An enhanced 3D gold nanodendrite and its electrochemical preparation method for hazardous substance detection and in-situ degradation

Abstract

The present invention discloses an enhanced 3D gold nanodendrite, its preparation method and application. The preparation method includes: using a gold nanomembrane as a working electrode, preparing an electrolyte solution with EDTA, K2HPO4, Na2SO3 and HAuCl4·3H2O, the pH value of the electrolytic solution being 5.5 - 7, and performing electrochemical deposition at a constant voltage of -0.65V - -0.85V to obtain a 3D gold nanodendrite, with the deposition time being 300 - 500s. Then, continue to apply a constant voltage of -0.55V - -0.8V for secondary electrochemical deposition to obtain the final enhanced 3D gold nanodendrite, where the deposition time is 200 - 500s. This preparation method has a short preparation time, and the prepared enhanced 3D gold nanodendrite can detect the concentration of harmful substances with high sensitivity, strong stability and fast detection speed and in-situ degrade the harmful substances.

Description

Technical Field

[0001] The present invention belongs to the field of compound detection, and relates to an enhanced 3D gold nanodendrite and its electrochemical preparation method for detecting harmful substances and in-situ degradation. Background Art

[0002] At present, the main method for detecting antibiotics is chromatography. Although it can achieve the detection of antibiotics, it also has disadvantages such as expensive instruments and cumbersome steps. The spectrophotometric detection method has the advantages of simplicity and rapidity, but low sensitivity. The electrochemical detection method is easily interfered by complex matrices. Surface-enhanced Raman spectroscopy (SERS) technology, as a fingerprint spectroscopy technology, has characteristics such as rapid response, strong specificity, and high sensitivity, and is expected to achieve the rapid detection of antibiotics.

[0003] The SERS substrate is the core component in SERS technology. In the SERS detection of antibiotics, the traditional monodisperse nanoparticle SERS substrate is prone to the coffee ring effect during the detection process, resulting in unstable SERS signals. When the commonly used solid-state SERS substrates are used to detect antibiotics, there are problems such as low detection sensitivity, poor SERS signal stability, and complex substrate preparation steps.

[0004] Electrochemical technology has been widely used in the preparation of various solid-state SERS substrates. For example, noble metal materials are electrochemically deposited in anodized aluminum oxide and silica nanochannels with adjustable pore sizes using the template method. After removing the template, metal nanorod structures with adjustable sizes can be synthesized. Secondly, nanostructures are prepared by lithography technology, and then the gaps of the nanostructures are reduced by electrochemically depositing noble metal materials on their surfaces to improve the SERS enhancement effect at the "hot spots".

[0005] However, the above-mentioned solid-state SERS substrates have certain limitations. The nanostructures directly synthesized on the electrodes often have poor SERS effects. The synthesis process by the template method often involves multi-step synthesis, requires expensive and complex instruments, and needs professional personnel to operate, with high costs. Therefore, it is of great significance to electrochemically synthesize SERS substrates with good SERS effects without templates and simply and rapidly for the rapid detection of harmful substances. Summary of the Invention

[0006] The present invention provides a preparation method for an enhanced 3D gold nanodendrite. The preparation method has a short preparation time, and the prepared enhanced 3D gold nanodendrite can detect the concentration of harmful substances with high sensitivity, strong stability, and fast detection speed and perform in-situ degradation of harmful substances.

[0007] The present invention provides a preparation method for an enhanced 3D gold nanodendrite, including:

[0008] (1) Using a gold nanomembrane as the working electrode, an electrolyte solution was prepared using EDTA, K2HPO4, Na2SO3, and HAuCl4·3H2O. The pH value of the electrolytic solution was 5.5 - 7, and 3D gold nanodendrites were obtained by electrochemical deposition at a constant voltage of -0.65V to -0.85V for a deposition time of 300 - 500s;

[0009] (2) In the system obtained in step (1), a constant voltage of -0.55V to -0.8V was continuously applied for secondary electrochemical deposition to enhance the 3D gold nanodendrites, where the deposition time was 200 - 500s.

