CN112875677A - Preparation method of ordered mesoporous carbon loaded with metal nanoparticles, product and application thereof - Google Patents
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Abstract
The invention relates to the technical field of nano composite materials and analysis and detection, in particular to a preparation method of ordered mesoporous carbon loaded with metal nano particles, a product and application thereof. The preparation method at least comprises the following steps: respectively preparing ordered mesoporous carbon and at least one sol containing metal nano particles; and carrying out positive charge modification treatment on the ordered mesoporous carbon, and then mixing the modified ordered mesoporous carbon with at least one sol containing metal nano particles to combine the metal nano particles with the ordered mesoporous carbon through electrostatic adsorption so as to prepare the ordered mesoporous carbon loaded with the metal nano particles. The preparation process is simple, and the prepared ordered mesoporous carbon loaded with the metal nanoparticles has stable mesoporous structure and high and uniform metal loading amount.
Description
Technical Field
The invention relates to the technical field of nano composite materials and analysis and detection, in particular to a preparation method of ordered mesoporous carbon loaded with metal nano particles, a product and application thereof.
Background
Water is a source of life. However, in recent years, with the rapid development of chemical, pharmaceutical, printing and dyeing, pesticide and other industries, the water pollution is increasing due to the illegal discharge of a large amount of organic wastewater, which seriously hinders the green development process of the country and poses a great threat to human health and life safety. Organic pollutants in water are difficult to degrade and extremely toxic, have carcinogenicity, teratogenicity and mutagenicity, are not easy to decompose after being ingested by organisms, can be concentrated and amplified along a food chain, and have great harm to human beings and animals. In the existing water quality detection standard, the chemical oxygen demand only measures the total content of organic substances in water, and has no pertinence to organic pollutants with small content and great harmfulness, so that a trace detection technology is urgently needed to carry out rapid quantitative detection on the organic pollutants, and a surface enhanced Raman scattering technology meets the requirements.
The Surface Enhanced Raman Scattering (SERS) has the advantages of molecular fingerprint specificity, high sensitivity, narrow spectral bandwidth, etc., and is widely used in biomedical detection, chemical analysis, environmental monitoring, etc. Noble metal nanomaterials are considered to be the SERS substrate materials with the strongest enhancement effect, and the surface plasmon resonance effect of the noble metal nanomaterials can generate a large number of "hot spots" at the gaps of the nanoparticles, so that the signals of analytes in the regions are significantly enhanced. And the proper carrier can better integrate the metal nano structure to manufacture more hot spots, generate a chemical enhancement effect and effectively improve the detection sensitivity of the substrate. In addition, the introduction of the high-stability carrier can improve the defects of easy oxidation and instability of the bare noble metal substrate so as to improve the stability of the substrate.
Ordered Mesoporous Carbon (OMC) as a novel carbon material has the characteristics of large specific surface area, high stability, adjustable pore structure, simple synthesis, easy operation and the like. Therefore, the ordered mesoporous carbon loaded metal nano material has unique advantages in SERS detection. On one hand, the ordered mesoporous carbon loaded metal nanoparticles can generate delicate nanometer gaps at the contact position to create enough 'hot spots'; on the other hand, the high specific surface area of the ordered mesoporous carbon enables the ordered mesoporous carbon to have a strong adsorption effect on organic molecules or microorganisms, a chemical enhancement effect can be generated, and the SERS detection performance is further enhanced.
At present, the preparation method of the ordered mesoporous carbon mainly comprises a soft template method and a hard template method. The soft template method can directly generate a pore structure by adding a surfactant or a block copolymer, and the hard template method is characterized in that a hard template with a fixed structure and a carbon precursor are combined and carbonized at high temperature, and then a pore structure is formed by chemical etching, so that the generated pore structure is regular and ordered and has narrow distribution.
The preparation of the ordered mesoporous carbon loaded metal composite material mostly adopts a hydrothermal synthesis method and an impregnation method. Both methods require the direct generation of metal nanoparticles on the surface of ordered mesoporous carbon through a high temperature calcination process. However, the mesoporous structure of the ordered mesoporous carbon composite material prepared in a high-temperature environment is easily damaged, and the pore channels are easily blocked, so that the specific surface area of the composite material is reduced, and the performance is reduced.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of ordered mesoporous carbon loaded with metal nanoparticles.
