CN110699646B - Preparation and application of resonance wavelength adjustable silver nanorod array - Google Patents
Preparation and application of resonance wavelength adjustable silver nanorod array Download PDFInfo
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- CN110699646B CN110699646B CN201910913078.5A CN201910913078A CN110699646B CN 110699646 B CN110699646 B CN 110699646B CN 201910913078 A CN201910913078 A CN 201910913078A CN 110699646 B CN110699646 B CN 110699646B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 31
- 239000004332 silver Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 4
- 239000002073 nanorod Substances 0.000 title abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 75
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000001514 detection method Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 19
- 239000004005 microsphere Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000005566 electron beam evaporation Methods 0.000 claims description 10
- 229940054441 o-phthalaldehyde Drugs 0.000 claims description 10
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical group O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 241000252506 Characiformes Species 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000002086 nanomaterial Substances 0.000 claims description 7
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- QPXZSVUBSZNWBF-UHFFFAOYSA-N 1,4-diaminocyclohexa-2,4-diene-1-carbaldehyde Chemical compound NC1=CCC(N)(C=O)C=C1 QPXZSVUBSZNWBF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
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- 238000005516 engineering process Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 241000894007 species Species 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000001237 Raman spectrum Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
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- 238000003892 spreading Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
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- 230000009885 systemic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of trace organic pollutant detection, and particularly relates to a method for preparing a silver nanorod array with adjustable resonance wavelength and quickly detecting trace hydrazine by utilizing the surface enhanced Raman effect of silver nanorods. The surface-enhanced raman substrate of the present invention comprises: the device comprises a substrate, wherein metal silver is deposited on the substrate and is formed into a nano inclined rod array with a forked top end. A substrate with excellent surface enhanced Raman effect is obtained by preparing a discrete silver nanorod array film with a branched top end, so that trace hydrazine is rapidly detected by utilizing the surface enhanced Raman effect. The method is simple, rapid, low in cost and high in sensitivity.
Description
Technical Field
The invention belongs to the technical field of trace organic pollutant detection, and particularly relates to a method for preparing a silver nanorod array with adjustable resonance wavelength and quickly detecting trace hydrazine by utilizing the surface enhanced Raman effect of silver nanorods.
Background
Hydrazine (N)2H4) The main fuel is a common main fuel of a liquid propellant, is used as an energy working medium of a rocket engine, and is widely applied to the fields of launching of missiles, satellites, spacecrafts and the like. Hydrazine has strong toxicity, can cause skin allergy and systemic poisoning, has great damage to the liver, kidney, nervous system and the like of a human body, and has potential carcinogenic risk. In each operation process of the liquid propellant, hydrazine is easy to pollute environment media such as atmosphere, water, soil, vegetation and the like due to running, overflowing, dripping, leaking, sudden accidents and the like. In the latest environmental quality standard for surface water (GB 3838-2002), the maximum allowable concentration of hydrazine is 0.0064mg/L (2X 10)-7mol/L). Water is a source of life, and the detection of trace hydrazine in the water body is enhanced, so that the method has great significance in the aspects of guaranteeing the health of personnel, issuing early warning of pollution in time, controlling environmental pollution and the like.
In recent years, researchers in various countries strive to establish a rapid and effective detection method for trace hydrazine in water, which mainly comprises a spectrophotometry method, an electrochemical method, an electrophoresis method, a titration method, a fluorescence analysis method, a gas chromatography/mass spectrometry analysis method and the like. However, these methods have disadvantages of requiring complicated pretreatment of hydrazine, expensive detection instruments, long time-consuming analysis and detection, and inability to perform real-time detection. Therefore, establishing a rapid, efficient and portable detection method for trace hydrazine is an important direction of research.
The nano structure of noble metal (Au, Ag, Cu, etc.) can generate local plasma resonance on the surface thereof under the induction of the photoelectric field in a specific wavelength range, and amplify the photoelectric field sensed by the detected molecules adsorbed on the surface by several orders of magnitude. When the adsorbed molecule is not more than 10nm away from its surface, the raman spectrum of the molecule is greatly enhanced due to the enhancement of the surface local electric field, a phenomenon known as the surface-enhanced raman effect.