[0010] In the present invention, through electrochemical operations on the gold nanomembrane, enhanced 3D gold nanodendrites with smaller spacings are grown on the surface of the gold nanomembrane. The top view of the enhanced 3D gold nanodendrites provided by the present invention is star-shaped, uniformly and independently dispersed on the gold nanomembrane, and the shape of the gold nanostructure is dendritic. The surface of the enhanced 3D gold nanodendrites consists of multiple branches and tips of different sizes. The morphological and structural characteristics of the enhanced 3D gold nanodendrites are determined by the interaction between EDTA, K2HPO4, Na2SO3, and HAuCl4·3H2O. Na2SO3 promotes the reduction of Au 3+ to Au + , and the introduced EDTA can chelate with Au + ions to form a stable Au-EDTA complex. K2HPO4, as a secondary complexing agent, can bind and stabilize Au + ions, which helps to form enhanced 3D gold nanodendrites with good spacing, height, and structure. By changing the pH and voltage of the electrolyte solution, the purpose of controlling the morphology of the enhanced 3D gold nanostructure can be achieved. Under the condition of pH 5.5, due to the high deposition rate, more growth sites are easily generated, forming a multinuclear gold nanostructure. When the pH value increases to 6.5, the nanostructure transforms into highly ordered enhanced 3D gold nanodendrites. As the pH further increases, the deposition rate decreases significantly.

[0011] Preferably, after obtaining the 3D gold nanodendrites, secondary electrochemical deposition is carried out, and a constant voltage of -0.55V to -0.8V is applied to obtain the final enhanced 3D gold nanodendrites, where the deposition time is 200s - 500s. Controlling the deposition time can control the size of the enhanced 3D gold nanodendrites. As the deposition time increases, the height of the enhanced 3D gold nanodendrites increases significantly, while the width remains basically unchanged. During the entire deposition process, the thickness of the underlying Au film does not change.

[0012] After the secondary electrochemical deposition provided by the present invention, the spacing of the enhanced 3D gold nanodendrites becomes significantly smaller, and the size of the gold nanodendrites shows an increasing trend. The small gap is conducive to the coupling between the enhanced 3D gold nanodendrites, enabling multiple SERS "hot spots" to be distributed on the enhanced 3D gold nanodendrites, indicating its high SERS enhancement performance.

[0013] Due to the relatively small spacing of the prepared enhanced 3D gold nanodendrites, the enhanced 3D gold nanodendrites can be used as an SERS substrate, resulting in denser local surface plasmon resonance "hot spots" and higher enhancement effects. The electric field intensity at the edge of the enhanced 3D gold nanodendrites is significantly stronger than that of ordinary 3D gold nanodendrites, thus significantly improving the SERS enhancement factor. SERS signals were collected at 200 different positions, and the surface-enhanced Raman scattering signal recorded at 1361 cm -1 remained stable, with a relative standard deviation of 4.72%, indicating that the enhanced 3D gold nanodendrite substrate has the characteristics of stability and sensitivity in quantitative analysis experiments. The special 3D gold nanodendrite shape can absorb a large amount of visible light, and the absorbed visible light can generate more hot carriers during the relaxation process, which can then be directly used for photoelectrochemical degradation.

[0014] Preferably, the concentration of the EDTA solution is 0.01 - 0.02 mol / L, the concentration of the K2HPO4 solution is 0.1 - 0.3 mol / L, the concentration of the Na2SO3 solution is 1 - 1.5 mol / L, and the concentration of the HAuCl4·3H2O solution is 0.02 - 0.04 mol / L. Na2SO3 promotes the reduction of Au 3+ to Au + and the introduced EDTA can chelate with Au + ions to form a stable Au-EDTA complex. K2HPO4, as a secondary complexing agent, can bind and stabilize Au + ions, which helps to form 3D gold nanodendrites with good spacing, height, and structure.

[0015] Preferably, the pH of the electrolyte is adjusted to 5.5 - 7 with hydrochloric acid.

[0016] Preferably, before adding the gold nanomembrane to the electrolyte, the gold nanomembrane is cleaned with a plasma cleaner.

[0017] More preferably, the cleaning time of the plasma cleaner is 1 - 10 min.

[0018] Preferably, in steps (1) and (2), a reference electrode and a counter electrode are further included, which form a three-electrode system with the working electrode of the gold nanomembrane. The reference electrode is Ag / AgCl, and the counter electrode is a platinum wire.

[0019] On the other hand, the present invention also provides an enhanced 3D gold nanodendrite, which is prepared by the preparation method of the enhanced 3D gold nanodendrite.