The second invention aims to provide the ordered mesoporous carbon loaded with the metal nanoparticles obtained by the preparation method.
The third invention of the invention aims to provide the application of the ordered mesoporous carbon loaded with the metal nano-particles.
In order to achieve the purpose of the invention, the technical scheme is as follows:
the invention provides a preparation method of ordered mesoporous carbon loaded with metal nanoparticles, which at least comprises the following steps:
s1, preparing ordered mesoporous carbon and at least one sol containing metal nanoparticles respectively;
s2, carrying out positive charge modification treatment on the ordered mesoporous carbon;
s3, mixing the processed ordered mesoporous carbon with at least one sol containing metal nanoparticles, and enabling the metal nanoparticles in the sol to be combined with the ordered mesoporous carbon through electrostatic adsorption to prepare the ordered mesoporous carbon loaded with the metal nanoparticles.
Optionally, the ordered mesoporous carbon is prepared by a hard mold method.
Optionally, the particle size of the metal nanoparticles is 20-25 nm,
the metal nanoparticles are preferably gold particles and silver particles; the particle size of the gold particles is 25nm, and the particle size of the silver particles is 20 nm;
the sol containing the metal nano-particles is silver sol or gold sol;
preferably, the preparation method of the silver sol comprises the following steps: 0.16-0.24 mg/mL AgNO3Heating 125mL of the solution to 85-95 ℃, and dropwise adding 4-6 mL of 0.8-1.2 wt% Na3C6H5O7·2H2O solution, preparing silver sol; further preferably, the concentration of the silver sol is 0.12 mg/mL;
more preferably, the preparation method of the gold sol comprises the following steps: 0.01 wt% HAuCl4·3H2Heating 100mL of O solution to 85-95 ℃, and dropwise adding 4-6 mL of Na with the concentration of 0.8-1.2 wt%3C6H5O7·2H2O solution, preparing gold sol; more preferably, the concentration of the gold sol is 0.05 mg/mL.
Optionally, the positive charge modification treatment comprises: soaking the ordered mesoporous carbon in a modifier containing positive charges, preferably, the modifier containing positive charges is selected from polyethyleneimine;
preferably, ultrasonic treatment is carried out while soaking, preferably, the ultrasonic treatment time is 25-40 min, the ultrasonic treatment frequency is 30-50 KHZ, preferably 40KHZ, and the power is 100-150W, preferably 120W.
Optionally, in step S3, ultrasonic treatment is performed while mixing, preferably, the ultrasonic treatment time is 25-40 min, the ultrasonic treatment frequency is 30-50 KHZ, preferably 40KHZ, and the power is 100-150W, preferably 120W.
Optionally, in step S3, the volume of the treated ordered mesoporous carbon and the metal nanoparticle-containing sol is 1: 4-6, preferably 1: 5.
optionally, in step S3, when the sol containing the metal nanoparticles is a silver sol or a gold sol, the volume ratio of the silver sol to the gold sol is 1: 0.5 to 1.5, preferably 1: 1.
the invention also relates to the ordered mesoporous carbon loaded with the metal nanoparticles, which is prepared by the preparation method.
The invention also relates to application of the ordered mesoporous carbon loaded with the metal nanoparticles in surface-enhanced Raman spectroscopy detection.
Optionally, the application includes the following steps:
and (3) mixing the ordered mesoporous carbon loaded with the metal nanoparticles and the solution to be detected in a volume ratio of 1: 1-3: 1, dropwise adding the mixed solution to a silicon wafer, and drying; and finally, placing the sample to be detected in a surface enhanced Raman spectrometer for detection.
The invention has at least the following beneficial effects:
the preparation process is simple, the prepared ordered mesoporous carbon loaded with the metal nanoparticles has a stable mesoporous structure and high and uniform metal loading amount, has the characteristics of high detection sensitivity, good repeatability and strong stability when being used as a surface enhanced Raman scattering technology substrate, and has great application potential in the field of organic matter and/or microorganism detection.
