Porous silver nanoplate / zinc oxide nanorod array structure, preparation method and use thereof

Abstract

The application discloses a porous silver nanosheet / zinc oxide nanorod array structure, a preparation method and application thereof. The zinc oxide nanorod is vertically grown on a conductive substrate, and then a layer of gold is decorated on the zinc oxide nanorod and the surface of the substrate where the zinc oxide nanorod is located; and porous silver nanosheets are grown in the gaps between the surface of the gold-plated zinc oxide nanorod and the gold-plated zinc oxide nanorod. The preparation method of the porous silver nanosheet / zinc oxide nanorod array structure is as follows: under the condition of a 90-98 DEG C water bath, zinc oxide nanorod arrays are grown on the surface of a conductive glass placed in a zinc-ammonia solution; then a small amount of gold is decorated on the surface of the zinc oxide nanorod by using a sputtering method; and finally, porous silver nanosheets are electrodeposited on the surface of the zinc oxide nanorod array by using an alkaline silver electrolyte, so as to obtain the target product. The product has high surface-enhanced Raman scattering (SERS) sensitivity, and can be widely applied to SERS detection of organic matters, such as rapid detection of rhodamine 6G.

Description

Technical Field

[0001] This invention relates to the field of composite nanomaterials technology, and in particular to a porous silver nanosheet / zinc oxide nanorod array structure, its preparation method, and its applications. Background Technology

[0002] Surface-enhanced Raman scattering (SERS) spectroscopy has broad application prospects in chemistry, biomedical detection, and materials analysis. The SERS effect in noble metal nanomaterials mainly originates from electromagnetic enhancement. Due to its dielectric properties, silver is the most significant material for SERS. The main contribution to the SERS signal comes from hot spots. SERS hot spots in noble metals are generally located at their sharp tips or edges, and in gaps or pores smaller than 10 nm. Among many silver nanostructures, silver nanosheets have advantages such as large specific surface area and tunable optical properties like localized plasmon resonance peaks. Furthermore, three-dimensional SERS substrates can provide more hot spots within a laser beam, thus attracting widespread attention. For example, patent application CN114956600A discloses a method of growing silver nanosheets on the surface of ZnO nanorods forming an array structure to obtain a three-dimensional SERS substrate. Since the SERS hot spots of typical silver nanosheets (i.e., complete nanosheets without pores) are located at the edges of the sheet, their SERS hot spot density needs to be further improved to enhance their SERS activity. Porous silver nanosheets not only possess the advantages of ordinary silver nanosheets, but their pores can also provide SERS hotspots, which is beneficial for obtaining high SERS activity. Therefore, preparing zinc oxide nanorod arrays modified with porous silver nanosheets holds promise for obtaining SERS substrates with higher SERS activity. However, currently, there are few reports on the preparation of porous silver nanosheets, especially one-step direct methods. Methods for preparing zinc oxide nanorod arrays modified with porous silver nanosheets are also rarely reported. Therefore, developing a method for preparing zinc oxide nanorod arrays modified with porous silver nanosheets is expected to improve SERS activity and has significant implications for the preparation and application of SERS substrates. Summary of the Invention

[0003] One objective of this invention is to provide a porous silver nanosheet / zinc oxide nanorod array structure to address the shortcomings of existing technologies, such as low SERS activity of silver nanosheet@zinc oxide nanorod arrays and the difficulty in directly preparing porous silver nanosheets in a one-step method.

[0004] To achieve the above objectives, the present invention employs the following technical solution: a porous silver nanosheet / zinc oxide nanorod array structure, comprising multiple zinc oxide nanorods arranged in a monolayer array on a conductive substrate to form a zinc oxide nanorod array; both the zinc oxide nanorod array and the surface of the conductive substrate on which the array is located are covered with a gold film, and porous silver nanosheets are vertically grown on the surface of the gold film at the locations of the zinc oxide nanorods and the conductive substrate; the height of the zinc oxide nanorods is 2-10 μm and the diameter is 200-700 nm; the porous silver nanosheets are irregularly shaped sheets with a diameter of 0.5-5 μm and a thickness of 5-30 nm, and the pores of the porous silver nanosheets are circular pores with a diameter of 2-8 nm or flat pores with a length of 5-60 nm and a width of 2-8 nm; the thickness of the gold film is 2-10 nm.

