CN114990489A - Preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array - Google Patents
Preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array Download PDFInfo
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Abstract
The invention relates to a preparation method and application of an ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array. The method comprises the steps of depositing a cobalt hydroxide nanometer flower structure array on the surface of a PAN thin film modified by gold nanometer particles through an electrochemical deposition method, then sputtering the gold nanometer particles again, soaking the cobalt hydroxide nanometer flower array thin film sputtered with the gold nanometer particles into a silver nitrate solution, and growing gold @ silver nanometer particles on the surface of the cobalt hydroxide nanometer flowers in a spontaneous in-situ mode to obtain an ordered gold @ silver nanometer particle @ cobalt hydroxide nanometer flower array thin film, wherein the ordered gold @ silver nanometer flower array thin film has good SERS signal uniformity and repeatability, and can be used as a substrate for carrying out surface enhanced Raman scattering spectrum detection on organic dye pollutant molecules rhodamine 6G and 4-aminobenzophenol.
Description
Technical Field
The invention belongs to the technical field of analysis, and particularly relates to a preparation method and application of an ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array.
Background
At present, the detection of organic pollutants in printing and dyeing wastewater is mainly based on traditional gas chromatography, gas chromatography/mass spectrometry combined method, high performance liquid chromatography and the like. Although the detection methods can realize the detection of organic pollutants in a laboratory, the operation processes of sample extraction and pretreatment are relatively complicated, the detection time is long, and the detection methods are not suitable for in-situ and on-site rapid analysis of printing and dyeing polluted wastewater. The surface enhanced Raman scattering spectroscopy (SERS) technology has the characteristics of rapidness, high sensitivity and fingerprint identification detection, is one of the most sensitive analysis technologies, and is expected to be used for rapid component analysis of organic pollutants in printing and dyeing wastewater. However, the key to the application of the SERS technology is to prepare a SERS structure substrate with high SERS activity and high uniformity, so that high-quality SERS signals with good repeatability can be obtained. In general, the SERS substrate based on noble metal (gold, silver, copper) nanoparticles has higher SERS activity, so the synthesis method of the SERS substrate based on noble metal nanostructures is receiving attention from researchers.
In order to obtain a SERS substrate having high sensitivity and good signal uniformity, photolithography, nanoimprint, self-assembly, and the like are used to prepare a large area and uniformityAn ordered precious metal nanostructure array SERS substrate, for example, a three-dimensional porous gold nanorod array (ACS appl. Mater. interfaces 2014,6(18),15667 plus material 15675) is prepared by electrodepositing Au-Ag alloy by taking a straight-hole porous alumina template (AAO) as a template, and the substrate has uniform appearance structure and good SERS activity and signal uniformity, but the AAO preparation process is complex and the AAO cost is high; wanmenhui et al used an electrostatic spinning process to add HAuCl to the spinning solution 4 Preparation of gold-containing nanoparticles of (SiO) 2 @ Au) nano fiber film, then carrying out reduction reaction to grow Ag nano particles in situ to obtain large-area Ag @ SiO 2 @ Au composite nanofiber substrate (Polymers,2020,12(12),3008), and the method can be used for preparing large-area three-dimensional network-shaped precious metal nanostructure SERS substrate, but the nanofiber membrane has too long spinning time and Ag @ SiO 2 The repeatability of the @ Au substrate is poor; sun et al prepared high-purity Au nano dendrites (AuNDs) by a simple electrochemical deposition method, and then further adsorbed Ag nanoparticles reduced by citrate on the surface of the AuNDs to form an Ag @ AuNDs composite SERS substrate (Food Control, 2021, 122, 107772), and the preparation method is simple and low in cost, but the size of the Au nano structure is not easy to Control and is not uniformly distributed, so that the uniformity of SERS signals of the substrate cannot be guaranteed.
The patent number "CN 201310015880.5" is named as "method for performing surface enhanced raman scattering spectroscopy detection by using silver surface molecularly imprinted polymer", taking silver as core and molecularly imprinted polymer as shell, changes the traditional method of mixing molecularly imprinted polymer with other substances such as silver colloid to have surface enhanced raman effect, but this method is also complicated to operate and difficult to ensure uniformity. Therefore, the development of a mature, stable, rapid and simple method for preparing the SERS substrate of the silver nano material with controllable and uniform appearance has important significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of an ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array, and aims to prepare a rapid, simple, controllable and uniform SERS (surface enhanced Raman Scattering) substrate made of silver nanomaterials.