Drawings
FIG. 1 is a TEM image of an OMC prepared in example 1 of the present invention;
FIG. 2 is a Zeta potential diagram before and after positive charge modification of OMC of example 1 of the present invention; FIG. a is before modification of PEI and FIG. b is after modification of PEI;
FIG. 3 is a thermogravimetric curve of OMC of example 1 of the present invention;
FIG. 4 is a thermogravimetric plot of OMC/Ag @ Au NPs of example 1 of the present invention;
FIG. 5 is a TEM image of Ag sol of example 1 of the present invention;
FIG. 6 is a TEM image of Au sol of example 1 of the present invention;
FIG. 7 is an SEM image of an OMC of example 1 according to the present invention;
FIG. 8 is a SEM image of Ag @ Au NPs composite of example 1 of the present invention;
FIG. 9 is an XRD spectrum of an OMC/Ag @ Au NPs composite material of example 1 of the present invention;
FIG. 10 is a nitrogen adsorption-desorption curve before and after OMC loading Ag/Au NPs in example 1 of the present invention;
FIG. 11 is a graph showing the pore size distribution before and after OMC loading Ag/Au NPs in example 1 of the present invention;
FIG. 12 is a graph showing the SERS sensitivity detection of OMC/Ag @ Au NPs composite material using rhodamine 6G as a probe;
FIG. 13 is a graph showing the SERS stability detection of OMC/Ag @ Au NPs composites using rhodamine 6G as a probe;
FIG. 14 is a surface enhanced Raman spectrum of gentian violet detected in example 3 according to the present invention;
FIG. 15 is a surface enhanced Raman spectrum of methylene blue detected in example 4 of the present invention;
FIG. 16 is a surface enhanced Raman spectrum of methyl green detected in example 5 of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to achieve the above object, an embodiment of the present invention provides a simple and effective method for preparing a metal nanoparticle-loaded ordered mesoporous carbon composite material, including the following steps: preparing ordered mesoporous carbon, and then performing modification treatment; preparing metal nano colloid; preparing the ordered mesoporous carbon loaded metal nanoparticle composite material by utilizing the electrostatic adsorption effect. The preparation process of the embodiment of the invention is simple, high-temperature calcination is not needed, and the mesoporous structure and the pipeline of the ordered mesoporous carbon are not damaged.
The embodiment of the invention relates to a preparation method of ordered mesoporous carbon loaded with metal nanoparticles, which at least comprises the following steps:
s1, preparing ordered mesoporous carbon and at least one sol containing metal nanoparticles respectively;
s2, carrying out positive charge modification treatment on the ordered mesoporous carbon;
s3, mixing the treated ordered mesoporous carbon with at least one sol containing metal nanoparticles, and combining the metal nanoparticles in the sol with the ordered mesoporous carbon through electrostatic adsorption to prepare the ordered mesoporous carbon loaded with the metal nanoparticles.
Optionally, the ordered mesoporous carbon is prepared by a hard mold method.
The preparation method of the ordered mesoporous carbon comprises the following steps: dissolving 1.25g of sucrose and 0.14g of concentrated sulfuric acid in 10g of deionized water, stirring for 1h, adding 1g of triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide (SBA-15), drying at 100 ℃ for 6h, and carbonizing at 160 ℃ for 6 h. Then, 0.8g of sucrose and 0.09g of concentrated sulfuric acid are dissolved in 8g of deionized water, stirred for 1 hour, added into an SBA-15 mixture containing partially carbonized sucrose, and the drying and carbonizing treatment steps at 100 ℃ and 160 ℃ are repeated; placing the obtained compound in a quartz boat with N2At 2 ℃ for min under the protection of atmosphere-1The temperature is increased to 900 ℃ at the temperature rising rate, and the temperature is kept for 3 hours until the carbonization is completed. And finally, soaking the carbon material by using 10 wt% of HF, stirring for 12 hours, filtering, washing to be neutral, and drying to obtain the ordered mesoporous carbon.
Alternatively, the metal nanoparticles of the present invention may be selected from gold (Au) particles, silver (Ag) particles. SERS detection is mainly focused on gold and silver, and due to the Surface Plasmon Resonance (SPR) effect of gold and silver nanostructures, ultra-sensitive analysis can be realized by SERS.