[0020] Preferably, the diameter of the enhanced 3D gold nanodendrite is 50 - 300 nm, and the inter-tree gap is 20 - 80 nm. There are multiple SERS "hot spot" regions on the enhanced 3D gold nanodendrite, indicating its potential for high SERS enhancement performance.

[0021] On the other hand, the present invention also provides the application of the enhanced 3D gold nanodendrite in detecting the content of levofloxacin, including:

[0022] Soaking the enhanced 3D gold nanodendrite in a levofloxacin solution with a concentration of 5×10 -7 mol / L - 1×10 -4 mol / L, collecting the SERS intensity by Raman spectroscopy microscope, and substituting the SERS intensity into the levofloxacin content - SERS intensity standard curve to obtain the levofloxacin content.

[0023] Preferably, the levofloxacin content - SERS intensity standard curve is:

[0024] I = 1118.2×lg C + 7389.5, R 2 = 0.9836, where I is the SERS intensity and C is the levofloxacin concentration.

[0025] On the other hand, the present invention also provides the application of the enhanced 3D gold nanodendrite in detecting malachite green, including:

[0026] Soaking the enhanced 3D gold nanodendrite in a malachite green solution with a concentration of 1.37 - 13.70 ng / L, collecting the SERS intensity by Raman spectroscopy microscope, and substituting the SERS intensity into the malachite green content - SERS intensity standard curve to obtain the malachite green content.

[0027] Preferably, the malachite green content - SERS intensity standard curve is:

[0028] I = 1928.1C - 1492.1, R 2 = 0.9927, where I is the SERS intensity and C is the malachite green concentration.

[0029] On the other hand, the present invention also provides the application of the enhanced 3D gold nanodendrite in in-situ degradation of harmful substances, including:

[0030] Insert the enhanced 3D gold nanodendrites into the sample to be tested containing the hazardous substance, apply a voltage of 1.0 - 1.6 V to the enhanced 3D gold nanodendrites, and perform in-situ degradation of the hazardous substance under illumination with λ > 400 nm.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0032] (1) The enhanced 3D gold nanodendrites are synthesized by an electrochemical method in the present invention, with a short synthesis time, and the synthesized enhanced 3D gold nanodendrites have a narrow spacing. The surface of the enhanced 3D gold nanodendrite SERS substrate contains a large number of SERS "hot spot" regions, so it is suitable as a SERS substrate for detecting hazardous substances. The prepared SERS sensor has the characteristics of a low detection limit and a wide linear detection range. Therefore, the enhanced 3D gold nanodendrites prepared by the electrochemical method provided by the present invention can ensure the rapid and simple determination of hazardous substance residues in complex food matrices.

[0033] (2) The template-free enhanced 3D gold nanodendrites provided by the present invention have the advantages of short material synthesis time, high sensitivity, and high stability, and can be used for SERS quantitative analysis of hazardous substance residues in samples and in-situ degradation of hazardous substances. It provides a basis for establishing a SERS detection platform without a template, simple and rapid, and capable of in-situ degrading hazardous substances to achieve repeated use of the SERS substrate. Description of the Drawings

[0034] Figure 1 Scanning electron microscope image of the enhanced 3D gold nanodendrites prepared in Example 1, scanning electron microscope image of the enhanced 3D gold nanodendrites magnified 20,000 times, wherein the partial enlarged view is the scanning electron microscope image of the enhanced 3D gold nanodendrites magnified to 50,000 times;

[0035] Figure 2 SERS spectrum and linear relationship of the enhanced 3D gold nanodendrites prepared in Example 1 for detecting levofloxacin solution Figure 2 a is the SERS spectrum of levofloxacin solution with a concentration of 5×10 -7 mol / L - 1×10 -4 mol / L collected on the enhanced 3D gold nanodendrites, Figure 2 b is the linear relationship established between the SERS intensity at 1405 cm -1 and the concentration using levofloxacin;

[0036] Figure 3 The linear relationship established between the SERS intensity at 1405 cm -1 and the concentration for detecting the content of levofloxacin in fish meat by the enhanced 3D gold nanodendrites prepared in Example 1;

[0037] Figure 4 SERS signal acquisition diagrams of different regions of the enhanced 3D gold nanodendrites prepared in Application Example 1 Figure 4 a shows the SERS spectra collected at 200 sites Figure 4 b shows the RSD value of the intensity at the characteristic peak of 1361 cm -1 -1

