An Ag-CuCo 0.5 Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater
By preparing an Ag-CuCo0.5Fe1.5O4 composite SERS substrate, the problems of insufficient sensitivity and stability in the detection of malachite green in the existing technology are solved, realizing efficient and rapid detection of malachite green, which is suitable for on-site detection and real-time control of industrial wastewater.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- LIAONING UNIVERSITY
- Filing Date
- 2026-06-29
- Publication Date
- 2026-07-24
AI Technical Summary
Existing technologies have not yet developed composite SERS substrates with high enhanced activity, excellent stability, and good practicality for the detection of malachite green in industrial wastewater, making it difficult to achieve high sensitivity and rapid trace detection.
Ag-CuCo0.5Fe1.5O4 composite material was used as the SERS substrate. Silver nanoparticles were grown on the surface of CuCo0.5Fe1.5O4 nanoparticles by in-situ reduction method to form Ag-CuCo0.5Fe1.5O4 composite SERS substrate for the detection of malachite green.
It enables trace detection of malachite green, possesses good chemical stability and anti-interference ability, can quickly capture Raman signals, and is suitable for batch rapid detection of malachite green in industrial wastewater, adaptable to on-site detection and real-time control.
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Figure CN122448824A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of SERS detection technology, specifically relating to an Ag-CuCo... 0.5 Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater. Background Technology
[0002] Industrial production processes generate large amounts of harmful wastewater. Malachite green (MG), a typical triphenylmethane organic dye, was once widely used in aquaculture, textile printing and dyeing, and related industries, and is one of the important pollutants in environmental water bodies. MG has strong biotoxicity, mutagenicity, and potential carcinogenicity, and easily accumulates in aquatic environments and organisms, even at extremely low concentrations, it can harm aquatic ecosystems. Therefore, establishing efficient trace detection methods for MG in water bodies has become an important issue that urgently needs to be addressed in the fields of environmental monitoring and water pollution control.
[0003] Surface-enhanced Raman scattering (SERS) technology boasts advantages such as fast detection speed, simple sample pretreatment, and strong ultra-trace identification capabilities, showing broad application prospects in the rapid analysis of organic dye pollutants. The construction of high-performance SERS substrates is crucial for achieving highly sensitive detection. The localized surface plasmon resonance effect of Ag NPs and CuCo... 0.5 Fe 1.5 The cation rearrangement and lattice distortion effects generated by O4 synergistically promote the separation and transport of photogenerated carriers. Simultaneously, the abundant defect sites and tunable electronic structure formed by the synergistic regulation of Co / Fe facilitate the establishment of efficient interfacial charge transfer channels, thereby significantly enhancing the Raman signal. Malachite green (MG), a typical triphenylmethane dye, exhibits strong biotoxicity and environmental persistence; its residues in industrial wastewater pose potential hazards to the ecological environment and human health. Existing research has not yet yielded results for Ag-CuCo... 0.5 Fe 1.5 There have been reports on the use of O4 composite materials as SERS substrates for the detection of malachite green in industrial wastewater. Therefore, there is an urgent need to develop a composite SERS substrate that combines high reinforcing activity, excellent stability, and good practicality to overcome the shortcomings of existing technologies and meet the practical needs of rapid detection of trace amounts of malachite green. Summary of the Invention
[0004] To address the problems of existing technologies, this invention provides an Ag-CuCo... 0.5 Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater.
[0005] The technical solution of the present invention is as follows: an Ag-CuCo 0.5Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater. The method is as follows: Ag-CuCo... 0.5 Fe 1.5 The O4 composite SERS substrate was immersed in a solution containing malachite green for 1 hour, then removed and air-dried. The dried Ag-CuCo substrate was then... 0.5 Fe 1.5 Raman scattering spectroscopy was performed on the O4 composite SERS substrate.
[0006] The above-mentioned Ag-CuCo 0.5 Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater, wherein the concentration of malachite green is 10. -3 M-10 -8 M.
[0007] The above-mentioned Ag-CuCo 0.5 Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater, the Ag-CuCo 0.5 Fe 1.5 The preparation method of O4 composite SERS substrate includes the following steps.
[0008] 1) Disperse copper nitrate, cobalt nitrate, ferric nitrate and citric acid in deionized water and stir to obtain a mixed solution.
