CN115194147A - SERS substrate material Au @ ZnAl-LDHs and preparation method and application thereof - Google Patents
SERS substrate material Au @ ZnAl-LDHs and preparation method and application thereof Download PDFInfo
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- 238000001514 detection method Methods 0.000 claims abstract description 24
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- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical group CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 5
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/18—Non-metallic particles coated with metal
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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Abstract
The invention belongs to the technical field of material preparation, and discloses an SERS substrate material Au @ ZnAl-LDHs and a preparation method and application thereof. The invention utilizes 1) the excellent SERS effect of the Au NPs, 2) the advantages of low cost, high chemical stability, ultrahigh adsorption performance and optical transparency of the ZnAl-LDHs, and 3) the synergistic effect of effectively inhibiting the gold nanoparticle agglomeration by loading the Au NPs on the surface of the ZnAl-LDHs, thereby greatly improving the performance of the Au NPs as the SERS substrate. The composite nano material for SERS detection based on the invention has the advantages of simple preparation method, low cost, high detection sensitivity and good repeatability, and has great application prospects in the aspects of trace analysis, qualitative detection and the like of target analytes.
Description
Technical Field
The invention belongs to the technical field of material preparation, and relates to a SERS substrate material, a preparation method and application thereof, in particular to preparation of an Au nanoparticle/two-dimensional semiconductor composite ZnAl-LDHs.
Background
The Raman spectrum can reveal the microstructure information of the sample by detecting the vibration spectrum of the sample, and has the advantages of high detection speed, simple operation and no need of sample preparation basically. However, because the raman signal generated by the small raman scattering cross section of the substance is weak and is easily interfered by the fluorescence signal, the raman spectrum of the sample is difficult to obtain in the actual detection process; especially, when the concentration of the sample to be detected is relatively low, the raman signal is difficult to be effectively monitored, so that the application of the raman spectrum detection technology is limited to a certain extent.
The Surface Enhanced Raman Scattering (SERS) spectrum overcomes the defect of weak signals of the traditional Raman spectrum, and is concerned by the advantages of high sensitivity, high detection speed, low detection limit and the like in the fields of chemical analysis, catalysis, biological medical treatment, food detection, environmental monitoring and the like. When the roughened metal surface is irradiated by incident light, the plasma on the metal surface is excited to high energy level, coupled with photon and resonated to increase the electromagnetic field on the metal surface and obtain enhanced Raman scattering effectEM) with the reinforcing effect of 10 6 -10 14 And (4) doubling. Since the discovery of the surface enhanced raman effect, the SERS substrate of noble metals and various nanostructures thereof has attracted much attention, but suffers from a series of problems of poor repeatability, low stability, high cost, and the like.
The development of introducing two-dimensional materials into new SERS substrates has numerous advantages as well: the nano-structure can be used as a protective layer of a metal plasma nano structure, so that the oxidation resistance of the substrate is improved, and the SERS substrate can obtain long-term detection cruising power; the surface active material can be used as a carrier of the noble metal nanoparticles, so that the noble metal nanoparticles are dispersed and attached to the surface of a two-dimensional material to effectively inhibit the aggregation of the two-dimensional material, and the excellent SERS performance of the noble metal nanoparticles is fully exerted; a large number of surface active sites exposed by the two-dimensional material have good affinity with molecules, so that the adsorption and modification of the molecules are easy, and the actual application detection capability can be improved; the two-dimensional material can also play a role in chemical enhancement (CM) by means of energy transfer, charge transfer and the like between the two-dimensional material and molecules to be detected, so that the detection sensitivity is improved; and background fluorescence can be quenched, so that the real usability of the Raman signal is ensured.
Based on the above factors, the combination of the noble metal nano material and the two-dimensional material is an effective way for developing a novel SERS substrate with low cost, high stability and good enhancement effect. The invention provides a composite nano material of ZnAl-LDHs loaded Au NPs as an SERS substrate, wherein the gold nano material has high enhancement factors, and is one of research hotspots in the SERS field, and ZnAl-LDHs is a two-dimensional material which has the advantages of rich raw material reserves, low price, simple preparation, high stability, good chemical adsorption performance and high optical transparency. The Au @ ZnAl-LDHs composite nano material is used for detecting organic matters, and the lowest detection limit reaches 10 -13 M (4-nitrothiophenol).
