CN108274015B - Preparation method and application of three-dimensional ordered mesoporous noble metal nanoparticles - Google Patents
Preparation method and application of three-dimensional ordered mesoporous noble metal nanoparticles Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a three-dimensional ordered mesoporous noble metal nanoparticle, wherein a mesoporous material KIT-6 molecular sieve is used as a template, the template is filled with chloroauric acid solution, after vacuum drying is carried out for 24 hours, n-hexane or dichloromethane is used as a solvent, 1,1,3, 3-tetramethyldisiloxane or n-butylamine is used as a reducing agent, and HF corrosion is used for removing the mesoporous material KIT-6 molecular sieve, so that the three-dimensional ordered mesoporous Au nanoparticle is obtained. The particle size is 50nm-500nm in diameter, and the pore size is 2-15 nm. The method can prepare the three-dimensional ordered mesoporous noble metal nano-particles with uniform size and controllable shape, and has the advantages of simple preparation process, short reaction time and controllable process. The obtained three-dimensional ordered mesoporous noble metal nano-particles have a periodically arranged ordered structure, high specific surface area, good biocompatibility and high photo-thermal conversion efficiency, and have good application prospects in the fields of surface-enhanced Raman scattering spectrum detection, photoelectrochemical catalysis, cancer photo-thermal and drug composite treatment and the like.
Description
Technical Field
The invention belongs to the crossing fields of nanotechnology, surface-enhanced Raman scattering spectroscopy, photoelectrochemical catalysis and biomedicine, and relates to a preparation method and application of three-dimensional ordered mesoporous noble metal nanoparticles.
Background
When the frequency of incident light is close to the vibration frequency of the metal surface plasma, plasmon resonance is generated on the metal surface, so that the metal surface local electromagnetic field is enhanced, and the Raman signal of the detection molecule adsorbed on the metal surface is enhanced. The noble metal nano structure has the characteristics of high density, good stability, capability of generating Surface Plasmon Resonance (SPR) and the like. When the size of the noble metal particles reaches the nanometer level, particularly less than 5nm, the active sites on the surfaces of the particles are increased due to the reasons that the specific surface area is large, the bonding state and the electronic state of the surfaces are different from those in the particles, the coordination of surface atoms is incomplete and the like, and excellent catalytic performance is shown. The noble metal nano structure not only has unique optical and electrical properties, but also modifies organic functional groups such as sulfhydryl and amino on the metal surface through covalent bond or non-covalent bond acting force, so that the Au nano structure has good biocompatibility, is easy to combine with biological macromolecules (such as protein, polypeptide and oligonucleotide), and is widely applied to the biological fields of drug loading and the like. Precious metal nanostructures of different sizes and shapes, such as precious metal nanoparticles, nanostars, nanorods, nanoflowers, nanosheets, nanocages, and the like, have been synthesized. Compared with the traditional noble metal nano-particles, the three-dimensional mesoporous noble metal nano-particles have obvious advantages of specific surface area and uniform pore size distribution, and have immeasurable application prospect. However, in the prior art, the preparation method is complex and has poor stability and reproducibility in the process of preparing the three-dimensional ordered mesoporous noble metal nanoparticles.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method and application of three-dimensional ordered mesoporous noble metal nanoparticles.
In order to achieve the above object, the preparation method of the three-dimensional ordered mesoporous noble metal nanoparticle of the present invention comprises the following steps:
dissolving mesoporous material powder in the solution at room temperature, then carrying out vacuum drying in a vacuum drying oven, then dropwise adding n-hexane or dichloromethane, dropwise adding 1,1,3, 3-tetramethyldisiloxane or n-butylamine for reduction, then washing and centrifuging, and finally dissolving the mesoporous material powder to obtain the three-dimensional ordered mesoporous noble metal nano-particles.
When the three-dimensional ordered mesoporous noble metal nanoparticles are three-dimensional ordered mesoporous Au nanoparticles, the method comprises the following steps:
dissolving a mesoporous material KIT-6 molecular sieve powder in HAuCl at room temperature4·4H2Dissolving in O ethanol solution, drying in vacuum drying oven to convert mesoporous material KIT-6 molecular sieve powder into yellow powder, adding n-hexane or dichlorohexane dropwise, adding 1,1,3, 3-tetramethyldisiloxane or n-butylamine dropwise for reduction to convert yellow powder into black powder, washing and centrifuging black powder, dissolving black powder in distilled water, adding HAnd F, standing, and finally centrifuging and washing to obtain the three-dimensional ordered mesoporous Au nano-particles.