[0009] 2) Dry the mixed solution obtained in step 1) until completely dry, grind and calcine thoroughly, allow it to cool naturally, wash several times and dry again to obtain CuCo. 0.5 Fe 1.5 O4 nanoparticles.
[0010] 3) CuCo 0.5 Fe 1.5 O4 nanoparticles were dispersed in deionized water, ultrasonically dispersed, and then silver nitrate solution was added and stirred.
[0011] 4) Add ascorbic acid solution to the mixed solution obtained in step 3), stir, and grow silver nanoparticles using in-situ reduction method.
[0012] 5) The mixed solution obtained in step 4) is washed, dried, and ground to obtain the target product Ag-CuCo. 0.5 Fe 1.5 O 4。
[0013] 6) Take the Ag-CuCo obtained in step 5) 0.5 Fe 1.5O4 was prepared into a solution, drop-coated onto a clean glass slide, and dried to obtain Ag-CuCo. 0.5 Fe 1.5 O4 composite SERS substrate.
[0014] The above-mentioned Ag-CuCo 0.5 Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater, in step 1), the ratio of copper nitrate trihydrate: cobalt nitrate hexahydrate: ferric nitrate nonahydrate: citric acid monohydrate = 0.966g±0.048g: 0.582g±0.029g: 2.424g±0.121g: 4.203g±0.210g.
[0015] The above-mentioned Ag-CuCo 0.5 Fe 1.5 In the application of O4 composite SERS substrate in the detection of malachite green in wastewater, in step 2), the calcination temperature is 500-600℃, the heating rate is 5℃ / min, and the time is 3-4h.
[0016] The above-mentioned Ag-CuCo 0.5 Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater, in steps 3) and 4), the CuCo 0.5 Fe 1.5 O4 nanoparticles: silver nitrate solution: ascorbic acid solution = 50mg: 2mL: 6mL.
[0017] The above-mentioned Ag-CuCo 0.5 Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater, in steps 3) and 4), the CuCo 0.5 Fe 1.5 The concentration of O4 nanoparticles was 2.5 ± 0.125 mg / mL, the concentration of silver nitrate solution was 50 mM, and the concentration of ascorbic acid solution was 50 mM.
[0018] The above-mentioned Ag-CuCo 0.5 Fe 1.5 In the application of O4 composite SERS substrate in the detection of malachite green in wastewater, step 4) describes the in-situ reduction method, which involves reacting at 20-25℃ for 1-1.5 hours.
[0019] The above-mentioned Ag-CuCo 0.5 Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater, step 6), Ag-CuCo 0.5 Fe 1.5The concentration of the O4 solution is 1 mg / mL.
[0020] The beneficial effects of this invention are as follows.
[0021] 1. This invention prepares an Ag-CuCo 0.5 Fe 1.5 The O4 composite SERS substrate can sample analytes in industrial wastewater, enabling trace detection of malachite green.
[0022] 2. The Ag-CuCo prepared by this invention 0.5 Fe 1.5 The O4 composite SERS substrate possesses excellent chemical stability and anti-interference capabilities. The localized surface plasmon resonance (LSPR) effect of Ag nanoparticles, combined with the abundant defect states brought about by Co / Fe synergistic regulation, can rapidly capture the Raman signal of malachite green molecules. The single detection time is short, enabling rapid batch detection of malachite green in industrial wastewater, which is suitable for the actual needs of on-site detection and real-time control of industrial wastewater discharge.
[0023] 3. The Ag-CuCo prepared by this invention 0.5 Fe 1.5 The O4 composite SERS substrate combines strong SERS enhancement effect, efficient targeted adsorption capacity for malachite green molecules, excellent structural stability, and simple operation performance, effectively solving the shortcomings of existing malachite green detection methods and substrates, and providing a reliable technical solution for efficient, sensitive, and rapid detection of malachite green in industrial wastewater. Attached Figure Description
[0024] Figure 1 CuCo prepared in Example 1 0.5 Fe 1.5 O4 and Ag-CuCo prepared in Example 2 0.5 Fe 1.5 X-ray diffraction pattern of O4-2.
[0025] Figure 2 Ag-CuCo 0.5 Fe 1.5 O4-1, Ag-CuCo 0.5 Fe 1.5 O4-2, Ag-CuCo 0.5 Fe 1.5 O4-3 composite SERS substrate detection MG solution (10) -3 Comparison of SERS spectra of M).