The Raman scattering is applied to trace detection of biological and chemical molecules, so that the method has the advantages of short detection time, fingerprint identification, short detection time, low cost, capability of realizing nondestructive detection and the like, but the method needs a high-sensitivity surface enhanced Raman substrate as a basis. A unique silver nanorod array film can be obtained by combining a substrate with a template by an oblique growth method. The film is used as a surface enhanced Raman substrate, has the characteristic of adjustable resonance wavelength, has excellent surface enhancement effect under the excitation of specific wavelength, and can realize the rapid detection of trace hydrazine by utilizing the surface enhanced Raman effect by adopting derivative pretreatment.
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a method for preparing a silver nanorod array with adjustable resonance wavelength and quickly detecting trace hydrazine by utilizing the surface enhanced Raman effect of silver nanorods.
Means for solving the technical problem
In view of the above problems, the present invention provides a surface enhanced raman substrate, comprising: the device comprises a substrate, wherein metal silver is deposited on the substrate and is formed into a nano inclined rod array with a forked top end.
According to a second aspect of the invention, a preparation method of a surface-enhanced raman substrate is provided, which comprises the steps of depositing metal silver on a substrate full of polystyrene microspheres by using an inclined growth method to obtain a nano inclined rod array film with a branched top end; the microspheres are preferably polystyrene microspheres or silica microspheres.
In one embodiment, after a silicon substrate or a glass substrate is treated by a piranha method, Polystyrene (PS) microspheres with different diameters (50-1000nm) are spread on the substrate.
In one embodiment, the silver nanostructure with the length of 500-1000 nm is grown on the substrate in an inclined way by adopting an electron beam evaporation coating technology.
In one embodiment, a surface enhanced raman substrate is prepared using the above method.
According to a third aspect of the present invention, there is provided a use of the above surface enhanced raman substrate in trace species detection.
According to a fourth aspect of the present invention, there is provided a method for detecting a trace amount of hydrazine, comprising:
(1) reacting a trace amount of hydrazine to be detected with an aldehyde reagent aqueous solution to obtain a solution to be detected; the aldehyde agent is selected from o-phthalaldehyde or p-diaminobenzaldehyde;
(2) putting the surface-enhanced Raman substrate into the solution to be detected prepared in the step (1), taking out the solution after soaking, and drying the solution by using nitrogen;
(3) and (3) putting the surface enhanced Raman substrate attached with the reactant of hydrazine and aldehyde reagent in the step (2) into a Raman spectrometer for measurement.
The invention has the advantages of
A substrate with excellent surface enhanced Raman effect is obtained by preparing a discrete silver nanorod array film with a branched top end, so that trace hydrazine is rapidly detected by utilizing the surface enhanced Raman effect. The method is simple, rapid, low in cost and high in sensitivity.
Further features of the present invention will become apparent from the following description of exemplary embodiments.
Drawings
FIG. 1 is a scanning electron micrograph of a silver thin film enhanced Raman substrate prepared in example 1;
FIG. 2 is a scanning electron micrograph of a silver thin film enhanced Raman substrate prepared in example 2;
FIG. 3 is a reflection spectrum of silver nanorod array films with different lengths and adjustable resonance wavelengths.
Detailed Description
One embodiment of the present disclosure will be specifically described below, but the present disclosure is not limited thereto.
The invention uses the oblique growth method to deposit metal silver on a silicon substrate or a glass substrate which is fully paved with polystyrene microspheres to obtain a nano oblique rod array film with good discreteness and branched top end, and the silver film is used as a surface enhanced Raman substrate; mixing trace hydrazine to be detected with an o-phthalaldehyde aqueous solution for water bath reaction to obtain a solution to be detected; soaking in the solution for 2min, taking out, and slowly blowing with nitrogen; and putting the surface enhanced Raman substrate into a Raman spectrum, and quickly detecting the trace hydrazine by using a Raman spectrometer. The detection of trace hydrazine can be realized by measuring the Raman spectrum line of the hydrazine derivative.