Disclosure of Invention
In consideration of the problems of the existing SERS substrate material, the invention provides a preparation method of layered double-metal hydroxide composite nano-gold particles and application of the layered double-metal hydroxide composite nano-gold particles as an SERS substrate.
The SERS substrate material comprises gold nanoparticles and layered two-dimensional bimetallic hydroxide ZnAl-LDHs, wherein the gold nanoparticles are dispersed on the surface of the ZnAl-LDHs, and the substrate material is expressed by Au @ ZnAl-LDHs. Preferably, the thickness of the layered two-dimensional bimetal hydroxide ZnAl-LDHs is less than 3nm, and the particle size of the gold nanoparticles is 20-28nm.
The preparation method of the SERS substrate material comprises the following steps: and mixing the ZnAl-LDHs dispersion liquid with the gold nanoparticle dispersion liquid, and stirring at room temperature for at least 5 hours to obtain the Au @ ZnAl-LDHs composite material suspension.
Preferably, the preparation process of the ZnAl-LDHs dispersion liquid comprises the following steps: dissolving a zinc source, an aluminum source and urea in ethylene glycol, transferring the obtained solution into a reaction kettle for solvent thermal reaction, naturally cooling, centrifuging, washing with ethanol, and dispersing in deionized water. Preferably, the zinc source is zinc nitrate hexahydrate, and the aluminum source is aluminum nitrate nonahydrate. Preferably, the concentration of the zinc source in the solution is 10mM, the concentration of the aluminum source is 5mM, and the concentration of the urea is 35mM. Preferably, the solvothermal reaction temperature is 100 ℃ and the reaction time is 24 hours.
Preferably, the preparation process of the gold nanoparticle dispersion liquid comprises the following steps: adding a tetrachloroauric acid solution into boiling deionized water under the stirring condition, then injecting a sodium citrate solution, reacting, and cooling to room temperature to obtain a gold nanoparticle dispersion liquid; preferably, the concentration of the tetrachloroauric acid solution is 25mM, the concentration of the sodium citrate solution is 5wt%, and the volume ratio of the tetrachloroauric acid solution to the deionized water to the sodium citrate solution is 1mL:99mL of: 2.3mL.
The substrate material can be applied to methods such as surface enhanced Raman scattering, organic molecule Raman detection and the like.
A method of detecting an organic molecule, the method comprising: mixing the suspension of the substrate material with an organic molecule aqueous solution with the same volume, stirring at room temperature, taking the mixed solution, performing suction filtration by using a water system filter membrane with the pore diameter of 0.22 mu m and the diameter of 25mm, performing vacuum drying, and performing Raman spectrum detection; the organic molecule is at least one of 4-nitrothiophenol and crystal violet.
As an exemplary technical scheme, the preparation method of the Au @ ZnAl-LDHs composite nano material specifically comprises the following preparation steps:
(1) Dissolving 0.8mmol of zinc nitrate hexahydrate, 0.4mmol of aluminum nitrate nonahydrate and 2.8mmol of urea in 80ml of ethylene glycol, transferring the mixture to a 100ml reaction kettle for solvothermal reaction, naturally cooling, centrifuging, washing with ethanol for three times, dispersing the mixture in deionized water for storage (solution A), and calibrating the solution concentration to be about 1.6g/L in a drying and weighing mode;
(2) Preparing gold nanoparticles: under the condition of magnetic stirring, 1ml of tetrachloroauric acid solution (25 mM) is added into 99ml of boiling deionized water, then 2.3ml of sodium citrate solution (5 wt%) is injected, reaction is carried out for 20min, and gold nanoparticle dispersion liquid-B liquid is obtained after cooling to room temperature;
(3) And mixing 20ml of solution A with 10ml of solution B, stirring for five hours at room temperature, and storing the prepared Au @ ZnAl-LDHs composite nano material for later use.
The prepared material is visible light transparent ultrathin two-dimensional ZnAl-LDHs loaded and dispersed Au nano particles, and has good stability and fluorescence quenching effect.
As an exemplary technical scheme of the invention, the Au @ ZnAl-LDHs composite nano material is used as an SERS substrate for detecting organic matters, and the specific implementation method comprises the following steps:
(1) Mixing the prepared Au @ ZnAl-LDHs composite nano-material dispersion liquid with the probe molecule solution with the same volume, and stirring for 1 hour at room temperature;
(2) Taking 2ml of the mixed solution, performing suction filtration by using a water system filter membrane with the pore diameter of 0.22 mu m and the diameter of 25mm, attaching the mixed solution on a carrier sheet, and performing vacuum drying at 60 ℃;
(3) Performing Raman spectrum test, wherein the wavelength is 785nm, the long-focus objective lens is 50 times, the exposure time is 10s, the excitation power is 1 percent, and the accumulated times are 8 times; 6 spots were selected for different positions on each filter.