[0026] Figure 3 CuCo 0.5 Fe 1.5 O4 composite SERS substrate and Ag-CuCo0.5 Fe 1.5 O4-2 composite SERS substrate detection MG solution (10) -3 Comparison of SERS spectra of M).
[0027] Figure 4 Ag-CuCo prepared in Example 2 0.5 Fe 1.5 SERS spectra of MG solutions of different concentrations obtained by detecting the O4-2 composite SERS substrate.
[0028] Figure 5 Ag-CuCo prepared in Example 2 0.5 Fe 1.5 O4-2 composite SERS substrate was immersed in MG solution (10) -3 After 1 hour, the solution was removed and dried. After one month at room temperature, MG solutions were obtained from 6 randomly selected points on the substrate (10). -3 M) Raman spectrum.
[0029] Figure 6 Ag-CuCo prepared in Example 2 0.5 Fe 1.5 Six test points were randomly selected from the O4-2 composite SERS substrate at the MG characteristic Raman peak at 1616 cm⁻¹. -1 A bar chart showing the intensity values at a given location. Detailed Implementation
[0030] Example 1.
[0031] CuCo 0.5 Fe 1.5 The preparation method of O4 is as follows.
[0032] 0.966 g of copper nitrate trihydrate, 2.424 g of ferric nitrate nonahydrate, 0.582 g of cobalt nitrate hexahydrate, and 4.203 g of citric acid monohydrate were dispersed in 20 mL of deionized water. After magnetic stirring for 30 min, the mixture was transferred to an oven at 80 °C and dried completely. After thorough grinding, the mixture was transferred to a muffle furnace and calcined at 500 °C for 3-4 h at a heating rate of 5 °C / min. After natural cooling, the mixture was washed three times with deionized water and dried to obtain CuCo. 0.5 Fe 1.5 O4 nanoparticles.
[0033] Example 2.
[0034] Ag-CuCo 0.5 Fe 1.5 The preparation method of O4 composite SERS substrate is as follows.
[0035] Take 50 mg of CuCo prepared in Example 1 0.5 Fe 1.5 O4 nanoparticles were dispersed in a beaker containing 20 mL of deionized water and ultrasonically dispersed for 30 min. Then, 2 mL of 50 mM silver nitrate solution was added, and the mixture was magnetically stirred for 10 min. Next, 6 mL of 50 mM ascorbic acid was added to the solution, and the mixture was magnetically stirred for another 50 min. Silver nanoparticles were grown using an in-situ reduction method. Finally, the mixture was centrifuged and washed three times (centrifugation rate 8000 r / min, centrifugation time 10 min), and then dried at 60 °C for 8 h to obtain the target product Ag-CuCo. 0.5 Fe 1.5 O4; Take 20 μL of CuCo 0.5 Fe 1.5 O4 solution (1 mg / mL) was dropped onto a clean 25 × 76 mm glass slide and dried to obtain Ag-CuCo. 0.5 Fe 1.5 O4 composite SERS substrate, labeled Ag-CuCo 0.5 Fe 1.5 O4-2.
[0036] Figure 1 Ag-CuCo prepared in Example 2 0.5 Fe 1.5 X-ray diffraction pattern of O4-2. Figure 1 In the figure, the characteristic diffraction peaks appearing at 2θ = 38.2°, 44.4°, 64.5°, and 77.5° correspond to the characteristic peaks of Ag; CuCo 0.5 Fe 1.5 O4 exhibits characteristic peaks at 2θ = 30.1°, 35.7°, 38.9°, 57°, and 62.9°. Ag-CuCo 0.5 Fe 1.5 CuCo can be observed in O4. 0.5 Fe 1.5 The characteristic peaks of O4 and Ag indicate that Ag-CuCo 0.5 Fe 1.5 O4 composite SERS substrate was successfully prepared.
[0037] Example 3.
[0038] Ag-CuCo 0.5 Fe 1.5 The preparation method of the O4 composite SERS substrate contrast sample is as follows.