[0005] The second objective of this invention is to provide a method for preparing the above-mentioned porous silver nanosheet / zinc oxide nanorod array structure, comprising the following steps:

[0006] S1. Prepare a Zn(NH3)4(NO3)2 solution, i.e., a zinc ammonia solution. Place the conductive substrate vertically into the zinc ammonia solution and grow it in a water bath at 90-98℃ for 60-120 minutes. Then remove it, wash it with deionized water and dry it to obtain a zinc oxide nanorod array on the conductive substrate.

[0007] S2. Sputter a gold film with a thickness of 2-10 nm onto the surface of the zinc oxide nanorod array and the conductive substrate on which the zinc oxide nanorod array is located, and a gold-plated zinc oxide nanorod array is prepared on the conductive substrate.

[0008] S3. Silver electrolyte is prepared by adding silver nitrate, NaOH, and hexadecyltrimethylammonium chloride to deionized water. The temperature of the silver electrolyte is maintained at 30-35℃ under water bath conditions. A conductive substrate with a gold-plated zinc oxide nanorod array is vertically placed in the silver electrolyte as the cathode, and a graphite sheet is used as the anode. An anode is applied at a current of 5-100 μA / cm. 2 After electrodeposition with current for 10-90 minutes, the sample is removed, washed with deionized water, and dried to fabricate a porous silver nanosheet / zinc oxide nanorod array structure on a conductive substrate.

[0009] Further improvements were made to the preparation method of porous silver nanosheet / zinc oxide nanorod array structures:

[0010] Preferably, the zinc ammonia solution in step S1 is prepared by adding 13-14 wt% ammonia water dropwise to a 0.16-0.3 mol / L zinc nitrate hexahydrate solution until the solution becomes clear.

[0011] Preferably, the sputtering method described in step S2 is ion sputtering.

[0012] Preferably, the silver electrolyte in step S3 is prepared as follows: AgNO3 and hexadecyltrimethylammonium chloride are added to water to form a mixed solution, wherein the concentration of AgNO3 is 0.2-0.5 mM and the concentration of hexadecyltrimethylammonium chloride is 3-10 mM. The mixed solution is placed in a water bath at 30-35°C, and 0.5 mL of 1 M NaOH solution is added. Then, 3 M NaOH aqueous solution is added dropwise until the pH of the mixed solution is 10-11.5, thus obtaining the silver electrolyte.

[0013] A third objective of this invention is to provide the use of the above-mentioned porous silver nanosheet / zinc oxide nanorod array structure as an active substrate for surface-enhanced Raman scattering.

[0014] Further improvements to the application of porous silver nanosheet / zinc oxide nanorod array structures:

[0015] Preferably, a porous silver nanosheet / zinc oxide nanorod array structure is used as an active substrate for surface-enhanced Raman scattering, and the content of the dye molecule Rhodamine 6G attached to it is measured using a laser Raman spectrometer.

[0016] Preferably, the excitation light of the laser Raman spectrometer has a wavelength of 514 nm, 532 nm, or 633 nm, a power of 0.01-1 mW, and an integration time of 0.1-60 s.

[0017] The advantages of this invention compared to the prior art are as follows:

[0018] Firstly, a simple electrodeposition method was used to grow a large number of porous silver nanosheets on zinc oxide nanorod arrays with gold films sputtered on their surfaces, and on the gold films containing the substrates between the zinc oxide nanorod arrays. Due to their porous structure, these silver nanosheets have a larger specific surface area than ordinary silver nanosheets. They possess characteristics such as dense small-sized pores, large specific surface area, and unique geometry, showing potential applications in numerous fields including the modulation of localized surface plasmon resonance (LSPR) properties and LSPR-based detection applications, SERS mechanism research, SERS spectral detection applications, transparent conductive materials, and antibacterial and bactericidal materials.

[0019] Secondly, porous silver nanosheets were prepared on sputtered zinc oxide nanorod arrays with gold. The densely packed pores formed numerous SERS hotspots, resulting in higher SERS activity than non-porous silver nanosheets. Using the prepared porous silver nanosheet / zinc oxide nanorod array composite structure as a SERS substrate, the experimentally measured detection limit for rhodamine 6G solution was 3.6 × 10⁻⁶. -16The concentration of mol / L is far below the lower limit for the determination of Rhodamine 6G by silver nanosheets@zinc oxide nanorod arrays disclosed in patent application CN114956600A, indicating that the porous silver nanosheet / zinc oxide nanorod array composite structure has higher SERS activity and detection sensitivity.