According to some embodiments of the invention, the probe molecule solution is an aqueous solution of organic molecules.
According to some embodiments of the invention, the probe molecule comprises at least one of crystal violet and 4-nitrothiophenol.
According to the application of the embodiment of the invention, at least the following beneficial effects are achieved:
(1) The invention utilizes 1) the excellent SERS effect of the Au NPs, 2) the advantages of low cost, high chemical stability, ultrahigh adsorption performance and optical transparency of the ZnAl-LDHs, and 3) the synergistic effect of effectively inhibiting the gold nanoparticle agglomeration by loading the Au NPs on the surface of the ZnAl-LDHs, thereby greatly improving the performance of the Au NPs as the SERS substrate. The invention fully utilizes the advantages of the two materials to obtain the SERS composite material substrate with excellent performance, low detection limit and high sensitivity, and particularly has the detection limit of 10 to 4-NBT probe molecules -13 M; the trace analysis and qualitative detection of the target analyte are realized.
(2) The method is simple and convenient to operate, and the cost of the traditional noble metal SERS substrate is reduced.
Drawings
Fig. 1 is an XRD curve of the ultra-thin two-dimensional ZnAl-LDHs deionized water suspension prepared in the first embodiment of the present invention, which is measured after being filtered and dried, and the diffraction peak of the sample measured experimentally corresponds to the data of JCPD No.48-1024, indicating that layered double hydroxide is generated. The insets are suspensions of ultrathin two-dimensional ZnAl-LDHs dispersed in water, and the Tyndall effect can be observed under the irradiation of a red laser pen, which shows that the ultrathin two-dimensional ZnAl-LDHs is uniformly dispersed in the water solution.
FIG. 2 is a TEM image of the ultrathin two-dimensional ZnAl-LDHs prepared in the first embodiment of the present invention, which shows that the ultrathin layered material is prepared, and the thickness does not exceed 3nm.
FIG. 3 is (a) a TEM image of the Au @ ZnAl-LDHs composite nanomaterial prepared in the first embodiment of the present invention, in which it can be seen that the gold nanoparticles are dispersed on the surface of the two-dimensional ZnAl-LDHs; (b) The high-resolution TEM image of the sample can clearly observe parallel crystal planes with the spacing of 0.262nm and 0.235nm, which respectively correspond to the (104) crystal plane of two-dimensional ZnAl-LDHs and the (111) crystal plane of Au NPs.
FIG. 4 is a graph of the ultraviolet absorption spectrum of the suspension of Au @ ZnAl-LDHs composite nanomaterial prepared in the first embodiment of the present invention, wherein the inset is the ultraviolet absorption spectrum of Au NPs in the first embodiment of the present invention. It can be seen from the figure that the complex with Au NPs causes Au @ ZnAl-LDHs to have a distinct absorption peak at 522nm, and the sample has weak absorption in the visible light region, because ZnAl-LDH is a wide band gap semiconductor material and needs to be excited by ultraviolet light to excite the transition from valence band electrons to conduction band.
FIG. 5 shows a solid line of the SERS substrate and 10 made of Au @ ZnAl-LDHs composite nanomaterial -5 Raman spectra measured after mixing of M concentration 4-NBT, clearly visible at 853, 1081, 1109, 1331 and 1572cm -1 Raman peaks of (2) respectively corresponding to NO of 4-NBT 2 C-H and C-N, C-H, C-N and N-O, C-C bond vibration modes. Concentration of pure as a comparison dotted line is 10 -3 Raman spectrum of M4-NBT measured under the same conditions. It can be obviously seen that Au @ ZnAl-LDHs can effectively enhance the Raman signal of 4-NBT.
FIG. 6 shows that the detection concentration of Au @ ZnAl-LDHs as the SERS substrate is 10 according to the first embodiment -5 M4-NBT method for preparing chips with 18 different points 1331cm in three batches -1 Change in intensity of raman peak. It can be seen that the samples have excellent reproducibility.