The reduction time is adjusted according to the size of the three-dimensional ordered mesoporous Au nano-particles, and the reduction time range is 1-72 h.
Mesoporous material KIT-6 molecular sieve powder and HAuCl4·4H2The proportion of O ethanol solution, n-hexane or dichloromethane, 1,3, 3-tetramethyldisiloxane or n-butylamine, distilled water and HF is 10 mg: 1m L: 100 ul: 10 ul: 4m L: 2m L, wherein, HAuCl4·4H2The concentration range of the O ethanol solution is 0.1 mM-1M; the volume concentration of HF is 20-40%.
The diameter of the three-dimensional ordered mesoporous Au nano-particles is 50nm-500nm, and the pore diameter is 2-15 nm.
Washing the black powder with absolute ethyl alcohol for several times, and then centrifuging;
dissolving mesoporous material KIT-6 molecular sieve powder by using HF, centrifuging, and washing for a plurality of times by using absolute ethyl alcohol;
and in the process of drying in the vacuum drying oven, the temperature in the vacuum drying oven is 30-50 ℃, and the drying time is 2-24 hours.
When the three-dimensional ordered mesoporous noble metal nanoparticles are three-dimensional ordered mesoporous Pt nanoparticles, the method comprises the following steps:
dissolving 10mg of mesoporous material KIT-6 powder in 0.1M K of 10M L at room temperature2PtCl4Drying the solution in a vacuum drying oven for 24 hours to convert white powder in the solution into orange powder, then dropwise adding 100ul of n-hexane or dichloromethane, then dropwise adding 1,1,3, 3-tetramethyldisiloxane or n-butylamine for reduction to convert the orange powder into black powder, then washing the black powder for a plurality of times by using absolute ethyl alcohol, dissolving mesoporous material KIT-6 powder by using HF with the volume concentration of 20% after centrifugation, and finally washing the powder for a plurality of times by using the absolute ethyl alcohol after centrifugation to obtain the three-dimensional ordered mesoporous Pt nano-particles;
when the three-dimensional ordered mesoporous noble metal nano-particles are three-dimensional ordered mesoporous Au-Ag nano-particles, the method comprises the following steps:
in the room10mg of the mesoporous material KIT-6 powder was dissolved in 1m L and 3mM HAuCl under mild conditions4·4H2Adding 25ul of 3mM AgNO dropwise into the O ethanol solution3Drying the powder in a vacuum drying oven for 24 hours to convert white powder in the solution into yellow powder, then dropwise adding 100ul of n-hexane or dichloromethane, then dropwise adding 10ul of 1,1,3, 3-tetramethyldisiloxane or n-butylamine for reduction to convert the yellow powder into black, then washing the black powder for a plurality of times by using absolute ethyl alcohol, dissolving mesoporous material KIT-6 powder by using HF with the volume concentration of 20% after centrifuging, and finally washing the powder for a plurality of times by using the absolute ethyl alcohol after centrifuging to obtain the three-dimensional ordered mesoporous Au-Ag alloy nano particles;
the three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles can be used for surface enhanced Raman scattering spectroscopy.
The three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles can be used for the photothermal and drug composite treatment of cancers.
The three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles can be used in photoelectrochemical catalysis.
The invention has the following beneficial effects:
the preparation method of the three-dimensional ordered mesoporous noble metal nano-particles has the advantages that during specific operation, the noble metal material grows in the mesoporous material powder, and then the mesoporous material powder is dissolved, so that the three-dimensional ordered mesoporous noble metal nano-particles are obtained. In addition, the three-dimensional ordered mesoporous noble metal nano-particles prepared by the method have good application in the fields of surface enhanced Raman scattering spectrum detection, photoelectrochemical catalysis, cancer photo-thermal and drug composite treatment and the like.