Optionally, the sol containing the metal nanoparticles is 0.1-0.15 mg/mL Ag sol or 0.05mg/mL Au sol;
optionally, 0.16-0.24 mg/mLAgNO3Heating 125mL of the solution to 85-95 ℃, and dropwise adding 4-6 mL of 0.8-1.2 wt% Na3C6H5O7·2H2Preparing an Ag sol from the O solution; more preferably, the concentration of the silver sol is 0.12 mg/mL.
Optionally, the preparation method of the Au sol comprises: 0.01 wt% HAuCl4·3H2Heating 100mL of O solution to 85-95 ℃, and dropwise adding 4-6 mL of Na with the concentration of 0.8-1.2 wt%3C6H5O7·2H2And O solution to prepare Au sol. More preferably, the concentration of the gold sol is 0.05 mg/mL.
Optionally, the positive charge modification treatment comprises: the ordered mesoporous carbon is soaked in a positive charge modifier, preferably selected from the group consisting of Polyethyleneimine (PEI). PEI is a water-soluble polymer with high cationic degree and is a good positive charge carrier. According to the invention, through screening positive charge carriers, the PEI is found to be capable of well realizing modification of the surface charge of mesoporous carbon from negative to positive, the modification of positive charge can be realized only through simple soaking treatment, and the amount of the carried positive charge is matched with the amount of the negative charge of the metal particles needing to be adsorbed and loaded, so that the electrostatic adsorption effect can be finally utilized to load the metal particles on the surface. The prepared metal particle loading is suitable for the application of surface enhanced Raman spectroscopy.
Preferably, ultrasonic treatment is carried out while soaking, preferably, the ultrasonic treatment time is 25-40 min, the ultrasonic treatment frequency is 30-50 KHZ, preferably 40KHZ, and the power is 100-150W, preferably 120W. The ultrasonic is added for uniform mixing, and uniform loading is realized. Optionally, in step S3, ultrasonic treatment is performed while mixing, preferably, the ultrasonic treatment time is 25-40 min, the ultrasonic treatment frequency is 30-50 KHZ, preferably 40KHZ, and the power is 100-150W, preferably 120W.
Optionally, in step S3, when multiple metal nanoparticles are loaded, different sols containing the metal nanoparticles are added in the ultrasonic process respectively;
preferably, when the sol containing the metal nanoparticles is Ag sol or Au sol, the Ag sol is added and mixed for 5-10 min, and then the Au sol is added and mixed for 20-30 min.
Optionally, in step S3, the volume or mass ratio of the processed ordered mesoporous carbon to the sol containing the metal nanoparticles is 1: 4-6, preferably 1: 5. if the amount of the ordered mesoporous carbon is too large, the relative loading of the metal particles is small, and if the amount of the ordered mesoporous carbon is too small, the loading of the metal particles is too large until an adsorption equilibrium state is reached.
Preferably, when the sol containing the metal nanoparticles is an Ag sol or an Au sol, the ratio of the Ag sol to the Au sol is 1: 0.5-1.5, preferably 1: 1. Because the SERS effect of silver alone is good, but silver nanoparticles are unstable, stability and SERS effect can be simultaneously considered by adopting the proportion. If the gold-doped nanoparticles are too much, the SERS effect is weakened; however, if the doped gold nanoparticles are too few, the silver nanoparticles account for more, and although the SERS effect will be good, the overall stability will be substantially reduced.
The embodiment of the invention also relates to the ordered mesoporous carbon loaded with the metal nano particles, which is prepared by the preparation method. The ordered mesoporous carbon loaded metal nanoparticle prepared by the embodiment of the invention has stable mesoporous structure and high and uniform metal loading.
The embodiment of the invention also relates to application of the ordered mesoporous carbon loaded with the metal nanoparticles in surface-enhanced Raman spectroscopy detection.