[0038] Figure 5 For the enhanced 3D gold nanodendrites prepared in Application Example 2, a linear relationship between the SERS intensity at 1612 cm -1 -1

[0039] Figure 6 and the concentration was established for detecting the malachite green content in fish t meat Detailed implementation manners

[0040] Example 1

[0041] This example provides a method for preparing enhanced 3D gold nanodendrites, including:

[0042] (1) Cleaning the electrode: Placing the gold nanomembrane in a plasma cleaner and cleaning for 2 minutes

[0043] (2) Preparation of enhanced 3D gold nanodendrites: Using a three-electrode system composed of a gold nanomembrane as the working electrode, Ag / AgCl as the reference electrode, and a platinum wire as the counter electrode for the electrochemical deposition of enhanced 3D gold nanodendrites. The electrolyte solution includes 0.017 mol / L EDTA, 0.17 mol / L K2HPO4, 1.27 mol / L Na2SO3, and 0.029 mol / L HAuCl4·3H2O. The pH of the electrolyte solution is adjusted to 6.5 with hydrochloric acid. At a constant potential of -0.8 V, the electrochemical deposition time is 500 s, and 3D gold nanodendrites are grown on the gold nanomembrane. Then, a voltage of -0.65 V is continuously applied, and the deposition time is 500 s to obtain enhanced 3D gold nanodendrites. Subsequently, it is rinsed clean with deionized water and dried with nitrogen

[0044] As Figure 1 shown, the diameter of the synthesized enhanced 3D gold nanodendrites is 141.22 ± 23.55 nm, and the inter-tree gap is 14.72 ± 4.06 nm. In the enlarged top view, the top view of the gold nanostructure is star-shaped, evenly and independently dispersed on the Au film, and the shape of the gold nanostructure is tree-like. The surface of the enhanced 3D gold nanodendrites consists of multiple branches and tips of different sizes, indicating the potential of the enhanced 3D gold nanodendrites to have high SERS enhancement performance

[0045] Application Example 1

[0046] Drawing of the working curve: The enhanced 3D gold nanodendrites were immersed in levofloxacin at different concentrations, specifically 0.025, 0.075, 0.126, 0.176, 0.251 μg / L. The test conditions were as follows: laser wavelength of 638 nm, power of 0.66 mW, acquisition time of 120 s, magnification of 50 times, and averaging 3 times for each measurement. The surface-enhanced Raman scattering signals were monitored at different spot positions.

[0047] As Figure 2 shown in Figure 2 a and -1 b, the SERS spectra of levofloxacin showed strong SERS characteristic peaks at 1405 cm -1 , 1569 cm -1 , and 1626 cm -1 . The characteristic peak at 1405 cm

[0048] was attributed to the stretching vibration of the quinolone ring and was selected as the characteristic peak for levofloxacin detection. -1 As the content of levofloxacin increased, the SERS intensity increased linearly. The intensity (SERS Intensity) corresponding to the Raman shift at 1405 cm Levofloxacin was used as the ordinate, and the logarithm of the levofloxacin concentration (lg(C Figure 3 / mol / L)) was used as the abscissa to plot the standard curve as 2 shown in -7 Figure, I = 10683C + 704.33, R

[0049] 2 Figure 4 = 0.994, where I is the SERS intensity and C is the levofloxacin concentration. The calculated detection limit was 1×10 Figure 4 mol / L. This method has a wide linear detection range, and the detection sensitivity meets the national standard (GB 31656.3 - 2021) method (GB 31656.3 - 2021 National Food Safety Standard - Determination of Residues of Norfloxacin, Ciprofloxacin, Enrofloxacin, Ofloxacin, Oxolinic Acid, and Flumequine in Aquatic Products - High Performance Liquid Chromatography). -1 As

[0050] Figure 4 shown in a and Figure 4 b, the SERS signal recorded at 1361 cm -1 remained stable, and the obtained relative standard deviation (RSD) was 4.72%. This indicates that the prepared enhanced 3D gold nanodendrite substrate has stability, reliability, and sensitivity in quantitative analysis experiments.