Drawings
FIG. 1 is a process diagram for constructing three-dimensional ordered mesoporous Au nanoparticles;
FIG. 2 is an SEM image of three-dimensional ordered mesoporous Au nanoparticles obtained in the first example;
FIG. 3a is a low power TEM image of three-dimensional ordered mesoporous Au nanoparticles;
FIG. 3b is an enlarged view of the right circular area of FIG. 3 a;
FIG. 4a is a schematic diagram of the initial state of black powder;
FIG. 4b is a schematic representation of the black powder after 2min reduction;
FIG. 4c is a schematic representation of the black powder after 8min reduction;
FIG. 4d is a schematic representation of the black powder after 15min reduction;
FIG. 4e is a schematic representation of the black powder after 2h reduction;
FIG. 4f is a schematic representation of the black powder after 6h reduction;
FIG. 5a is a TEM image of three-dimensional ordered mesoporous Au-Ag alloy nanoparticles;
FIG. 5b is a mapping diagram of Au elements of the three-dimensional ordered mesoporous Au-Ag alloy nanoparticles in the rectangular frame in FIG. 5 a;
FIG. 5c is a mapping diagram of Ag element of the three-dimensional ordered mesoporous Au-Ag alloy nanoparticles in the rectangular frame in FIG. 5 a;
FIG. 6a is an SEM image of Au nanoparticles obtained with n-butylamine as the reducing agent and n-hexane as the solvent;
FIG. 6b is an SEM image of Au nanoparticles obtained with dichloromethane as solvent and TMDS as reducing agent;
FIG. 7 is an SEM image of a three-dimensional ordered mesoporous Pt prepared by taking KIT-6 as a template;
FIG. 8 is a Raman test chart of rhodamine 6G molecular molecules adsorbed on three-dimensional ordered mesoporous Au nanoparticles;
FIG. 9a is a cyclic voltammogram of methanol electrocatalysis during electrochemical performance test of three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles;
FIG. 9b is a timing current diagram of the three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles during electrochemical performance test;
FIG. 9c is a graph showing the oxide dissolution during the electrochemical performance test of the three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles;
FIG. 9d is a histogram of mass activity and site activity of three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles during electrochemical performance testing;
FIG. 10a is a schematic diagram of photothermal effect release of anticancer drug Doxorubicin (DOX) after modification of ordered mesoporous Au surface by dodecanoic acid polyethylene glycol (L C-PEG);
FIG. 10b shows the power density of the mixed solution of pure water and Au L C-PEG/DOX at different concentrations at 1w/cm2A photo-thermal curve chart of 808nm laser irradiation for 5 min;
FIG. 10c shows the measured power density at 1w/cm2Temperature change diagram of Au L C-PEG/DOX (100 μ g/ml) during 4 cycles under 808nm laser irradiation;
FIG. 11a is a confocal fluorescence microscopy of co-culture of three-dimensional ordered Au nanoparticles with 4T1 cancer cells without laser irradiation of 4T1 cancer cells;
FIG. 11b shows that 1W/cm is used in the co-culture process of three-dimensional ordered Au nanoparticles and 4T1 cancer cells2Confocal fluorescence microscopy of 4T1 cancer cells after 5 minutes of laser irradiation.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
the preparation method of the three-dimensional ordered mesoporous noble metal nano-particles comprises the following steps: dissolving mesoporous material powder in the solution at room temperature, then carrying out vacuum drying in a vacuum drying oven, then dropwise adding n-hexane or dichloromethane, subsequently dropwise adding 1,1,3, 3-tetramethyldisiloxane or n-butylamine for reduction, then washing and centrifuging, and finally dissolving the mesoporous material powder to obtain the three-dimensional ordered mesoporous noble metal nano-particles.
The three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles can be used for surface enhanced Raman scattering spectroscopy; the three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles can be used for the photothermal and drug composite treatment of cancer; the three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles can be used in photoelectrochemical catalysis.
Example one
10mg of mesoporous material KIT-6 powder was dissolved in 1m L, 3mM HAuCl at room temperature4·4H2Drying in a vacuum drying oven for 24h in an O ethanol solution to convert white powder into yellow powder; 100ul of n-hexane and 10ul of 1,1,3, 3-tetramethyldisiloxane are sequentially dropped to change yellow powder into black powder; washing the black powder twice with absolute ethyl alcohol, centrifuging, dissolving the mesoporous material KIT-6 powder with HF with the volume concentration of 20%, centrifuging again, and washing with absolute ethyl alcohol for several times to obtain the three-dimensional ordered mesoporous Au nanoparticles, as shown in figures 2 and 3.
Fig. 2 and 3 are SEM and TEM images of three-dimensional ordered mesoporous Au nanoparticles, respectively. As shown in FIGS. 2 and 3, the three-dimensional ordered mesoporous Au nanoparticle has a single component, a size of about 100nm, and a pore diameter of 5-10 nm. Furthermore, the three-dimensional ordered mesoporous Au nanoparticles duplicate a mesoporous material KIT-6 three-dimensional bicontinuous spiral icosahedral pore canal, and have a face-centered cubic configuration.