[0039] According to the preparation method of Example 2, CuCo 0.5 Fe 1.5The amount of O4 nanoparticles remained constant at 50 mg, while the amount of silver nitrate solution was changed to 1 mL and 4 mL, respectively. After magnetic stirring until homogeneous, 3 mL and 8 mL of ascorbic acid solution were added to the above solution, and the mixture was magnetically stirred for 50 min. Finally, the mixed solution was centrifuged and washed three times (centrifugation rate 8000 r / min, centrifugation time 10 min) and dried at 60 °C for 8 h to obtain the target product. 20 μL of the target product solution (1 mg / mL) was dropped onto a clean glass slide of 25 × 76 mm to obtain Ag-CuCo. 0.5 Fe 1.5 O4 composite SERS substrate comparison samples, labeled Ag-CuCo, were used. 0.5 Fe 1.5 O4-1 and Ag-CuCo 0.5 Fe 1.5 O4-3.
[0040] Ag-CuCo 0.5 Fe 1.5 O4-1, Ag-CuCo 0.5 Fe 1.5 O4-2, Ag-CuCo 0.5 Fe 1.5 O4-3 composite SERS substrates were immersed in a concentration of 10... -3 The substrate was immersed in MG solution for 1 hour, then removed and dried in air. The dried composite SERS substrate was then subjected to Raman scattering spectroscopy.
[0041] Figure 2 Ag-CuCo 0.5 Fe 1.5 O4-1, Ag-CuCo 0.5 Fe 1.5 O4-2, Ag-CuCo 0.5 Fe 1.5 O4-3 composite SERS substrate detection MG solution (10) -3 Comparison of SERS spectra of M).
[0042] Example 4.
[0043] CuCo 0.5 Fe 1.5 The preparation method of O4 composite SERS substrate is as follows.
[0044] Take 20 μL of CuCo 0.5 Fe 1.5 O4 solution (1 mg / mL) was dropped onto a clean glass slide (25 × 76 mm) to obtain CuCo. 0.5 Fe 1.5 O4 composite SERS substrate.
[0045] CuCo 0.5 Fe 1.5 O4 composite SERS substrate was immersed in a concentration of 10 -3 The substrate was immersed in MG solution for 1 hour, then removed and dried in air. The dried composite SERS substrate was then subjected to Raman scattering spectroscopy.
[0046] Figure 3 CuCo 0.5 Fe 1.5 O4 composite SERS substrate and Ag-CuCo 0.5 Fe 1.5 O4-2 composite SERS substrate detection MG solution (10) -3 Comparison of SERS spectra of M).
[0047] Example 5.
[0048] Ag-CuCo 0.5 Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater.
[0049] Ag-CuCo 0.5 Fe 1.5 O4-2 composite SERS substrate was immersed in different concentrations (10) -3 M-10 -8 The substrate was immersed in a solution of MG for 1 hour, then removed and dried in air. The dried composite SERS substrate was then subjected to Raman scattering spectroscopy.
[0050] Figure 4 For this Ag-CuCo 0.5 Fe 1.5 O4-2 composite SERS substrate detection MG solution (10) -3 M-10 -8 SERS spectrum of M). Figure 4 As shown, the intensity of the characteristic peak SERS increases significantly with increasing MG solution concentration, even when the MG concentration is as low as 10. -8 M, 1616cm can still be clearly observed. -1 The characteristic peaks of the SERS spectrum at that location.
[0051] Figure 5 Ag-CuCo prepared in Example 2 0.5 Fe 1.5 O4-2 composite SERS substrate was immersed in MG solution (10) -3 After 1 hour, the solution was removed and dried. After one month at room temperature, MG solutions were obtained from 7 randomly selected points on the substrate (10). -3M) Raman spectrum. It can be seen from the figure that the intensity of its Raman characteristic peaks has not decreased significantly compared with a month ago, and the peak position and peak height of the 6 spectral curves are consistent, indicating that the signal response of the SERS substrate at different sites has good consistency. Figure 6 Therefore, the seven test points are located at 1616 cm on the Raman peak characteristic of the MG. -1 The intensity histogram at the specified location shows an RSD of 9.72%, indicating that the substrate maintains good signal reproducibility even after being placed at room temperature for one month. These results demonstrate that Ag-CuCo... 0.5 Fe 1.5 The O4-2 composite SERS substrate exhibits good sensitivity, stability, and uniformity, making it a reliable SERS substrate for detection.