[0050] Sample pretreatment: After adding levofloxacin standard to the fish meat, sample pretreatment was carried out on the fish meat. The fish meat was crushed into a homogenate with a blender. 5 g of the fish meat homogenate was weighed, and the extraction method referred to the national standard (GB 31656.3-2021). The supernatant after extraction was passed through a C18 solid-phase extraction column. After collecting the eluate, it was dried with nitrogen at 50 °C, dissolved with 5 mL of acetonitrile, and then passed through a 0.22 μm microporous filter membrane for SERS and spectrophotometric measurement. After adding the levofloxacin standard sample to the aquaculture water body, it was directly passed through a 0.22 μm filter membrane, evaporated to near dryness, and fixed to 5 mL with acetonitrile.

[0051] Determination of levofloxacin concentration in the sample: Different known concentrations of levofloxacin were added to the sample, specifically 0.10, 0.19, 0.18, 0.038 μg / g. The spectra were collected with a Raman spectroscopy microscope, and the concentration of levofloxacin in the sample to be measured was obtained according to the established standard curve. As shown in Table 1, there was a very high consistency between the spiked concentration and the measured content. The recovery rates in the aquaculture water body and fish meat were in the ranges of 91.78% - 97.80% and 85.22% - 93.59% respectively. The good recovery rate and relative standard deviation value in the table also indicated that there was no potential matrix interference, so it had the reliability for analyzing complex food matrices.

[0052] Table 1. Analysis of levofloxacin in pretreated fish meat and aquaculture water body by this method

[0053]

[0054] Note: The values are the average ± standard deviation of three repeated experiments

[0055] Application Example 2

[0056] Drawing of the working curve: The enhanced 3D gold nanodendrites prepared in Example 1 were immersed in malachite green with different concentrations, specifically 1.37, 4.11, 6.85, 9.59, 13.70 ng / L. The test conditions were: laser wavelength 638 nm, power 0.66 mW, acquisition time 120 s, magnification 50 times, and each measurement was averaged 3 times. The intensity (SERS Intensity) corresponding to the Raman shift at 1612 cm -1 of different concentrations of malachite green was used as the ordinate, and the malachite green concentration (C Malachite green / mol / L) was used as the abscissa to draw the standard curve as Figure 5 shown, I = 1928.1C - 1492.1, R 2 = 0.9927, where I is the SERS intensity and C is the malachite green concentration. The calculated detection limit was 5×10 -10 mol / L;

[0057] Sample pretreatment: the same as (5) in Application Example 1;

[0058] Determination of malachite green concentration in the sample: Different known concentrations of malachite green were added to the sample, specifically 1.37, 1.64, and 6.85 ng / g. Raman spectroscopy microscope was used to collect the spectra, and the concentration of malachite green in the sample to be measured was obtained according to the established standard curve. As shown in Table 2, there is a very high consistency between the spiked concentration and the measured content, and the recovery rates in the aquaculture water and fish meat are in the ranges of 92.73% - 98.57% and 78.01% - 95.50% respectively.

[0059] Table 2. Analysis of malachite green in pretreated fish meat and aquaculture water by this method

[0060]

[0061] Note: The values are the average ± standard deviation of three repeated experiments

[0062] Application Example 3

[0063] The same as (1)-(2) in Example 1;

[0064] The prepared enhanced 3D gold nanodendrite electrode was inserted into the actual aquaculture water containing malachite green, and the real-time concentration of malachite green was measured by SERS technology. The SERS spectrum acquisition conditions were: laser wavelength 638 nm, power 33 mW, acquisition time 0.1 s, magnification 5 times, and averaged three times for each measurement. The peak intensity measured at 1612 cm -1 was used as the signal, and the real-time concentration of malachite green in the aquaculture water was calculated according to the established working curve.

[0065] After detection, switch to the optoelectronic mode, apply a voltage of 1.2 V to the electrode, and under illumination with λ>400 nm, in-situ degradation of malachite green was carried out. Every 20 min, switch to the SERS mode again for real-time determination of the pollutant concentration. The results are as Figure 6 shown, Figure 6 For the enhanced 3D gold nanodendrite as the electrode, the change of C t / C0 of malachite green in the real sample during the degradation process. As the degradation time increases, the concentration of malachite green in the aquaculture water continuously decreases. By monitoring the concentration of malachite green during the in-situ degradation process with this electrode, the results show that when the degradation times are 0, 20, 40, and 60 min, the malachite green concentrations decrease to 97.04±3.54, 44.51±0.61, 15.66±1.21, and 4.50±0.24 μmol / L respectively.