Example two
Dissolving 10mg of mesoporous material KIT-6 powder in 1ml of 3mM HAuCl at room temperature4·4H2Drying in a vacuum drying oven for 24h in an O ethanol solution to convert white powder into yellow powder; dropping 100ul n-hexane and 10ul 1,1,3, 3-tetramethyldisiloxane in sequence to turn yellow powder into black powder, standing the black powder for 2min (FIG. 4b), 8min (FIG. 4c), 15min (FIG. 4d), 2h (FIG. 4e) and 6h (FIG. 4f), respectively; washing the black powder twice with absolute ethyl alcohol, centrifuging, dissolving the mesoporous material KIT-6 powder with HF with the volume concentration of 20%, centrifuging, and washing with absolute ethyl alcohol for a plurality of times to obtain the three-dimensional ordered mesoporous Au nanoparticles.
EXAMPLE III
10mg of mesoporous material KIT-6 powder was dissolved in 1m L, 3mM HAuCl at room temperature4·4H2Adding 25ul of AgNO3 with the concentration of 3mM dropwise into the O ethanol solution, and drying in a vacuum drying oven for 24h to obtain yellow powder; 100ul of n-hexane and 100ul of n-butylamine are sequentially added dropwise, and the yellow powder is gradually changed into black powder; washing black powder with anhydrous ethanol for several times, centrifuging, and concentrating with volume concentration of 20%The HF dissolves the mesoporous material KIT-6 powder, and the three-dimensional ordered mesoporous Au-Ag nano-particles are obtained by centrifuging and washing the powder for a plurality of times by using absolute ethyl alcohol, as shown in figures 5a and 5 b.
Example four
10mg of mesoporous material KIT-6 powder was dissolved in 1m L, 3mM HAuCl at room temperature4·4H2Drying in a vacuum drying oven for 24h in an O ethanol solution to convert white powder into yellow powder; 100ul of n-hexane and 10ul of n-butylamine are sequentially added dropwise, and the yellow powder is gradually changed into black powder; washing the black powder with absolute ethyl alcohol for several times, centrifuging, dissolving the mesoporous material KIT-6 powder with HF with the volume concentration of 20%, centrifuging, and washing with absolute ethyl alcohol for several times to obtain the three-dimensional ordered mesoporous Au nanoparticles, as shown in figure 6 a.
EXAMPLE five
10mg of mesoporous material KIT-6 powder was dissolved in 1m L, 3mM HAuCl at room temperature4·4H2Drying in a vacuum drying oven for 24h in an O ethanol solution to convert white powder into yellow powder; 100ul of dichloromethane and 10ul of 1,1,3, 3-tetramethyldisiloxane are sequentially added dropwise, and the yellow powder is changed into black powder; washing the black powder with absolute ethyl alcohol for several times, centrifuging, dissolving the mesoporous material KIT-6 powder with HF with the volume concentration of 20%, centrifuging, and washing with absolute ethyl alcohol for several times to obtain the three-dimensional ordered mesoporous Au nanoparticles, as shown in figure 6 b.
EXAMPLE six
Dissolving 10mg of mesoporous material KIT-6 powder in 0.1M K of 10M L at room temperature2PtCl4Drying in a vacuum drying oven for 24h in the aqueous solution to obtain an orange powder; 100ul of n-hexane and 10ul of 1,1,3, 3-tetramethyldisiloxane were sequentially added dropwise, and the orange powder turned into black; washing the black powder with absolute ethyl alcohol for several times, centrifuging, dissolving the mesoporous material KIT-6 powder by HF with the volume concentration of 20%, centrifuging, and washing with absolute ethyl alcohol for several times to obtain the three-dimensional ordered mesoporous Pt nanoparticles, as shown in figure 7.
1. Application of three-dimensional ordered mesoporous Au nanoparticles in detection of organic molecule rhodamine 6G
The three-dimensional ordered mesoporous Au nanoparticle prepared in the first embodiment and ethanol are used for preparing a suspension of the three-dimensional ordered mesoporous Au nanoparticle, and then the suspension of the three-dimensional ordered mesoporous Au nanoparticle is used for detecting organic molecules, such as rhodamine 6G. The specific method for carrying out Raman detection on the organic molecules comprises the following steps: dripping the suspension of the three-dimensional ordered mesoporous Au nano particles on 5 silicon chips respectively, and then carrying out natural volatilization drying to obtain the Au nano particles with the concentration of 20ul being 10 respectively-7M、10-9M、10-10M and 10-11And sequentially dripping M rhodamine 6G molecular solution on the substrate of the 3 three-dimensional ordered mesoporous Au nanoparticles, and performing surface enhanced Raman scattering spectroscopy (SERS) detection after natural volatilization and drying, wherein the detection is shown in figure 8. In the SERS performance test process, the test instrument is a portable Raman spectrometer, a lens is a 100x objective lens, the wavelength of laser is 785nm, the laser power is 50mW, and the diameter of a laser spot is 21 microns.