Specifically, the application comprises the following steps: orderly mesoporous carbon loaded with metal nanoparticles and a solution to be detected are mixed according to a volume ratio of 1: 1-3: 1, dropwise adding the mixed solution to a silicon wafer, and drying; and finally, immediately placing the sample to be detected in a surface enhanced Raman spectrometer for detection. Specifically, the solution to be tested can be prepared to have a gradient concentration of 10-3～10-8Solution of M。
The following describes the preparation and SERS performance detection of Ordered Mesoporous Carbon (OMC), Ag sol, Au sol and ordered mesoporous carbon (OMC/Ag @ Au NPs composite material) loaded with Ag and Au nanoparticles, positive charge modification pretreatment of the OMC, and an embodiment of detecting organic pollutants in water by using the OMC/Ag @ Au NPs composite material as an SERS substrate. The detection is carried out by using a BWS465 portable Raman spectrometer with 100W of excitation power and 10s of scanning time.
Example 1
1. Dissolving 1.25g of sucrose and 0.14g of concentrated sulfuric acid in 10g of deionized water, stirring for 1h, adding 1g of SBA-15, drying at 100 ℃ for 6h, and carbonizing at 160 ℃ for 6 h. Then, 0.8g of sucrose and 0.09g of concentrated sulfuric acid are dissolved in 8g of deionized water, stirred for 1 hour, added into an SBA-15 mixture containing partially carbonized sucrose, and the drying and carbonizing treatment steps at 100 ℃ and 160 ℃ are repeated; placing the obtained compound in a quartz boat with N2At 2 ℃ for min under the protection of atmosphere-1The temperature is increased to 900 ℃ at the temperature rising rate, and the temperature is kept for 3 hours until the carbonization is completed. And finally, soaking the obtained product in 10 wt% of HF, stirring for 12 hours, filtering, washing with water to be neutral, and drying to obtain the ordered mesoporous carbon OMC. The TEM image is shown in FIG. 1.
2. OMC was pretreated with positive charge modification. And (3) soaking the OMC in a PEI solution, and carrying out ultrasonic treatment for 30min to obtain a black uniform mixed solution. As shown in FIG. 2, which is a Zeta potential diagram before and after positive charge modification, PEI successfully achieves negative to positive modification of the OMC surface charge.
The thermogravimetric plot of the OMC is shown in figure 3. As can be seen from FIG. 3, the weight loss of OMC is more pronounced before 550 ℃, while the weight loss of OMC is increasingly pronounced as the temperature is increased to 550 ℃ and 650 ℃ with increasing weight loss. FIG. 4 is a TG plot of OMC/Ag @ Au NPs, and it can be seen from FIG. 4 that there is almost no weight loss before 550 ℃ in OMC/Ag @ Au NPs compared to OMC alone, since PEI modification is a non-covalent modification and bonds to the surface of OMC with a large amount of negative charge through electrostatic interaction. The difference of the obvious weight loss change trends of the two shows that the PEI modification not only realizes the reversal of the potential from negative to positive, but also improves the stability of the PEI modification.
3. Preparing Ag sol: the preparation concentration is 1wt％Na3C6H5O7·2H2O solution for later use, 0.2mg/mL AgNO3125mL of the solution was heated to 90 ℃ and 5mL of 1 wt% Na was added dropwise3C6H5O7·2H2Preparing an Ag sol from the O solution; a TEM image of the Ag sol is shown in fig. 5.
Preparing Au sol: the preparation concentration is 1 wt% Na3C6H5O7·2H2O solution is ready for use, 0.01 wt% HAuCl4·3H2O100 mL was heated to 90 ℃ and 5mL of 1 wt% Na was added dropwise3C6H5O7·2H2And O solution to prepare Au sol. A TEM image of the Au sol is shown in fig. 6.
4. Carrying out positive charge modification pretreatment on OMC, soaking the OMC in a PEI solution, and carrying out ultrasonic treatment for 30min to obtain a black uniform mixed solution;
5. adding silver sol into the OMC after treatment, performing ultrasonic treatment for 5min, then adding gold sol, and performing ultrasonic treatment for 25min, wherein the volume ratio of the ordered mesoporous carbon to the silver sol to the gold sol is 1: 2.5: and 2.5, centrifugally washing the composite material for 3 times by using deionized water, and washing away the Au/Ag NPs and PEI which are not combined to form the OMC-loaded nano Ag/Au composite material which is called OMC/Ag @ Au NPs.