[0066] Example 2

[0067] Compared with Example 1, the difference is that the concentration of the EDTA solution is 0.015 mol / L, the concentration of the K4HPO4 solution is 0.2 mol / L, the concentration of the Na2SO3 solution is 1.5 mol / L, the concentration of the HAuCl4·3H2O solution is 0.04 mol / L, the pH value of the electrolytic solution is 6, 3D gold nanodendrites are obtained by electrochemical deposition at a constant voltage of -0.85 V for a deposition time of 400 s, and enhanced 3D gold nanodendrites are obtained by secondary electrochemical deposition at a constant voltage of -0.65 V for a deposition time of 400 s.

Claims

1. Application of an enhanced 3D gold nanodendrite in detecting the content of levofloxacin or in detecting malachite green or in in-situ degrading malachite green, characterized in that, Preparation method of enhanced 3D gold nanodendrites, comprising: (1) Using a gold nanomembrane as a working electrode, preparing an electrolyte solution with EDTA, K2HPO4, Na2SO3, and HAuCl4·3H2O, where the pH value of the electrolytic solution is 5.5 - 7, and performing electrochemical deposition at a constant voltage of -0.8 V - -0.85 V to obtain 3D gold nanodendrites, with a deposition time of 300 - 500 s; (2) Continuing to apply a constant voltage of -0.55 V - -0.65 V in the system obtained in step (1) for secondary electrochemical deposition of enhanced 3D gold nanodendrites, where the deposition time is 200 - 500 s; The diameter of the enhanced 3D gold nanodendrites is 50 - 300 nm, and the tree gap is 20 - 80 nm.

2. Use of the enhanced 3D gold nanodendrites according to claim 1 in detecting the content of levofloxacin or in detecting malachite green or in in-situ degrading malachite green, characterized in that, The concentration of the EDTA solution is 0.01 - 0.02 mol / L, the concentration of the K2HPO4 solution is 0.1 - 0.3 mol / L, the concentration of the Na2SO3 solution is 1 - 1.5 mol / L, and the concentration of the HAuCl4·3H2O solution is 0.02 - 0.04 mol / L.

3. Use of the enhanced 3D gold nanodendrites according to claim 1 in detecting the content of levofloxacin or in detecting malachite green or in in-situ degrading malachite green, characterized in that, Before adding the gold nanomembrane to the electrolyte solution, the gold nanomembrane is cleaned using a plasma cleaner.

4. Use of the enhanced 3D gold nanodendrites according to claim 1 in detecting the content of levofloxacin or in detecting malachite green or in in-situ degrading malachite green, characterized in that, In steps (1) and (2), a reference electrode and a counter electrode are also included, which together with the working electrode of the gold nanomembrane form a three-electrode system. The reference electrode is Ag / AgCl, and the counter electrode is a platinum wire.

5. Use of the enhanced 3D gold nanodendrites according to claim 1 in detecting the content of levofloxacin or in detecting malachite green or in in-situ degrading malachite green, characterized in that, Application of the enhanced 3D gold nanodendrites in detecting the content of levofloxacin, comprising: Soak the enhanced 3D gold nanodendrites in levofloxacin solution with a concentration of 5 × 10 -7 mol / L - 1 × 10 -4 mol / L, collect the SERS intensity by Raman spectroscopic microscopy, and substitute the SERS intensity into the levofloxacin content - SERS intensity standard curve to obtain the levofloxacin content.

6. Use of the enhanced 3D gold nanodendrites according to claim 1 in detecting the content of levofloxacin or in detecting malachite green or in in-situ degrading malachite green, characterized in that, Application of the enhanced 3D gold nanodendrites in detecting malachite green, comprising: Immersing the enhanced 3D gold nanodendrites in a malachite green solution with a concentration of 1.37 - 13.70 ng / L, collecting the SERS intensity by Raman spectroscopy microscope, and substituting the SERS intensity into the malachite green content - SERS intensity standard curve to obtain the malachite green content.

7. Use of the enhanced 3D gold nanodendrites according to claim 1 in detecting the content of levofloxacin or in detecting malachite green or in in-situ degrading malachite green, characterized in that, Application of the enhanced 3D gold nanodendrites in in-situ degradation of malachite green, comprising: Inserting the enhanced 3D gold nanodendrites into a test sample containing malachite green, applying a voltage of 1.0 - 1.6 V to the enhanced 3D gold nanodendrites, and performing in-situ degradation of malachite green under illumination with λ > 400 nm.

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