In order to solve the technical problems, one of the purposes of the invention is to provide a preparation method of an ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array, which comprises the following steps:
s1 preparation of PAN film
Uniformly dispersing a certain mass fraction of PAN (polyacrylonitrile) solution on a silicon wafer template with a regular nano-pore array structure, drying and stripping the solution from the silicon wafer template to obtain a PAN (polyacrylonitrile) film with an ordered nano-pillar array structure on one side;
s2, first sputtering
Sputtering a layer of gold nanoparticles on the surface of the PAN film for the first time by using an ion sputtering instrument to obtain the PAN film modified by the gold nanoparticles;
s3, preparing cobalt hydroxide nano-flower array film
Preparing an electrolyte solution, and depositing a cobalt hydroxide nanoflower structure array on the surface of the gold nanoparticle modified PAN thin film by an electrochemical deposition method to obtain a cobalt hydroxide nanoflower array thin film;
s4, second sputtering
Sputtering gold nanoparticles on the surface of the cobalt hydroxide nanoflower array film for the second time by using an ion sputtering instrument;
s5, in-situ synthesis of gold @ silver nanoparticle @ cobalt hydroxide nanoflower array
The cobalt hydroxide nanometer flower array film sputtered with the gold nanoparticles is soaked in a silver nitrate solution under a dark condition, and the ordered gold @ silver nanometer particle @ cobalt hydroxide nanometer flower array is spontaneously synthesized in situ on the surface of the cobalt hydroxide nanometer flower by utilizing the reduction characteristic of cobalt ions and the seed crystal induced growth action of the gold nanoparticles.
Preferably, the PAN solution in S1 is prepared by dissolving polyacrylonitrile powder in N, N-dimethylformamide solution, and stirring in water bath until completely dissolved to obtain PAN solution with mass fraction of 6-10%.
Preferably, the time for sputtering the gold nanoparticles for the first time in S2 is 3-5min, and the time for sputtering the gold nanoparticles for the second time in S4 is 30S-2 min.
Preferably, the electrolyte solution in S3 is a mixed aqueous solution of cobalt nitrate and potassium chloride, wherein the concentration of cobalt nitrate is 0.01-0.04mol/L, and the concentration of potassium chloride is 0.04-0.2 mol/L.
Further, the electrochemical deposition method is that the PAN thin film substrate modified by the gold nanoparticles is placed in an electrolyte solution, deposition is carried out in a constant current mode in an electrochemical workstation, the deposition current is 0.2-2mA, and the electrodeposition time is 2-15 min.
Further, the concentration of the silver nitrate solution in the S5 is 0.01-0.1 mol/L.
The second purpose of the invention is to provide the application of the ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array prepared by the method, wherein the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array is used as a substrate to carry out surface enhanced Raman scattering spectrum detection on organic dye pollutant molecules rhodamine 6G and organic reagent 4-aminothiophenol.
Further, the surface enhanced Raman scattering spectrum detection is carried out by taking an organic dye pollutant rhodamine 6G and an organic reagent 4-amino thiophenol as detection molecules, taking a gold @ silver nanoparticle @ cobalt hydroxide nanoflower array which is soaked in an aqueous solution of rhodamine 6G and an ethanol solution of 4-amino thiophenol and dried in the air as a substrate, and carrying out Raman detection by adopting a laser Raman spectrometer.
In a further scheme, the excitation wavelength of the laser Raman spectrometer is 532nm and 785nm, the laser power is 5-10mW, and the excitation time is 1-10 s.
Due to the adoption of the technical scheme, the invention achieves the technical effects that:
1. by adopting the preparation method of the ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array, the SERS substrate with the high-performance composite noble metal nanostructure is prepared based on spontaneous reduction reaction, so that the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array with large area, uniform distribution and ordered appearance is prepared on the surface of the PAN film. The method is simple to operate and low in cost, a large-area cobalt hydroxide nanoflower array is obtained through an electrochemical deposition method, and the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array which is uniformly distributed in a large area and consistent in appearance can be spontaneously and rapidly generated on the surface of the cobalt hydroxide nanoflower by utilizing the reduction characteristic of cobalt ions and the induction effect of gold nanoparticles on the growth of silver nanoparticles.