[0020] Thirdly, this invention provides a method for preparing a porous silver nanosheet / zinc oxide nanorod array structure. This method is based on the following technical principles: sputtering gold onto the surface of zinc oxide nanorods can improve their conductivity; furthermore, due to the relatively compatible lattices of gold and silver, the presence of gold is conducive to the formation of silver crystal nuclei. A solution containing silver nitrate and hexadecyltrimethylammonium chloride (as a surfactant, dispersant, complexing agent, etc.) is mixed with a certain concentration of NaOH solution to form a complex containing silver ions. This complex is water-soluble and can be uniformly dispersed in the solution. During electrodeposition, the silver ions in the complex are reduced to silver atoms and deposited on the cathode to form silver crystal nuclei. Hexadecyltrimethylammonium chloride in the solution can be firmly adsorbed onto the surface of the silver crystal nuclei. Furthermore, the aqueous solution containing hexadecyltrimethylammonium chloride generates a large number of microbubbles during stirring and dissolution. The hexadecyltrimethylammonium chloride and microbubbles adsorbed on the silver surface will hinder the local growth of silver crystals, thereby forming a porous structure. The selective adsorption of hexadecyltrimethylammonium chloride on specific surfaces of silver nanocrystals, coupled with a suitable deposition current density, facilitates the formation of silver nanosheets. These two factors combined ultimately lead to the formation of porous silver nanosheets. Attached Figure Description

[0021] Figure 1 The results are obtained by characterizing the zinc oxide nanorod array, the intermediate product of Example 1 of the present invention, using scanning electron microscopy (SEM) at different magnifications; wherein (a) has a magnification of 2500, (b) has a magnification of 8000, (c) has a magnification of 40000, and (d) has a magnification of 320000.

[0022] Figure 2 To use the target product of Example 1 of the present invention as a substrate for enhanced Raman scattering, a confocal laser Raman spectrometer was used to detect the presence of 10 -15 One of the results of mol / L rhodamine 6G. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0024] First, obtain it from the market or make it yourself:

[0025] Indium tin oxide (ITO) glass as a conductive substrate;

[0026] Zinc nitrate hexahydrate; ammonia; silver nitrate; glucose; hexadecyltrimethylammonium chloride; deionized water; graphite sheets.

[0027] Example 1

[0028] This embodiment provides a method for preparing a porous silver nanosheet / zinc oxide nanorod array structure, which specifically includes the following steps:

[0029] S1. Preparation of Zn(NH3)4(NO3)2 solution, i.e. zinc ammonia solution: Add 13wt% ammonia water dropwise to a 0.16mol / L zinc nitrate hexahydrate solution until the solution becomes clear.

[0030] The conductive substrate was vertically placed in a zinc ammonia solution and grown in a water bath at 96°C for 100 min. After being removed, it was washed with deionized water and dried to obtain a zinc oxide nanorod array on the conductive substrate.

[0031] S2. A gold film with a thickness of 8 nm is ion-sputtered onto the surface of the zinc oxide nanorod array to prepare a gold-plated zinc oxide nanorod array on a conductive substrate.

[0032] S3. Preparation of silver electrolyte: Add AgNO3 and hexadecyltrimethylammonium chloride to water to form a mixed solution, wherein the concentration of AgNO3 is 0.2mM and the concentration of hexadecyltrimethylammonium chloride is 3mM. Place the solution in a water bath at 30℃, add 0.5mL of 1M NaOH solution, and add 3M NaOH aqueous solution dropwise until the pH of the mixed solution is 10.

[0033] The silver electrolyte was kept at 30°C in a water bath. A conductive substrate with a gold-plated zinc oxide nanorod array was vertically placed in the silver electrolyte as the cathode, and a graphite sheet was used as the anode. An anode was applied at 80 μA / cm². 2 After electrodeposition with current for 15 minutes, the sample was removed, washed with deionized water and dried to fabricate a porous silver nanosheet / zinc oxide nanorod array composite structure on a conductive substrate.