FIG. 7 (a) shows that the detected concentrations of Au @ ZnAl-LDHs as the SERS substrate are 10 respectively in the first embodiment of the present invention -5 M to 10 -13 Raman spectrum of 4-NBT of M; it can be seen from the figure that the raman peak intensity decreases with decreasing concentration, but until the concentration decreases to 10 -13 M can still observe a Raman peak corresponding to 4-NBT (see figure b), which indicates that Au @ ZnAl-LDHs has high sensitivity as an SERS substrate.
FIG. 8 shows a solid line of the detection 10 of the Au @ ZnAl-LDHs composite nanomaterial as the substrate in the second embodiment of the present invention -5 The crystal violet raman spectrum of the M concentration was taken as a raman spectrum measured under the same conditions as for the crystal violet powder whose broken line was pure. It can be obviously seen that Au @ ZnAl-LDHs can enhance the Raman signal of crystal violet.
Detailed Description
In order to explain the technical content of the present invention in detail, the purpose and effect thereof will be described below with reference to the accompanying drawings.
The first embodiment of the invention comprises the following steps:
firstly, preparing ultrathin two-dimensional zinc-aluminum layered double hydroxides by a solvothermal method, namely dissolving 0.8mmol of zinc nitrate hexahydrate, 0.4mmol of aluminum nitrate nonahydrate and 2.8mmol of urea in 80ml of ethylene glycol, transferring the mixture into a 100ml reaction kettle for solvothermal reaction, naturally cooling the mixture, centrifuging the mixture, washing the mixture with ethanol for three times, dispersing the mixture in deionized water for storage (solution A), and calibrating the concentration of the solution to be about 1.6g/L in a drying and weighing mode;
step two, preparing gold nanoparticles: under the condition of magnetic stirring, adding 1ml of tetrachloroauric acid solution (25 mM) into 99ml of boiling deionized water, then injecting 2.3ml of sodium citrate solution (5 wt%), reacting for 20min, and cooling to room temperature to obtain gold nanoparticle dispersion liquid-B liquid;
and thirdly, mixing 20ml of solution A with 10ml of solution B, stirring for five hours at room temperature, and storing the prepared Au @ ZnAl-LDHs composite nano material for later use.
Fourthly, 2ml of the prepared Au @ ZnAl-LDHs composite nano material suspension is mixed and stirred with the probe molecule 4-NBT aqueous solution in an equal volume, so that the final 4-NBT concentration of the mixed solution is 1x10 -5 And M, performing suction filtration after stirring is finished, fixing the filter membrane on a glass slide, and finally performing vacuum drying treatment. The above steps were repeated twice, and three batches of samples were produced in total.
Fifthly, carrying out Raman spectrum test, wherein the wavelength is 785nm, the object lens is in a long focus of 50 times, the exposure time is 10s, the excitation power is 1 percent, and the accumulated times are 8 times; 6 spots were selected at different positions on each filter.
Sixth step, repeat the fourth step and the fifth step, respectively detect the concentration to be 1 × 10 -5 To 10 -13 4-NBT of M.
The second embodiment of the invention comprises the following steps:
firstly, preparing ultrathin two-dimensional zinc-aluminum layered double hydroxides by a solvothermal method, namely dissolving 0.8mmol of zinc nitrate hexahydrate, 0.4mmol of aluminum nitrate nonahydrate and 2.8mmol of urea in 80ml of ethylene glycol, transferring the mixture into a 100ml reaction kettle for solvothermal reaction, naturally cooling the mixture, centrifuging the mixture, washing the mixture with ethanol for three times, dispersing the mixture in deionized water for storage (solution A), and calibrating the concentration of the solution to be about 1.6g/L in a drying and weighing mode;
step two, preparing gold nanoparticles: under the condition of magnetic stirring, 1ml of tetrachloroauric acid solution (25 mM) is added into 99ml of boiling deionized water, then 2.3ml of sodium citrate solution (5 wt%) is injected, reaction is carried out for 20min, and gold nanoparticle dispersion liquid-B liquid is obtained after cooling to room temperature;
and thirdly, mixing 20ml of the solution A with 10ml of the solution B, stirring for five hours at room temperature, and storing the prepared Au @ ZnAl-LDHs composite nano material for later use.
Fourthly, 2ml of the prepared Au @ ZnAl-LDHs composite nano material suspension is taken to be mixed and stirred with the probe molecule crystal violet solution in the same volume, so that the final crystal violet concentration of the mixed solution is 1x10 -5 And M, performing suction filtration after stirring is finished, fixing the filter membrane on a glass slide, and finally performing vacuum drying treatment.
