the material CuS / Fe3O4@C. Detailed Implementation
[0029] Example 1 Preparation of a multifunctional magnetic nanomaterial (CuS / Fe3O4@C) (I) Preparation of CuS / Fe3O4@C
[0030] 1. Pretreatment of loofah sponge:
[0031] Add sodium hydroxide solution (4wt%) to the chopped loofah sponge, soak for 1-2 hours to remove fat, rinse with water, and then dry at 110℃ for 24 hours.
[0032] 2. Preparation of Fe3O4@C
[0033] Completely immerse the loofah sponge in a 0.1M Fe(NO3)3·9H2O aqueous solution and stir magnetically at 80℃ for 3-4 hours to allow the Fe... 3+ Adsorb as much of the material as possible onto the loofah sponge, then add KOH until the KOH concentration reaches 1.0 M, and stir at 100°C until all the water evaporates. Subsequently, carbonize the obtained material at 600°C under a N2 atmosphere for 2 hours. Rinse the resulting material with water to remove K. + Then, it is dried at 60℃ to obtain the composite material, namely Fe3O4@C.
[0034] 3. Preparation of CuS / Fe3O4@C
[0035] CuCl2 (0.17 g, 0.001 mol) was dissolved in 60 mL of ethylene glycol solution, and 0.00398 mol of thiourea was added. The mixture was stirred at room temperature for 4 h, then 0.2 g of Fe3O4@C was added, and the mixture was stirred for 3 h. The reaction was then carried out hydrothermally at 120 °C for 12 h. The resulting product was washed and dried at 60 °C to obtain CuS / Fe3O4@C. The preparation process is as follows: Figure 8 As shown.
[0036] (II) Testing
[0037] 1. The morphology of CuS / Fe3O4@C was studied and analyzed using SEM.
[0038] Figure 1 (a) is a scanning electron microscope (SEM) image of loofah sponge, and (b) is a scanning electron microscope (SEM) image of CuS / Fe3O4@C. The magnetic porous carbon composite material CuS / Fe3O4@C was obtained using a one-pot carbonization method. It can be clearly seen that the biochar surface is loaded with nanoparticles, exhibiting a good morphology.
[0039] Figure 2 These are the full XPS spectra (a) and electron binding energy spectra of Cu 2p (b) and Fe 2p (c) of CuS / Fe3O4@C materials. Figure 2 Prove that CuS / Fe3O4@C has the metals Cu and Fe in variable valence states.
[0040] 2. Optimization of peroxidase activity of CuS / Fe3O4@C.
[0041] The conditions for CuS / Fe3O4@C were optimized as follows: 30 μL of CuS / Fe3O4@C (0.3 mg / mL) was added... -1 50 μL of H₂O₂ (30%) and 50 μL of TMB (10 mM) were added to an acetate-sodium acetate buffer solution, incubated for 10 min, and the absorbance was recorded at 652 nm. Optimal conditions were obtained by varying the pH of the acetate-sodium acetate buffer solution (3-6.5) and the reaction temperature (-4-50℃).
[0042] Figure 3 This is the condition optimization diagram for the material CuS / Fe3O4@C. Figure 3 (a) describes the pH optimization of the acetate-sodium acetate buffer solution. Figure 3 It can be seen that the optimal pH range is 3-6.5, with the optimal pH being 4.5. Figure 3 (b) optimizes the temperature, by Figure 3 It can be seen that the optimal temperature is 20℃.
[0043] 3. Mechanism study on peroxidase activity of CuS / Fe3O4@C.
[0044] To gain a deeper understanding of the mechanism of peroxidase-like catalytic activity of CuS / Fe3O4@C, an experiment was conducted. The method is as follows: 30 μL of CuS / Fe3O4@C (0.3 mg / mL) was added... -1 50 μL of H₂O₂ (30%) was added to different scavenging agents, followed by 50 μL of TMB (10 mM) and 870 μL of acetate-sodium acetate buffer solution (pH 4.0), and the absorbance was recorded. Benzoquinone was used as a superoxide radical scavenger, histidine as a singlet oxygen scavenger, and isopropanol as a hydroxyl radical scavenger. The results were compared with those of the blank sample.
[0045] Figure 4 This is a free radical capture diagram of the material CuS / Fe3O4@C, demonstrating that the peroxidase-like activity of CuS / Fe3O4@C is generated by hydroxyl radicals (·OH) and singlet oxygen. The principle is as follows: Figure 9 CuS / Fe3O4@C, as a multifunctional application material, enables the detection and adsorption of metal ions and the degradation of organic dyes under light conditions. The CuS / Fe3O4@C of this invention can accelerate the decomposition of hydrogen peroxide to generate hydroxyl radicals (·OH) and singlet oxygen.
[0046] Example 2: Application of multifunctional magnetic nanomaterial CuS / Fe3O4@C in colorimetric detection of Hg(II)
[0047] Use a concentration of 1 mg / mL -1 Hg(II) was detected in CuS / Fe3O4@C at pH=4.5 and temperature=20℃.
[0048] The method is as follows: Add 50 μL of Hg(II) solution of different concentrations to 20 μL of 1 mg·mL⁻¹ solution. -1 The sample was incubated in a mixture of CuS / Fe3O4@C solution and 870 μL of acetate-sodium acetate buffer solution at pH 4.5. After waiting for 10 min, 50 μL of TMB (10 mM) and 50 μL of 15 wt% H2O2 solution were added, and the mixture was incubated for 10 min. The absorbance was then measured at a wavelength of 652 nm.