[0034] The intermediate and target products were characterized using scanning electron microscopy (SEM) at different magnifications, and the results are as follows: Figure 1 As shown, the magnification of (a) is 2500, (b) is 8000, (c) is 40000, and (d) is 320000. From... Figure 1 (b) It can be seen that the intermediate product, zinc oxide nanorods, grow densely and upright on the surface of the conductive glass. Figure 1As shown in (a)-(d), after sputtering gold and electrodeposition, the target product obtained is a porous silver nanosheet-modified zinc oxide nanorod array. Figure 1 As shown in (a)-(c), the porous silver nanosheets on the zinc oxide nanorods are irregular sheets with a size of 0.5-5 μm and a thickness of 5-30 nm; Figure 1 (d) It can be seen that the pores of the porous silver nanosheets are circular or elongated. The diameter of the circular pores is 2-8 nm, and the width of the elongated pores is 2-8 nm and the length is 5-60 nm.

[0035] The optical absorption spectrum of the target product in Example 1 was measured, and the optical absorption peak of the porous silver nanosheets was found to be located at 496 nm. The target product of Example 1 was immersed in R6G solutions of different concentrations for 2 hours, and the detection limit for R6G of this substrate was determined to be 3.6 × 10⁻⁶. -16 The concentration of mol / L indicates that the substrate exhibits extremely high sensitivity to R6G.

[0036] Example 2

[0037] This embodiment provides a method for preparing a porous silver nanosheet / zinc oxide nanorod array structure, which specifically includes the following steps:

[0038] S1. Preparation of Zn(NH3)4(NO3)2 solution, i.e. zinc ammonia solution: Add 14wt% ammonia water dropwise to a 0.3mol / L zinc nitrate hexahydrate solution until the solution becomes clear.

[0039] The conductive substrate was vertically placed in a zinc ammonia solution and grown in a water bath at 92°C for 80 minutes. After being removed, it was washed with deionized water and dried to obtain a zinc oxide nanorod array on the conductive substrate.

[0040] S2. A 4 nm thick gold film is ion-sputtered onto the surface of the zinc oxide nanorod array to prepare a gold-plated zinc oxide nanorod array on a conductive substrate.

[0041] S3. Preparation of silver electrolyte: Add AgNO3 and hexadecyltrimethylammonium chloride to water to form a mixed solution, wherein the concentration of AgNO3 is 0.5 mM and the concentration of hexadecyltrimethylammonium chloride is 10 mM. Place the solution in a water bath at 35°C, add 0.5 mL of 1 M NaOH solution, and add 3 M NaOH aqueous solution dropwise until the pH of the mixed solution is 11.5.

[0042] The silver electrolyte was kept at 35°C in a water bath. A conductive substrate with a gold-plated zinc oxide nanorod array was vertically placed in the silver electrolyte as the cathode, and a graphite sheet was used as the anode. An anode was applied at a current of 40 μA / cm². 2After electrodeposition with current for 70 min, the sample was removed, washed with deionized water and dried to fabricate a porous silver nanosheet / zinc oxide nanorod array composite structure on a conductive substrate.

[0043] The optical absorption spectrum of the target product in Example 2 was measured, and the optical absorption peak of the porous silver nanosheets was found to be located at 512 nm. The target product was immersed in R6G solutions of different concentrations for 2 hours, and the detection limit for R6G of this substrate was determined to be 4.0 × 10⁻⁶. -16 The concentration of mol / L indicates that the substrate exhibits extremely high sensitivity to R6G.

[0044] Example 3

[0045] This embodiment provides a method for preparing a porous silver nanosheet / zinc oxide nanorod array structure, which specifically includes the following steps:

[0046] S1. Preparation of Zn(NH3)4(NO3)2 solution, i.e., zinc ammonia solution: Add 13.5wt% ammonia water dropwise to a 0.2mol / L zinc nitrate hexahydrate solution until the solution becomes clear.

[0047] The conductive substrate was vertically placed in a zinc ammonia solution and grown in a water bath at 92°C for 110 min. After being removed, it was washed with deionized water and dried to obtain a zinc oxide nanorod array on the conductive substrate.

[0048] S2. A 6 nm thick gold film is ion sputtered onto the surface of the zinc oxide nanorod array.