Claims
1. An Ag-CuCo 0.5 Fe 1.5 Application of O4 composite SERS substrate in the detection of malachite green in wastewater.
2. The Ag-CuCo according to claim 1 0.5 Fe 1.5 The application of O4 composite SERS substrate in the detection of malachite green in wastewater is characterized by... The method is as follows: Add Ag-CuCo 0.5 Fe 1.5 The O4 composite SERS substrate was immersed in a solution containing malachite green for 1 hour, then removed and air-dried. The dried Ag-CuCo substrate was then... 0.5 Fe 1.5 Raman scattering spectroscopy was performed on the O4 composite SERS substrate.
3. An Ag-CuCo according to claim 2 0.5 Fe 1.5 The application of O4 composite SERS substrate in the detection of malachite green in wastewater is characterized by... The concentration of the malachite green was 10. -3 M-10 -8 M.
4. An Ag-CuCo according to any one of claims 1-3 0.5 Fe 1.5 The application of O4 composite SERS substrate in the detection of malachite green in wastewater is characterized by... The Ag-CuCo 0.5 Fe 1.5 The preparation method of O4 composite SERS substrate includes the following steps: 1) Disperse copper nitrate trihydrate, cobalt nitrate hexahydrate, ferric nitrate nonahydrate, and citric acid monohydrate in deionized water and stir to obtain a mixed solution; 2) Dry the mixed solution obtained in step 1) until completely dry, grind and calcine thoroughly, allow it to cool naturally, wash several times and dry again to obtain CuCo. 0.5 Fe 1.5 O4 nanoparticles; 3) CuCo 0.5 Fe 1.5 O4 nanoparticles were dispersed in deionized water, ultrasonically dispersed, and then silver nitrate solution was added and stirred. 4) Add ascorbic acid solution to the mixed solution obtained in step 3), stir, and grow silver nanoparticles using in-situ reduction method; 5) The mixed solution obtained in step 4) is washed, dried, and ground to obtain the target product Ag-CuCo. 0.5 Fe 1.5 O4; 6) Take the Ag-CuCo obtained in step 5) 0.5 Fe 1.5 O4 was prepared into a solution, drop-coated onto a clean glass slide, and dried to obtain Ag-CuCo. 0.5 Fe 1.5 O4 composite SERS substrate.
5. An Ag-CuCo according to claim 4 0.5 Fe 1.5 The application of O4 composite SERS substrate in the detection of malachite green in wastewater is characterized by... In step 1), the ratios of copper nitrate trihydrate, cobalt nitrate hexahydrate, ferric nitrate nonahydrate, and citric acid monohydrate are 0.966g ± 0.048g, 0.582g ± 0.029g, 2.424g ± 0.121g, and 4.203g ± 0.210g, respectively.
6. An Ag-CuCo according to claim 4 0.5 Fe 1.5 The application of O4 composite SERS substrate in the detection of malachite green in wastewater is characterized by... In step 2), the calcination temperature is 500-600℃, the heating rate is 5℃ / min, and the time is 3-4h.
7. An Ag-CuCo according to claim 4 0.5 Fe 1.5 The application of O4 composite SERS substrate in the detection of malachite green in wastewater is characterized by... In steps 3) and 4), the CuCo 0.5 Fe 1.5 O4 nanoparticles: silver nitrate solution: ascorbic acid solution = 50mg: 2mL: 6mL.
8. An Ag-CuCo according to claim 7 0.5 Fe 1.5 The application of O4 composite SERS substrate in the detection of malachite green in wastewater is characterized by... In steps 3) and 4), the CuCo 0.5 Fe 1.5 The concentration of O4 nanoparticles was 2.5 ± 0.125 mg / mL, the concentration of silver nitrate solution was 50 mM, and the concentration of ascorbic acid solution was 50 mM.
9. An Ag-CuCo according to claim 4 0.5 Fe 1.5 The application of O4 composite SERS substrate in the detection of malachite green in wastewater is characterized by... In step 4), the in-situ reduction method involves reacting at 20-25°C for 1-1.5 hours.
10. An Ag-CuCo according to claim 4 0.5 Fe 1.5 The application of O4 composite SERS substrate in the detection of malachite green in wastewater is characterized by... In step 6), Ag-CuCo 0.5 Fe 1.5 The concentration of the O4 solution is 1 mg / mL.