[0049] The detection mechanism mainly involves the adsorption of Hg(II) by biochar and the formation of HgS by S and Hg(II). Figure 5 This is a linear relationship graph between the materials CuS / Fe3O4@C and Hg(II). For example... Figure 5 As shown, the absorbance signal weakens with increasing Hg(II) concentration. Furthermore, there is a linear relationship between absorbance and concentration.
[0050] Example 3: Application of multifunctional magnetic nanomaterial CuS / Fe3O4@C in the adsorption of Hg(II)
[0051] The method is as follows: 5.0 mg CuS / Fe3O4@C was added to 25 mL of Hg(II) aqueous solution (100 mg / L), and the mixture was stirred and adsorbed for 60 min. Then, it was filtered through a 0.22 μm microfiltration membrane. The concentration of the remaining Hg(II) was determined using inductively coupled plasma optical emission spectrometry (ICP-OES), and the corresponding Hg(II) removal efficiency was calculated.
[0052] Figure 6 This is a graph showing the removal efficiency of Hg(II) by the material CuS / Fe3O4@C. (The graph is derived from...) Figure 6 It can be seen that the removal efficiency gradually increases with time, reaching 93% at 50 minutes. Then, with further time, the removal rate tends to balance, and remains basically unchanged at 80 minutes.
[0053] Example 4: Application of multifunctional magnetic nanomaterial CuS / Fe3O4@C in the degradation of organic dyes
[0054] The method is as follows: Add 25 mL of organic dye (10 mg·L⁻¹) -1Methylene blue (MB) was added to a first 50 mL Erlenmeyer flask, and 2 mL of deionized water was added to a second Erlenmeyer flask. Subsequently, 0.5 mg of CuS / Fe3O4@C and 2 mL of hydrogen peroxide solution were added to each flask. After irradiation for 5–40 min, 2 mL of the suspension was extracted, filtered through a syringe using a 0.22 μm mixed fiber membrane, and absorbance was measured.
[0055] Figure 7 This is a graph showing the degradation efficiency of organic dyes by CuS / Fe3O4@C. (Source: [Graph showing degradation efficiency of CuS / Fe3O4@C]) Figure 7 As can be seen, the degradation efficiency gradually increases and the dye color gradually lightens as time goes on. When the time reaches 40 minutes, the degradation efficiency is close to 100%.
Claims
1. The application of a multifunctional magnetic nanomaterial CuS / Fe3O4@C in colorimetric detection of Hg(II) or degradation of organic dyes, characterized in that, Hydrogen peroxide was added to the colorimetric detection of Hg(II); hydrogen peroxide was added to the degradation of organic dyes and then subjected to light irradiation; The preparation method of the multifunctional magnetic nanomaterial CuS / Fe3O4@C includes the following steps: 1) Preparation of Fe3O4@C: The pretreated loofah sponge was completely immersed in Fe(NO3)3·9H2O aqueous solution and magnetically stirred at 75-85 ℃ for 3-4 h. Then KOH solution was added and stirred at 95-105 ℃ until the water was completely evaporated. The obtained material was carbonized at 600 ℃ under N2 atmosphere for 2-3 h. The obtained material was washed with water and dried to obtain the composite material Fe3O4@C. 2) Preparation of CuS / Fe3O4@C: Copper chloride was dissolved in ethylene glycol solution, thiourea was added, and the mixture was stirred at room temperature for 4-5 h. Fe3O4@C was then added, and the mixture was stirred at room temperature for another 3-4 h. The resulting product was subjected to a hydrothermal reaction. After the reaction was completed, the product was washed and dried to obtain CuS / Fe3O4@C.
2. The application of the multifunctional magnetic nanomaterial CuS / Fe3O4@C according to claim 1 in colorimetric detection of Hg(II) or degradation of organic dyes, characterized in that, In step 1), the pretreatment of the loofah sponge involves adding sodium hydroxide solution to the chopped loofah sponge, soaking for 1-2 hours, rinsing with deionized water, and then drying at 100-120 °C for 20-24 hours.
3. The application of the multifunctional magnetic nanomaterial CuS / Fe3O4@C according to claim 2 in colorimetric detection of Hg(II) or degradation of organic dyes, characterized in that, The concentration of the sodium hydroxide solution is 3-5 wt%.
4. The application of the multifunctional magnetic nanomaterial CuS / Fe3O4@C according to claim 1 in colorimetric detection of Hg(II) or degradation of organic dyes, characterized in that, In step 1), the concentration ratio of Fe(NO3)3·9H2O to KOH is 1:
10.
5. The application of the multifunctional magnetic nanomaterial CuS / Fe3O4@C according to claim 1 in colorimetric detection of Hg(II) or degradation of organic dyes, characterized in that, In step 2), the molar ratio of copper chloride to thiourea is 1:
4.
6. The application of the multifunctional magnetic nanomaterial CuS / Fe3O4@C according to claim 1 in colorimetric detection of Hg(II) or degradation of organic dyes, characterized in that, In step 2), the hydrothermal reaction is carried out at a temperature of 120 °C for a heating time of 12 h.
7. The application of the multifunctional magnetic nanomaterial CuS / Fe3O4@C according to claim 1 in colorimetric detection of Hg(II) or degradation of organic dyes, characterized in that, In step 2), the mass ratio of copper chloride to Fe3O4@C is 1:1.0-1.5.