[0049] S3. Preparation of silver electrolyte: Add AgNO3 and hexadecyltrimethylammonium chloride to water to form a mixed solution, wherein the concentration of AgNO3 is 0.3mM and the concentration of hexadecyltrimethylammonium chloride is 5mM. Place the solution in a water bath at 32℃, add 0.5mL of 1M NaOH solution, and add 3M NaOH aqueous solution dropwise until the pH of the mixed solution is 11.

[0050] The silver electrolyte was kept at 30°C in a water bath. A conductive substrate with a gold-plated zinc oxide nanorod array was vertically placed in the silver electrolyte as the cathode, and a graphite sheet was used as the anode. An anode was applied at a current of 10 μA / cm². 2 After electrodeposition with current for 50 min, the sample was removed, washed with deionized water and dried to fabricate a porous silver nanosheet / zinc oxide nanorod array composite structure on a conductive substrate.

[0051] The optical absorption spectrum of the target product in Example 3 was measured, and the optical absorption peak of the porous silver nanosheets was found to be located at 551 nm. The target product was immersed in R6G solutions of different concentrations for 2 hours, and the detection limit for R6G of this substrate was determined to be 3.1 × 10⁻⁶. -16 The concentration of mol / L indicates that the substrate exhibits extremely high sensitivity to R6G.

[0052] Example 4

[0053] This embodiment provides a method for preparing a porous silver nanosheet / zinc oxide nanorod array structure, which specifically includes the following steps:

[0054] S1. Preparation of Zn(NH3)4(NO3)2 solution, i.e., zinc ammonia solution: Add 13.5wt% ammonia water dropwise to a 0.25mol / L zinc nitrate hexahydrate solution until the solution becomes clear.

[0055] The conductive substrate was vertically placed in a zinc ammonia solution and grown in a water bath at 92°C for 110 min. After being removed, it was washed with deionized water and dried to obtain a zinc oxide nanorod array on the conductive substrate.

[0056] S2. A 3 nm thick gold film is ion sputtered onto the surface of the zinc oxide nanorod array;

[0057] S3. Preparation of silver electrolyte: Add AgNO3 and hexadecyltrimethylammonium chloride to water to form a mixed solution, wherein the concentration of AgNO3 is 0.4 mM and the concentration of hexadecyltrimethylammonium chloride is 6 mM. Place the solution in a water bath at 33°C, add 0.5 mL of 1 M NaOH solution, and add 3 M NaOH aqueous solution dropwise until the pH of the mixed solution is 11.

[0058] The silver electrolyte was kept at 33°C in a water bath. A conductive substrate with a gold-plated zinc oxide nanorod array was vertically placed in the silver electrolyte as the cathode, and a graphite sheet was used as the anode. An anode was applied at a current of 30 μA / cm². 2 After electrodeposition with current for 80 min, the sample was removed, washed with deionized water and dried to fabricate a porous silver nanosheet / zinc oxide nanorod array composite structure on a conductive substrate.

[0059] The optical absorption spectrum of the target product in Example 4 was measured, and the optical absorption peak of the porous silver nanosheets was found to be located at 506 nm. The target product was immersed in R6G solutions of different concentrations for 2 h, and the detection limit for R6G of this substrate was determined to be 2.5 × 10⁻⁶. -16 The concentration of mol / L indicates that the substrate exhibits extremely high sensitivity to R6G.

[0060] Example 5

[0061] This embodiment provides a method for preparing a porous silver nanosheet / zinc oxide nanorod array structure, which specifically includes the following steps:

[0062] S1. Preparation of Zn(NH3)4(NO3)2 solution, i.e. zinc ammonia solution: Add 13wt% ammonia water dropwise to a 0.3mol / L zinc nitrate hexahydrate solution until the solution becomes clear.

[0063] The conductive substrate was vertically placed in a zinc ammonia solution and grown in a water bath at 92°C for 110 min. After being removed, it was washed with deionized water and dried to obtain a zinc oxide nanorod array on the conductive substrate.

[0064] S2. A 10 nm thick gold film is ion sputtered onto the surface of the zinc oxide nanorod array.

[0065] S3. Preparation of silver electrolyte: Add AgNO3 and hexadecyltrimethylammonium chloride to water to form a mixed solution, wherein the concentration of AgNO3 is 0.4 mM and the concentration of hexadecyltrimethylammonium chloride is 8 mM. Place the solution in a water bath at 34°C, add 0.5 mL of 1 M NaOH solution, and add 3 M NaOH aqueous solution dropwise until the pH of the mixed solution is 11.