2. The ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array prepared by the method not only combines the high SERS activity of the gold @ silver nanoparticles, but also can load more gold @ silver nanoparticles by large-area ordered cobalt hydroxide nanoflowers, so that the SERS activity is further improved; meanwhile, the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array is uniformly distributed on the surface of the PAN film, so that the uniformity and repeatability of an SERS signal of the substrate are guaranteed.
3. The ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array prepared by the method has potential application prospects in the fields of chemical analysis, pollutant detection, biosensors and the like based on an SERS technology, is used as an SERS substrate, realizes quick detection and identification of organic pollutants rhodamine 6G and 4-aminothiophenol, and has important development significance in realizing quick trace detection of the organic pollutants in printing and dyeing wastewater through an SERS effect.
Drawings
FIG. 1 is a schematic diagram of a process for preparing gold @ silver nanoparticle @ cobalt hydroxide nanoflower arrays;
FIG. 2 is a Scanning Electron Microscope (SEM) characterization of nanopillar arrays on PAN films;
FIG. 3 is SEM photographs of cobalt hydroxide nanoflower arrays obtained after 3, 6, 9 and 12min of electrodeposition in examples 1-4, respectively;
FIG. 4 is a transmission electron micrograph of cobalt hydroxide nanoflower;
FIG. 5 is an EDS spectrum of cobalt hydroxide nanoflower;
FIG. 6 is an X-ray diffraction line of cobalt hydroxide nanoflower;
FIG. 7 is an SEM photograph of gold @ silver nanoparticle @ cobalt hydroxide nanoflower arrays obtained after dipping in silver nitrate solution for 10 min;
FIG. 8 is an X-ray diffraction line of a gold @ silver nanoparticle @ cobalt hydroxide nanoflower array;
FIG. 9 is an EDS spectrum of gold @ silver nanoparticle @ cobalt hydroxide nanoflower arrays;
FIG. 10 SERS spectra of gold @ silver nanoparticles @ cobalt hydroxide nanoflower arrays for different concentrations of rhodamine 6G;
FIG. 11 is a SERS spectrum of gold @ silver nanoparticle @ cobalt hydroxide nanoflower arrays with different concentrations of 4-aminothiophenol;
FIG. 12 shows the concentration of 10 pairs of gold @ silver nanoparticles @ cobalt hydroxide nanoflower arrays at 20 randomly selected spots - 5 SERS spectrum of 4-aminothiophenol of M;
fig. 13 is an SEM topography of the gold @ silver nanoparticle @ cobalt hydroxide nanoflower arrays obtained after the cobalt hydroxide nanoflowers were immersed in silver nitrate solutions for 2min, 10min, and 20min in examples 3, 9, and 10, respectively.
Detailed Description
The invention will be further elucidated with reference to the specific embodiments and the accompanying figures 1-12.
Example 1 preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array
S1, uniformly dripping 0.25ml of PAN (polyacrylonitrile) solution on a silicon wafer template with a regular ordered nano-pore array structure, then drying in a 70 ℃ oven for 30min, removing the cured PAN film from the template after drying, and transferring the surface with the nano-column array to the silicon wafer to obtain the PAN film with the ordered nano-column array structure on one surface; as shown in fig. 2, the nano-pillar array on the film is characterized by a Scanning Electron Microscope (SEM) with regular shape and uniform structure, the center-to-center distance of the nano-pillars is about 1500nm, and the diameter of the nano-pillars is 800 nm;
the preparation method of the PAN solution comprises the steps of dissolving polyacrylonitrile powder in an N, N-dimethylformamide solution, and stirring in a water bath at 60 ℃ for 30min to obtain the PAN solution with the mass fraction of 8%.
And S2, placing the prepared PAN film with the front side facing upwards in an ion sputtering instrument for sputtering the gold nanoparticles for 4min to obtain the PAN film modified by the gold nanoparticles.
S3, using gold nanoparticle modified PAN film as a working electrode, graphite as a counter electrode and Co (NO) with the concentration of 0.02mol/L 3 ) 2 And taking a mixed aqueous solution of 0.1mol/L KCl as an electrolyte solution, controlling the deposition current to be 0.75mA, and depositing for 3min to obtain the cobalt hydroxide nanoflower array film.
S4, placing the prepared cobalt hydroxide nanoflower array film with the right side facing upwards in an ion sputtering instrument for sputtering gold nanoparticles for 1 min.