As shown in FIG. 8, the three-dimensional ordered mesoporous Au nanoparticle SERS active substrate detects rhodamine 6G molecules, and the concentration of the rhodamine 6G molecules is reduced to 10-11The time signal is still obvious, and the detection sensitivity is high.
2. Electrochemical test of three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles
The three-dimensional ordered mesoporous Au and Au-Ag alloy nanoparticles prepared in the first embodiment are applied to the electro-catalysis test of methanol. The electrochemical catalysis experiment uses a Versa STAT 3 electrochemical workstation, adopts a three-electrode system, the working electrode is a glassy carbon rotating disk electrode (GCE, the diameter is 5mm), and the area of the electrode is 1cm2The reference electrode was an Ag/AgCl electrode. Three-dimensional ordered mesoporous Au-Ag nanoparticles, three-dimensional ordered mesoporous Au nanoparticles, Au-Ag nanoparticles with the diameter of 100nm, Au nanoparticles with the diameter of 4nm and Au nanoparticles with the diameter of 70nm are selected as controls. The catalytic performance of the catalyst was determined in a deoxygenated solution of 0.5m KOH and 2m methanol at a scan rate of 10 mV/s. Determination of H at 0.5m for different catalysts by means of CV curves2SO4The active specific surface area in the aqueous solution and the scanning rate are 10 mV/s; in an aqueous solution of 0.5MKOH and 2M CH3OH saturated with oxygen at a rate of 10mV/s at-0.15The accelerated durability test was carried out under a condition of about 0.55v (vsag/agcl). FIG. 9a is a cyclic voltammogram for methanol electrocatalysis; FIG. 9b is a timing current diagram; FIG. 9c is an oxide dissolution profile; figure 9d is a mass activity and site activity histogram.
Compared with three-dimensional ordered mesoporous Au nanoparticles, Au-Ag nanoparticles with the diameter of 100nm, Au-Ag nanoparticles with the diameter of 4nm and Au-Au nanoparticles with the diameter of 70nm, the three-dimensional ordered mesoporous Au-Ag nanoparticles have higher reduction potential and lower oxidation potential in the test of methanol electrochemical catalysis, the circulating stability is good, and the mass activity and the site activity are 3 times of those of the 4nm-Au nanoparticles and 24 times of those of the 70nm-Au nanoparticles.
3. Three-dimensional ordered mesoporous Au nanoparticle photo-thermal and drug composite treatment application
FIG. 10a shows the drug loading and release process of the three-dimensional ordered mesoporous Au nanoparticles, wherein the mesoporous gold surface is modified by polyethylene glycol dodecanoate (L C-PEG), and then the anticancer drug Doxorubicin (DOX) is loaded, the three-dimensional ordered mesoporous Au nanoparticles prepared in example one are prepared with water into Au L C-PEG/DOX solutions with the concentrations of 0.1mg/ml, 0.2mg/ml, 0.4mg/ml and 1.0mg/ml, and pure water solutions at the power density of 1w/cm2Fig. 10C shows the temperature rise curve of Au L C-PEG/DOX (100 μ g/ml) when the laser of the nanoparticle is cycled 4 times (6 min per cycle) under the irradiation of light, and as can be seen from fig. 10b and 10C, the nanoparticle has good stability.
The method comprises the steps of compounding three-dimensional ordered mesoporous Au nanoparticles modified by dodecanoic acid polyethylene glycol (L C-PEG) with anticancer drug adriamycin (DOX), adding a certain amount of a composite structure into cancer cells filled with 4T1 for culturing for 24 hours, irradiating the cells for 5 minutes by using infrared laser with the wavelength of 808nm under the condition that the power density is 1W/cm2, immediately dyeing the dead cells by using dye, dripping the dyed suspension onto a glass sheet, and observing the death condition of the cells by using a confocal fluorescence microscope.