In order to illustrate the technical solution of the present invention, the implementation of the method of the present invention optionally comprises the following steps:
(1) treating a silicon substrate or a glass substrate by adopting a piranha method, and then fully spreading Polystyrene (PS) microspheres with different diameters (50-1000nm) on the substrate; the basic steps of the piranha method are as follows: i. putting the silicon wafer substrate into a beaker, and performing ultrasonic treatment for 30min by using acetone, alcohol and deionized water respectively to remove surface pollutants; preparing sulfuric acid and hydrogen peroxide solution with a volume ratio of 3:1, soaking the substrate in the sulfuric acid and hydrogen peroxide solution, standing for 8 hours, then carrying out ultrasonic cleaning for 30min, and changing and washing for several times by using deionized water; and iii, soaking the substrate in ammonia water and hydrogen peroxide solution with the volume ratio of 3:1, ultrasonically cleaning for 30min, changing and cleaning with deionized water for several times, and soaking in the deionized water for later use.
(2) Fixing the substrate prepared in the step (1) on a sample table of an electron beam evaporation coating machine or a magnetron sputtering coating machine;
(3) using metallic silver as targetPumping the chamber of the electron beam evaporation coating machine to 3 x 10－5～2×10－4High vacuum of Pa;
(4) adjusting the incident angle of an electron beam to 75-85 ℃, enabling a sample stage to be static, obliquely growing a silver nanostructure film with the length of 500-1000 nm on a substrate of the sample stage, wherein the top of each nanorod is provided with a plurality of branched structures.
(5) The plasma resonance excitation wavelength of the nanorod array can be adjusted by adjusting the length of the silver nanorods, so that the optimal enhancement under a specific Raman laser light source is obtained.
(6) The trace hydrazine to be detected and the concentration of the hydrazine to be detected are 10-3mixing mol/L o-phthalaldehyde aqueous solution (the volume ratio of the trace hydrazine to the o-phthalaldehyde aqueous solution to be detected is 10:1), reacting for 5-15min at the water bath temperature of 40-70 ℃ to obtain the solution to be detected;
(7) putting the surface enhanced Raman substrate into the solution to be detected prepared in the step (6), taking out the solution after soaking, and slowly blowing the solution to be detected by nitrogen;
(8) and (3) putting the surface enhanced Raman substrate attached with the reactant of hydrazine and o-phthalaldehyde in the step (7) into a Raman spectrometer, selecting a light source with the wavelength of 785nm, and measuring the Raman spectrum with the laser intensity of 60 mW.
The present invention will be described in detail with reference to the accompanying drawings 1 to 3. The following examples are illustrative and not intended to be limiting, and are not intended to limit the scope of the invention.
Example 1
(1) Treating a silicon substrate or a glass substrate by adopting a piranha method, and then fully spreading Polystyrene (PS) microspheres with different diameters (50-1000nm) on the substrate;
(2) fixing the substrate prepared in the step (1) on a sample table of an electron beam evaporation coating machine;
(3) taking metallic silver as a target material, pumping a cavity of an electron beam evaporation coating machine to 3 multiplied by 10－5～2×10－4High vacuum of Pa;
(4) adjusting the incident angle of an electron beam to 75-85 ℃, enabling a sample stage to be static, obliquely growing a silver nano-structure film with the rod length of 647nm on a substrate of the sample stage, wherein the top of each nano-rod is provided with a plurality of branched structures.
(5) The plasma resonance excitation wavelength of the nanorod array can be adjusted by adjusting the length of the silver nanorods, so that the optimal enhancement under a specific Raman laser light source is obtained.
Example 2
(1) Processing a silicon substrate or a glass substrate by adopting a piranha method, and then fully paving Polystyrene (PS) microspheres with the diameter of 500nm on the substrate;
(2) fixing the substrate prepared in the step (1) on a sample table of an electron beam evaporation coating machine;
(3) taking metallic silver as a target material, pumping a cavity of an electron beam evaporation coating machine to 3 multiplied by 10－5～2×10－4High vacuum of Pa;
(4) adjusting the incident angle of an electron beam to 75-85 degrees, enabling a sample table to be static, obliquely growing a silver nano-structure film with a 771nm rod length on a substrate of the sample table, wherein the top of each nano-rod is provided with a plurality of branched structures.
(5) The plasma resonance excitation wavelength of the nanorod array can be adjusted by adjusting the length of the silver nanorods, so that the optimal enhancement under a specific Raman laser light source is obtained.