S5, soaking the cobalt hydroxide nanoflower array film sputtered with the gold nanoparticles into 0.05mol/L silver nitrate solution in the dark for 10min, and spontaneously synthesizing the ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array on the surface of the cobalt hydroxide nanoflower in situ by utilizing the reduction characteristic of cobalt ions and the seed crystal induced growth action of the gold nanoparticles.
S6, testing SERS performance of the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array, soaking the prepared gold @ silver nanoparticle @ cobalt hydroxide nanoflower array substrate into rhodamine 6G aqueous solutions with different concentrations, taking out the substrate after 4 hours, naturally drying the substrate, and testing Raman spectrum by using a laser Raman spectrometer after drying. Wherein the excitation wavelength of the laser Raman spectrometer is 532nm, the power is 5 milliwatts, and the excitation time is 2 seconds.
Transferring the prepared gold @ silver nanoparticle @ cobalt hydroxide nanoflower substrate into 4-aminothiophenol/ethanol solutions with different concentrations, taking out the substrate after 4 hours, naturally drying the substrate, and testing the Raman spectrum by using a laser Raman spectrometer after drying. Wherein the laser Raman spectrometer has an excitation wavelength of 785nm, a power of 5 milliwatts and an excitation time of 2 seconds.
Example 2 preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array
The present embodiment is different from embodiment 1 in that the deposition time in the step of S3 is 6 min.
Example 3 preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array
The present embodiment is different from embodiment 1 in that the deposition time in the step of S3 is 9 min.
Example 4 preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array
The present embodiment is different from embodiment 1 in that the deposition time in the step of S3 is 12 min.
Example 5 preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array
S1, uniformly dripping 0.25ml of PAN (polyacrylonitrile) solution on a silicon wafer template with a regular ordered nano-pore array structure, then drying in a 70 ℃ oven for 30min, removing the cured PAN film from the template after drying, and transferring the surface with the nano-column array to the silicon wafer to obtain the PAN film with the ordered nano-column array structure on one surface;
the preparation method of the PAN solution comprises the steps of dissolving polyacrylonitrile powder in an N, N-dimethylformamide solution, and stirring in a water bath at 60 ℃ for 30min to obtain the PAN solution with the mass fraction of 6%.
And S2, placing the prepared PAN film with the front side facing upwards into an ion sputtering instrument to sputter gold nanoparticles for 3min to obtain the PAN film modified by the gold nanoparticles.
S3, using gold nanoparticle modified PAN film as a working electrode, graphite as a counter electrode and 0.01mol/L Co (NO) as a catalyst 3 ) 2 And taking a mixed aqueous solution of 0.2mol/L KCl as an electrolyte solution, controlling the deposition current to be 0.2mA, and depositing for 9min to obtain the cobalt hydroxide nanoflower array film.
S4, placing the prepared cobalt hydroxide nanoflower array film with the right side facing upwards in an ion sputtering instrument for sputtering gold nanoparticles for 30S.
S5, soaking the cobalt hydroxide nanoflower array film sputtered with the gold nanoparticles into 0.01mol/L silver nitrate solution in the dark for 10min, and spontaneously synthesizing the ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array on the surface of the cobalt hydroxide nanoflower in situ by utilizing the reduction characteristic of cobalt ions and the seed crystal induced growth effect of the gold nanoparticles.
S6, testing SERS performance of the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array, soaking the prepared gold @ silver nanoparticle @ cobalt hydroxide nanoflower array substrate into rhodamine 6G aqueous solutions with different concentrations, taking out the substrate after 4 hours, naturally drying the substrate, and testing Raman spectrum by using a laser Raman spectrometer after drying the substrate in the air. Wherein the excitation wavelength of the laser Raman spectrometer is 532nm, the power is 10 milliwatts, and the excitation time is 1 second.
Transferring the prepared gold @ silver nanoparticle @ cobalt hydroxide nanoflower substrate into 4-aminothiophenol/ethanol solutions with different concentrations, taking out the substrate after 4 hours, naturally drying the substrate, and testing the Raman spectrum by using a laser Raman spectrometer after drying. Wherein the laser Raman spectrometer has an excitation wavelength of 785nm, a power of 5 milliwatts and an excitation time of 1 second.