And fifthly, carrying out Raman spectrum test, wherein the Raman spectrum test is carried out for 8 times with 785nm excitation wavelength, 50 times of long-focus objective lens, 10s exposure time, 1% excitation power and accumulation times.
In example one, 4-NBT and the substrate are mixed and stirred, wherein the 4-NBT has a concentration in the order of magnitude of 10 -5 M to 10 -13 M。
In example two, a crystal violet solution and the substrate were mixed and stirred, wherein the concentration of the crystal violet solution was on the order of 10 -5 M, for pure crystal violet powder, the number of crystal violet molecules in a measurement interval is greatly reduced when a Raman spectrum is tested, raman signals cannot be detected by using a crystal violet solution with the concentration, the crystal violet molecules can be adsorbed on the surface of ZnAl LDHs in the embodiment, the Raman signals belonging to crystal violet can still be clearly seen at the moment, the crystal violet is indicated to have no chemical reaction, and Au @ ZnAl-LDHs has the effect of enhancing the Raman signals, and the weakening of the fluorescence background can be caused by that charge transfer occurs between the crystal violet and the Au @ ZnAl-LDHs.
In conclusion, the SERS substrate prepared by the invention has excellent surface enhanced Raman scattering capability, and the preparation method is simple and easy to implement, good in enhancement effect, high in detection sensitivity and good in stability, and has great application prospects in various fields, particularly in the aspects of trace analysis, qualitative detection and the like of target analytes.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. The SERS substrate material is characterized by comprising gold nanoparticles and layered two-dimensional double-metal hydroxide ZnAl-LDHs, wherein the gold nanoparticles are dispersed on the surface of the ZnAl-LDHs, and the substrate material is expressed by Au @ ZnAl-LDHs.
2. The SERS substrate material as recited in claim 1, wherein the layered two-dimensional double hydroxide ZnAl-LDHs has a thickness of less than 3nm, and the gold nanoparticles have a particle size of 20-28nm.
3. A method of preparing a SERS substrate material according to claim 1 or 2, comprising: and mixing the ZnAl-LDHs dispersion liquid with the gold nanoparticle dispersion liquid, and stirring at room temperature for at least 5 hours to obtain the Au @ ZnAl-LDHs composite material.
4. The method for preparing the SERS substrate material as recited in claim 3, wherein the ZnAl-LDHs dispersion is prepared by a process comprising: dissolving a zinc source, an aluminum source and urea in ethylene glycol, transferring the obtained solution into a reaction kettle for solvent thermal reaction, naturally cooling, centrifuging, washing with ethanol, and dispersing in deionized water.
5. The method for preparing a SERS substrate material as recited in claim 4, wherein the zinc source is zinc nitrate hexahydrate and the aluminum source is aluminum nitrate nonahydrate.
6. The method of preparing a SERS substrate material according to claim 4, wherein the concentration of the zinc source in the solution is 10mM, the concentration of the aluminum source is 5mM, and the concentration of the urea is 35mM.
7. The method for preparing a SERS substrate material according to claim 4, wherein the solvothermal reaction is performed at 100 ℃ for 24 hours.
8. The method for preparing a SERS substrate material as claimed in claim 4, wherein the gold nanoparticle dispersion is prepared by a process comprising: adding a tetrachloroauric acid solution into boiling deionized water under the stirring condition, then injecting a sodium citrate solution, reacting, and cooling to room temperature to obtain a gold nanoparticle dispersion liquid; preferably, the concentration of the tetrachloroauric acid solution is 25mM, the concentration of the sodium citrate solution is 5wt%, and the volume ratio of the tetrachloroauric acid solution to the deionized water to the sodium citrate solution is 1mL:99mL of: 2.3mL.
9. Use of the substrate material of claim 1 or 2 for surface enhanced raman scattering, organic molecular raman detection.
10. A method for detecting an organic molecule, the method comprising: mixing the suspension of the substrate material of claim 1 or 2 with an equal volume of organic molecule aqueous solution, stirring at room temperature, vacuum filtering the mixture with a water system filter membrane with a pore size of 0.22 μm and a diameter of 25mm, vacuum drying, and performing Raman spectrum detection; the organic molecule is at least one of 4-nitrothiophenol and crystal violet.
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