FIG. 7 is an SEM image of OMC, FIG. 8 is an SEM image of an OMC/Ag @ Au NPs composite, and FIG. 9 is an XRD spectrum of the OMC/Ag @ Au NPs composite.
It is also obvious from comparing the SEM images of the OMC and the loaded metal that the OMC becomes rough and the surface particles are dense after the metal is loaded on the surface, which shows that the composite material prepared by the invention has large metal loading.
The nitrogen adsorption-desorption curves before and after OMC loading Ag/Au NPs are shown in FIG. 10. As can be seen from the nitrogen isothermal adsorption curve, the relative pressure P/P before and after the metal particle loading0When the concentration is close to 0.5, the adsorption of the IV curve has obvious leap, and the material is a typical mesoporous material.
FIG. 11 is a plot of pore size distribution using BJH model analysis, showing that the average pore sizes of OMC and OMC/Ag @ Au NPs are 5.7nm and 5.9nm, respectively. In conclusion, compared with OMC, the pore diameter change of OMC/Ag @ Au NPs is small, the specific surface area is slightly reduced, and the result proves that the mesoporous structure of the material is not changed after the nano particles are loaded, and the enrichment adsorption effect on the object to be detected is not influenced.
Example 2
The ordered mesoporous carbon-loaded Ag/Au NPs composite material is used for SERS performance detection.
1. Preparing gradient concentration of 10-3～10-8M in rhodamine 6G (R6G) solution for standby;
2. ultrasonically mixing OMC/Ag @ Au NPs prepared in example 1 and a solution to be detected according to the volume ratio of 2:1, dropwise adding the mixed solution to a silicon wafer, and drying;
3. and (3) placing the sample to be detected under a laser of a spectrometer for analysis and detection.
The sensitivity test results are shown in FIG. 12, and it can be seen from FIG. 12 that rhodamine is used as the probe molecule, and the detection limit can reach 10- 8mol/L。
At room temperature, with 45d as a period and every 5 days, OMC/Ag @ Au NPs are used as an SERS substrate, and the pair 10 is-2M R6 solution 6G was tested once, and the results of the stability test are shown in FIG. 13. As can be seen from FIG. 13, the prepared ordered mesoporous carbon supported Ag/Au NPs composite material has good stability.
Example 3
1. Preparing gradient concentration of 10-3～10-9Taking the gentian violet solution of M as a solution to be detected for later use;
2. ultrasonically mixing OMC/Ag @ Au NPs prepared in the embodiment 1 and a solution to be detected according to the volume ratio of 2:1, dropwise adding the mixed solution to a silicon wafer, and drying the silicon wafer to be wet and thick;
3. and (3) placing the sample to be detected under a laser of the spectrometer for Raman signal detection. The results of the experiment are shown in FIG. 14.
As shown in FIG. 14, the solution concentration was set to 10-3～10-9The peak intensity of the M, Raman spectrum is weakened along with the reduction of the concentration of the gentian violet solution, and the detection limit can reach 10-9And M. Shows that OMC/Ag @ Au NPs have obvious Raman spectrum peak to gentian violet solution as SERS substrateAnd (4) a Mandarin effect.
Example 4
1. Preparing gradient concentration of 10-3～10-8Taking the methylene blue solution of M as a solution to be detected for later use;
2. ultrasonically mixing OMC/Ag @ Au NPs prepared in example 1 and a solution to be tested according to the volume ratio of 2:1, dropwise adding the mixed solution to a silicon wafer, and drying the silicon wafer to be wet and thick;
3. and (3) placing the sample to be detected under a laser of the spectrometer for Raman signal detection. The results of the experiment are shown in FIG. 15.