Example 6 preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array
S1, uniformly dripping 0.25ml of PAN (polyacrylonitrile) solution on a silicon wafer template with a regular ordered nano-pore array structure, then drying in a 70 ℃ oven for 30min, removing the cured PAN film from the template after drying, and transferring the surface with the nano-column array to the silicon wafer to obtain the PAN film with the ordered nano-column array structure on one surface;
the preparation method of the PAN solution comprises the steps of dissolving polyacrylonitrile powder in an N, N-dimethylformamide solution, and stirring in a water bath at 60 ℃ for 30min to obtain the PAN solution with the mass fraction of 10%.
And S2, placing the prepared PAN film with the front side facing upwards in an ion sputtering instrument for sputtering the gold nanoparticles for 5min to obtain the PAN film modified by the gold nanoparticles.
S3, using gold nanoparticle modified PAN film as a working electrode, graphite as a counter electrode and Co (NO) with the concentration of 0.04mol/L 3 ) 2 And taking a mixed aqueous solution of 0.04mol/L KCl as an electrolyte solution, controlling the deposition current to be 2mA, and controlling the deposition time to be 3min to obtain the cobalt hydroxide nanoflower array film.
S4, placing the prepared cobalt hydroxide nanoflower array film with the right side facing upwards in an ion sputtering instrument for sputtering gold nanoparticles for 2 min.
S5, soaking the cobalt hydroxide nanoflower array film sputtered with the gold nanoparticles into 0.1mol/L silver nitrate solution in the dark for 6min, and spontaneously synthesizing the ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array on the surface of the cobalt hydroxide nanoflower in situ by utilizing the reduction characteristic of cobalt ions and the seed crystal induced growth effect of the gold nanoparticles.
S6, testing SERS performance of the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array, soaking the prepared gold @ silver nanoparticle @ cobalt hydroxide nanoflower array substrate into rhodamine 6G aqueous solutions with different concentrations, taking out the substrate after 4 hours, naturally drying the substrate, and testing Raman spectrum by using a laser Raman spectrometer after drying. Wherein the excitation wavelength of the laser Raman spectrometer is 532nm, the power is 5 milliwatts, and the excitation time is 10 seconds.
Transferring the prepared gold @ silver nanoparticle @ cobalt hydroxide nanoflower substrate into 4-aminothiophenol/ethanol solutions with different concentrations, taking out the substrate after 4 hours, naturally drying the substrate, and testing the Raman spectrum by using a laser Raman spectrometer after drying. Wherein the laser Raman spectrometer has an excitation wavelength of 785nm, a power of 5 milliwatts, and an excitation time of 3 seconds.
Example 7 preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array
The present embodiment is different from embodiment 3 in that the deposition current in the step of S3 is 0.2 mA.
Example 8 preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array
The present embodiment is different from embodiment 3 in that the deposition current in the step of S3 is 2 mA.
Example 9 preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array
The present embodiment is different from embodiment 3 in that the soaking time in the step S5 is 2 min.
Example 10 preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array
The present embodiment is different from embodiment 3 in that the soaking time in the step S5 is 20 min.
Examples 1-4 different electrochemical deposition times, control of the deposition time, can affect the substrate topography and SERS performance. When the deposition time is shorter, the size of the cobalt hydroxide nanosheet growing on the surface of the PAN nanorod is smaller. With the prolonging of the deposition time, the size of the cobalt hydroxide nanosheet is continuously increased, and an ordered nanoflower cluster structure is formed on the surface of the PAN nano-column. When the deposition time is too long, the size of the nanosheets is further increased, and the gaps among the nanoflower clusters are gradually reduced to disappear. As shown in fig. 3, the size of the obtained cobalt hydroxide nanosheet array gradually increased with the increase of deposition time. When the deposition time was relatively short at 3min (fig. 3a), cobalt hydroxide nanoplates with a diameter of about 300nm were deposited on the surface of the PAN nanopillar film. The spacing between adjacent cobalt hydroxide nanoflowers was about 300 nm. As the deposition time increased to 6min (fig. 3b), the size of the cobalt hydroxide nanosheets deposited on the surface of the thin film gradually increased, and the distance between adjacent nanoflowers was reduced to around 260 nm. When the deposition time was increased to 9min (fig. 3c), the cobalt hydroxide nanoflower diameter significantly increased and the distance between the corresponding adjacent nanoflowers decreased to around 200 nm. The deposition time is further extended to 12min (fig. 3d), at this time, the density of the nanosheets is continuously increased, the size of the single nanosheet is further increased, and the distance between adjacent nanoflowers is reduced to about 130 nm.