(6) 200 mu L of trace hydrazine to be detected and 20 mu L of hydrazine with the concentration of 10-3mixing mol/L o-phthalaldehyde aqueous solution, reacting for 8min at the water bath temperature of 50 ℃ to obtain solution to be detected;
(7) putting the surface-enhanced Raman substrate into the solution to be detected prepared in the step (6), soaking the surface-enhanced Raman substrate in the solution for 2min, taking out the surface-enhanced Raman substrate, and slowly blowing the surface-enhanced Raman substrate with nitrogen;
(8) putting the surface enhanced Raman substrate attached with the reactant of hydrazine and o-phthalaldehyde in the step (7) into a Raman spectrometer, selecting a light source with the wavelength of 785nm and the laser intensity of 60mW, and measuring the Raman spectrum
Example 3
(1) Processing a silicon substrate or a glass substrate by adopting a piranha method, and then fully paving Polystyrene (PS) microspheres with the diameter of 500nm on the substrate;
(2) fixing the substrate prepared in the step (1) on a sample table of an electron beam evaporation coating machine;
(3) taking metallic silver as a target material, pumping a cavity of an electron beam evaporation coating machine to 3 multiplied by 10－5～2×10－4High vacuum of Pa;
(4) adjusting the incident angle of an electron beam to 75-85 ℃, enabling a sample stage to be static, obliquely growing a silver nano-structure film with the length of 892nm on a substrate of the sample stage, wherein the top of each nano-rod is provided with a plurality of branched structures.
(5) The plasma resonance excitation wavelength of the nanorod array can be adjusted by adjusting the length of the silver nanorods, so that the optimal enhancement under a specific Raman laser light source is obtained.
(6) 200 mu L of trace hydrazine to be detected and 20 mu L of hydrazine with the concentration of 10-3mixing mol/L o-phthalaldehyde aqueous solution, reacting for 8min at the water bath temperature of 50 ℃ to obtain solution to be detected;
(7) putting the surface-enhanced Raman substrate into the solution to be detected prepared in the step (6), soaking the surface-enhanced Raman substrate in the solution for 2min, taking out the surface-enhanced Raman substrate, and slowly blowing the surface-enhanced Raman substrate with nitrogen;
(8) putting the surface enhanced Raman substrate attached with the reactant of hydrazine and o-phthalaldehyde in the step (7) into a Raman spectrometer, selecting a light source with the wavelength of 785nm and the laser intensity of 60mW, and measuring the Raman spectrum
The silver film enhanced raman substrate prepared in the above example was subjected to morphology characterization, and scanning electron micrographs were obtained as shown in fig. 1 and fig. 2, respectively.
Industrial applicability
The technical scheme of the invention is beneficial to establishing a rapid, efficient and portable detection method for trace hydrazine.
The present invention is not limited to the above embodiments, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. A method of making a surface enhanced raman substrate, wherein the surface enhanced raman substrate comprises: the device comprises a substrate, wherein Polystyrene (PS) microspheres or silicon dioxide microspheres with different diameters are fully paved on the substrate, metal silver is deposited on the substrate, and the metal silver is formed into a nano inclined rod array with a forked top end; the preparation method comprises the steps of depositing metal silver on a substrate fully paved with polystyrene microspheres or silicon dioxide microspheres by using an inclined growth method to obtain a nano inclined rod array film with a branched top end; the Polystyrene (PS) microspheres have a diameter of 50-1000nm, wherein a silver nanostructure with a rod length of 500-1000 nm is obliquely grown on a substrate by adopting an electron beam evaporation coating technology.
2. The method of claim 1, wherein the silicon or glass substrate is treated by the piranha method and then filled with Polystyrene (PS) microspheres of different diameters.
3. A surface enhanced raman substrate, characterized by being produced by the method of any one of claims 1 to 2.
4. Use of a surface enhanced raman substrate as defined in claim 3 for trace species detection.
5. A method for detecting trace hydrazine is characterized in that:
(1) reacting a trace amount of hydrazine to be detected with an aldehyde reagent aqueous solution to obtain a solution to be detected; the aldehyde agent is selected from o-phthalaldehyde or p-diaminobenzaldehyde;
(2) placing the surface-enhanced Raman substrate of claim 3 into the solution to be tested prepared in step (1), taking out after soaking, and drying by using nitrogen;
(3) and (3) putting the surface enhanced Raman substrate attached with the reactant of hydrazine and aldehyde reagent in the step (2) into a Raman spectrometer for measurement.
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