As shown in FIG. 15, the concentration of methylene blue solution was set to 10-3、10-4、10-5、10-6、10-7And 10-8M, as can be seen in the figure, by using OMC/Ag @ Au NP as an SERS substrate, the detection limit of methylene blue solution can reach 10-8M。
Example 5
1. Preparing gradient concentration of 10-3～10-6Taking the methyl green solution of M as a solution to be detected for later use;
2. ultrasonically mixing OMC/Ag @ Au NPs prepared in example 1 and a solution to be detected according to the volume ratio of 2:1, dropwise adding the mixed solution to a silicon wafer, and drying the silicon wafer to be wet and thick;
3. and (3) placing the sample to be detected under a laser of the spectrometer for Raman signal detection. The results of the experiment are shown in FIG. 16.
As shown in FIG. 16, the concentration range of 10 was selected-3～10-6The raman spectral peak data of M was analyzed. The OMC/Ag @ Au NPs serving as the SERS substrate has an obvious Raman effect on a Raman spectrum peak of the gentian violet solution.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
Claims (10)
1. A preparation method of ordered mesoporous carbon loaded with metal nanoparticles is characterized by at least comprising the following steps:
s1, preparing ordered mesoporous carbon and at least one sol containing metal nanoparticles respectively;
s2, carrying out positive charge modification treatment on the ordered mesoporous carbon;
s3, mixing the processed ordered mesoporous carbon with at least one sol containing metal nanoparticles, and enabling the metal nanoparticles in the sol to be combined with the ordered mesoporous carbon through electrostatic adsorption to prepare the ordered mesoporous carbon loaded with the metal nanoparticles.
2. The method of claim 1, wherein the ordered mesoporous carbon is prepared using a hard mold method.
3. The method according to claim 1, wherein the metal nanoparticles have a particle size of 20 to 25nm,
the metal nanoparticles are preferably gold particles and silver particles; the particle size of the gold particles is 25nm, and the particle size of the silver particles is 20 nm;
the sol containing the metal nano-particles is silver sol or gold sol;
preferably, the preparation method of the silver sol comprises the following steps: 0.16-0.24 mg/mL AgNO3Heating 125mL of the solution to 85-95 ℃, and dropwise adding 4-6 mL of 0.8-1.2 wt% Na3C6H5O7·2H2O solution, preparing silver sol; further preferably, the concentration of the silver sol is 0.12 mg/mL;
more preferably, the preparation method of the gold sol comprises the following steps: 0.01 wt% HAuCl4·3H2Heating 100mL of O solution to 85-95 ℃, and dropwise adding 4-6 mL of Na with the concentration of 0.8-1.2 wt%3C6H5O7·2H2O solution, preparing gold sol; more preferably, the concentration of the gold sol is 0.05 mg/mL.
4. The method for producing according to claim 1, wherein the positive charge modification treatment comprises: soaking the ordered mesoporous carbon in a modifier containing positive charges, preferably, the modifier containing positive charges is selected from polyethyleneimine;
preferably, ultrasonic treatment is carried out while soaking, preferably, the ultrasonic treatment time is 25-40 min, the ultrasonic treatment frequency is 30-50 KHZ, preferably 40KHZ, and the power is 100-150W, preferably 120W.
5. The method of claim 1, wherein the mixing is performed simultaneously with the ultrasonic treatment in step S3, preferably the ultrasonic treatment is performed for 25-40 min, the ultrasonic treatment is performed at a frequency of 30-50 KHZ, preferably 40KHZ, and at a power of 100-150W, preferably 120W.
6. The method according to claim 1, wherein in step S3, the volume of the treated ordered mesoporous carbon to the metal nanoparticle-containing sol is 1: 4-6, preferably 1: 5.
7. the method according to claim 1, wherein in step S3, when the sol containing metal nanoparticles is a silver sol or a gold sol, the volume ratio of the silver sol to the gold sol is 1: 0.5 to 1.5, preferably 1: 1.
8. the ordered mesoporous carbon loaded with the metal nanoparticles, which is prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the metal nanoparticle loaded ordered mesoporous carbon of claim 8 for surface enhanced raman spectroscopy detection.
10. The application according to claim 9, characterized in that it comprises the following steps:
and (3) mixing the ordered mesoporous carbon loaded with the metal nanoparticles and the solution to be detected in a volume ratio of 1: 1-3: 1, dropwise adding the mixed solution to a silicon wafer, and drying; and finally, placing the sample to be detected in a surface enhanced Raman spectrometer for detection.
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