The deposition current at step S3 in examples 3, 7 and 8 was different, and the remaining parameters were unchanged. When the same deposition time is kept and the deposition current is prolonged, the density of the prepared cobalt hydroxide nanosheets is gradually increased, the size of the single nanosheets is gradually increased, and the diameter of a nano flower cluster formed by the cobalt hydroxide nanosheets growing around the PAN nano column is increased. When the deposition current is small, the cobalt hydroxide nanosheets grow slowly, and the nanosheets are small in size. With the increase of the deposition current, the cobalt hydroxide nanosheets grow rapidly on the surface of the substrate, and the size of the nanosheets is increased to form a nanoflower cluster structure.
In addition, with the prolonging of the deposition time or the increasing of the deposition current, the SERS activity of the prepared substrate shows the trend of increasing firstly and then decreasing, which shows that the appearance of the substrate can be regulated and controlled by controlling the deposition time and the deposition current, so that the SERS performance of the substrate is further regulated and controlled.
Fig. 4 is a transmission electron micrograph of the cobalt hydroxide nanoflowers stacked on top of each other, and the result shows that the synthesized cobalt hydroxide nanoflowers are composed of alternating flaky cobalt hydroxide sheets, and the in-plane size of the synthesized cobalt hydroxide nanoflowers is about 400 nm. Fig. 5 is an EDS spectrum of the cobalt hydroxide nanoflower, which indicates that the nanoflower is mainly composed of Co and O, and the prepared cobalt hydroxide nanoflower is relatively pure without other impurities. Fig. 6 shows X-ray diffraction line results of cobalt hydroxide nanoflower, and three distinct diffraction peaks were observed at 2 θ angles of 11.68 °, 33.85 ° and 59.38 °, and respectively assigned to the (003), (101) and (110) crystal planes of the cobalt hydroxide crystal.
FIG. 7 is an SEM topography of gold @ silver nanoparticles @ cobalt hydroxide nanoflowers obtained after the cobalt hydroxide nanoflowers are immersed in a silver nitrate solution for 10 min. Fig. 7a shows that the sample still maintains the structure of the nano flower-like array as a whole, but the diameter of the single cluster nano flower is obviously reduced, and the complete sheet-like structure is difficult to observe. At the same time, a large number of granular structures grow on the sample surface, making the sample surface rough (fig. 7 b).
Fig. 8 is an XRD test result of gold @ silver nanoparticles @ cobalt hydroxide nanoflower, in which in addition to the (003) plane diffraction peak of cobalt hydroxide crystals observed at an angle of 11.95 ° 2 θ, four distinct diffraction peaks were observed at positions 38.95 °, 45.25 °, 65.4 °, and 78.1 °, which were respectively assigned to the (111), (200) planes of gold and the (220), (311) planes of silver. In addition, fig. 9 is an EDS spectrum of the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array, which indicates that the prepared substrate mainly consists of Co, O, and Ag, and further demonstrates that the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array is successfully prepared.
When the concentrations of rhodamine 6G (FIG. 10) and 4-aminothiophenol (FIG. 11) were as low as 10, respectively -11 M and 10 -9 M, the substrate can still observe a certain Raman signal. The result shows that the prepared substrate has good SERS activity.
FIG. 12 shows the concentration of 10 pairs of gold @ silver nanoparticles @ cobalt hydroxide nanoflower array substrate at 20 randomly selected spots -5 The SERS spectrum of the 4-aminothiophenol of M shows that the prepared substrate has good uniformity of SERS signals.
Fig. 13 is an SEM topography of the gold @ silver nanoparticle @ cobalt hydroxide nanoflower arrays obtained after the cobalt hydroxide nanoflowers were immersed in silver nitrate solutions for 2min, 10min, and 20min in examples 3, 9, and 10, respectively. The results show that the sample still retains the nanoflower-like array structure overall, but the single cluster nanoflower diameter decreases significantly with the immersion time. When the dipping time is shorter than 2min (fig. 13a, b), a granular structure with the size of about 50nm is obviously observed on the cobalt hydroxide sheet, at the moment, the nano flower-shaped structure is clear, the nano sheet structure is complete, and the change of the appearance size is small. When the dipping time was prolonged to 10min (fig. 13c, d), a large amount of granular structures grew on the sample surface, making the sample surface rough, it was difficult to observe a complete sheet structure, and the nanoflower diameter was significantly reduced. When the dipping time is prolonged to 20min (fig. 13e, f), the diameter of the nanoflower is further reduced, the size of the nanosheets is reduced, and the abundant lamellar structure is gradually destroyed along with the prolonging of the dipping time. Fig. 13 shows that the time for dipping the silver nitrate solution is prolonged, the sample still has a regular nanometer flower-like cluster structure, however, as the dipping time is prolonged, the reduction reaction occurs on the nanometer sheet, the diameter of the cobalt hydroxide nanometer flower cluster is gradually reduced, the surface texture of the sample becomes rougher, and the content of Ag in the sample is increased. In addition, the process also directly influences the SERS performance of the substrate, and when the time for dipping the silver nitrate solution is prolonged, the content of the gold @ silver nanoparticles is increased, so that the SERS activity of the substrate is promoted. With the continuous increase of the soaking time, the surface of the nanosheet becomes rougher, but the silver nanoparticles on the surface agglomerate to be not beneficial to the improvement of the SERS signal, so that the SERS activity of the substrate tends to increase firstly and then decrease along with the extension of the soaking time.