[0066] The silver electrolyte was kept at 34°C in a water bath. A conductive substrate with a gold-plated zinc oxide nanorod array was vertically placed in the silver electrolyte as the cathode, and a graphite sheet was used as the anode. An anode was applied at a current of 50 μA / cm². 2 After electrodeposition with current for 60 min, the sample was removed, washed with deionized water and dried to fabricate a porous silver nanosheet / zinc oxide nanorod array composite structure on a conductive substrate.

[0067] The optical absorption spectrum of the target product in Example 5 was measured, and the optical absorption peak of the porous silver nanosheets was found to be located at 490 nm. The target product was immersed in R6G solutions of different concentrations for 2 h, and the detection limit for R6G of this substrate was determined to be 2.8 × 10⁻⁶. -16 The concentration of mol / L indicates that the substrate exhibits extremely high sensitivity to R6G.

[0068] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments. It should be noted that many modifications and improvements can be made by those skilled in the art, and all modifications or improvements not exceeding the scope of the claims should be considered within the protection scope of the present invention.

Claims

1. A porous silver nanoplate / zinc oxide nanorod array structure, characterized in that, The porous silver nanosheet / zinc oxide nanorod array structure is prepared by a preparation method comprising the following steps: S1, preparing a Zn(NH3)4(NO3)2 solution, i.e., a zinc ammonia solution, and vertically placing a conductive substrate in the zinc ammonia solution, and then taking out the conductive substrate after growing for 60-120 min under the condition of a water bath at 90-98 ℃, and then cleaning and drying the conductive substrate to prepare a zinc oxide nanorod array on the conductive substrate; S2, sputtering a gold film with a thickness of 2-10 nm on the surface of the zinc oxide nanorod array and the conductive substrate to prepare a gold-plated zinc oxide nanorod array on the conductive substrate; The preparation method of the zinc ammonia solution in step S1 is as follows: 0.16-0.3 mol / L zinc nitrate hexahydrate solution is added dropwise into ammonia water with a concentration of 13-14 wt% until the solution is clear. S3, silver nitrate, NaOH, cetyl trimethyl ammonium chloride were added into deionized water to prepare silver electrolyte, the temperature of silver electrolyte was kept at 30-35°C under water bath condition, the conductive substrate of gold-plated zinc oxide nanorod array was vertically put into silver electrolyte and served as cathode, graphite sheet was served as anode, the porous silver nanosheet / zinc oxide nanorod array structure was prepared on the conductive substrate after electrodeposition for 10-90 min at a current of 5-100 μA / cm 2 .

2. The porous silver nanoplate / zinc oxide nanorod array structure of claim 1, wherein, The sputtering method in step S2 is ion sputtering.

3. The porous silver nanoplate / zinc oxide nanorod array structure of claim 1, wherein, The preparation method of the silver electrolyte in step S3 is as follows: AgNO3 and cetyltrimethylammonium chloride are added to water to form a mixed solution, wherein the concentration of AgNO3 is 0.2-0.5 mM, and the concentration of cetyltrimethylammonium chloride is 3-10 mM, the mixed solution is placed in a water bath at 30-35 ℃, 0.5 mL of 1 M NaOH solution is added, and 3 M NaOH aqueous solution is added dropwise until the pH value of the mixed solution is 10-11.5, and the silver electrolyte is prepared.

4. The porous silver nanoplate / zinc oxide nanorod array structure of claim 1, wherein, 5. Use of the porous silver nanosheet / zinc oxide nanorod array structure as claimed in claim 1 as an active substrate for surface-enhanced Raman scattering. The porous silver nanosheet / zinc oxide nanorod array structure is used as an active substrate for surface-enhanced Raman scattering, and the content of dye molecules rhodamine 6G attached thereto is measured by using a laser Raman spectrometer.

6. Use of the porous silver nanoplate / zinc oxide nanorod array structure according to claim 5, characterized in that, The excitation light of the laser Raman spectrometer has a wavelength of 514 nm, 532 nm or 633 nm, a power of 0.01-1 mW, and an integration time of 0.1-60 s.

7. Use of the porous silver nanoplate / zinc oxide nanorod array structure according to claim 6, characterized in that, ​

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