The gold @ silver nanoparticle @ cobalt hydroxide nanoflower arrays prepared in examples 1-10 are tested, and all show good SERS activity and signal uniformity, so that the rapid detection and identification of organic pollutants rhodamine 6G and 4-aminothiophenol are realized, and the potential application value of the gold @ silver nanoparticle @ cobalt hydroxide nanoflower arrays in the aspect of detecting dye molecules in printing and dyeing wastewater is proved.
Unless otherwise specified, the proportions are mass proportions, and the percentages are mass percentages; the raw materials are all purchased from the market.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array is characterized by comprising the steps of preparing a PAN (polyacrylonitrile) film, performing first sputtering, preparing a cobalt hydroxide nanoflower array film, performing second sputtering and synthesizing the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array in situ.
2. The method for preparing an ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array according to claim 1, wherein the PAN film is prepared by uniformly dispersing a certain mass fraction of PAN (polyacrylonitrile) solution on a silicon wafer template with a regular nano-pore array structure, drying, and peeling from the silicon wafer template to obtain the PAN film with an ordered nano-pillar array structure on one surface.
3. The method for preparing an ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array according to claim 1, wherein the first sputtering is performed by using an ion sputtering apparatus to sputter a layer of gold nanoparticles on the surface of the PAN film for the first time, so as to obtain the PAN film modified by the gold nanoparticles.
4. The method for preparing an ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array according to claim 1, wherein the cobalt hydroxide nanoflower array film is prepared by preparing an electrolyte solution and depositing a cobalt hydroxide nanoflower structure array on the surface of the gold nanoparticle modified PAN film by an electrochemical deposition method to obtain the cobalt hydroxide nanoflower array film.
5. The method for preparing an ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array according to claim 1, wherein the second sputtering is performed by using an ion sputtering apparatus to sputter gold nanoparticles on the surface of the cobalt hydroxide nanoflower array film for the second time.
6. The method for preparing an ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array according to claim 1, wherein the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array is synthesized in situ, and the cobalt hydroxide nanoflower array film sputtered with gold nanoparticles is soaked in a silver nitrate solution under dark conditions to synthesize the gold @ silver nanoparticle @ cobalt hydroxide nanoflower array in situ.
7. The method as claimed in claim 5, wherein the sputtering time in the first sputtering is 3-5min, and the sputtering time in the second sputtering is 30s-2 min.
8. The method for preparing an ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array as claimed in claim 4, wherein the electrolyte solution is a mixed aqueous solution of cobalt nitrate and potassium chloride, wherein the concentration of cobalt nitrate is 0.01-0.04mol/L, and the concentration of potassium chloride is 0.04-0.2 mol/L;
the deposition current of the electrochemical deposition is 0.2-2mA, and the electrodeposition time is 2-15 min.
9. The method for preparing the ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array according to claim 6, wherein the concentration of the silver nitrate solution is 0.01-0.1 mol/L.
10. The use of gold @ silver nanoparticle @ cobalt hydroxide nanoflower arrays prepared by the method of claim 1, wherein: performing surface enhanced Raman scattering spectrum detection on organic dye pollutant molecule rhodamine 6G and organic reagent 4-aminothiophenol by taking the gold @ silver nano particles @ cobalt hydroxide nanoflower as a substrate; the detection adopts a laser Raman spectrometer, the excitation wavelength is 532nm and 785nm, the laser power is 5-10mW, and the excitation time is 1-10 s.
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