Claims (9)
1. A preparation method of three-dimensional ordered mesoporous noble metal nanoparticles is characterized by comprising the following steps:
dissolving mesoporous material powder in a solution at room temperature, performing vacuum drying in a vacuum drying oven, then dropwise adding n-hexane or dichloromethane, dropwise adding 1,1,3, 3-tetramethyldisiloxane for reduction, washing and centrifuging, and finally dissolving the mesoporous material powder to obtain three-dimensional ordered mesoporous noble metal nanoparticles;
when the three-dimensional ordered mesoporous noble metal nanoparticles are three-dimensional ordered mesoporous Au nanoparticles, the method comprises the following steps:
dissolving a mesoporous material KIT-6 molecular sieve powder in HAuCl at room temperature4.4H2In an O ethanol solution, drying in a vacuum drying oven to convert mesoporous material KIT-6 molecular sieve powder into yellow powder, then dropwise adding n-hexane or dichloromethane, then dropwise adding 1,1,3, 3-tetramethyldisiloxane for reduction to convert the yellow powder into black powder, then washing and centrifuging the black powder, then dissolving the black powder in distilled water, then adding HF for standing, and finally centrifuging and washing to obtain three-dimensional ordered mesoporous Au nanoparticles;
in the process of drying in the vacuum drying oven, the temperature in the vacuum drying oven is 30-50 ℃, and the drying time is 24 hours.
2. The method for preparing three-dimensional ordered mesoporous noble metal nanoparticles as claimed in claim 1, wherein the reduction time is adjusted according to the size of the three-dimensional ordered mesoporous Au nanoparticles, and the reduction time ranges from 1h to 72 h.
3. The method for preparing three-dimensional ordered mesoporous noble metal nanoparticles of claim 1, wherein the mesoporous material is KIT-6 molecular sieve powder, HAuCl4.4H2The proportion of O ethanol solution, n-hexane or dichloromethane, 1,3, 3-tetramethyldisiloxane, distilled water and HF is 10 mg: 1m L: 100 ul: 10 ul: 4m L: 2m L, wherein, HAuCl4.4H2The concentration range of the O ethanol solution is 0.1 mM-1M; the volume concentration of HF is 20-40%.
4. The method for preparing three-dimensional ordered mesoporous noble metal nanoparticles of claim 1, wherein the diameter of the three-dimensional ordered mesoporous Au nanoparticles is 50nm to 500nm, and the pore diameter is 2 nm to 15 nm.
5. The method for preparing three-dimensional ordered mesoporous noble metal nanoparticles according to claim 1, wherein,
washing the black powder with absolute ethyl alcohol for several times, and then centrifuging;
dissolving mesoporous material KIT-6 molecular sieve powder by using HF, centrifuging, and washing for a plurality of times by using absolute ethyl alcohol.
6. The method for preparing three-dimensional ordered mesoporous noble metal nanoparticles according to claim 1, wherein when the three-dimensional ordered mesoporous noble metal nanoparticles are three-dimensional ordered mesoporous Pt nanoparticles, the method comprises the following steps:
dissolving 10mg of mesoporous material KIT-6 powder in 0.1M K of 10M L at room temperature2PtCl4Drying in vacuum drying oven for 24 hr to convert white powder into orange powder, adding 100ul n-hexane or dichloromethane dropwise, adding 1,1,3, 3-tetramethyldisiloxane dropwise for reduction to convert orange powder into black powder, and washing black powder with anhydrous ethanolDrying, dissolving the mesoporous material KIT-6 powder by using HF with the volume concentration of 20% after centrifugation, and washing for a plurality of times by using absolute ethyl alcohol after centrifugation to obtain three-dimensional ordered mesoporous Pt nanoparticles;
when the three-dimensional ordered mesoporous noble metal nano-particles are three-dimensional ordered mesoporous Au-Ag nano-particles, the method comprises the following steps:
10mg of mesoporous material KIT-6 powder was dissolved in 1m L, 3mM HAuCl at room temperature4.4H2Adding 25ul of 3mM AgNO dropwise into the O ethanol solution3And then drying the powder in a vacuum drying oven for 24 hours to convert white powder in the solution into yellow powder, then dropwise adding 100ul of n-hexane or dichloromethane, then dropwise adding 10ul of 1,1,3, 3-tetramethyldisiloxane for reduction to convert the yellow powder into black, then washing the black powder for a plurality of times by using absolute ethyl alcohol, dissolving the mesoporous material KIT-6 powder by using HF with the volume concentration of 20% after centrifuging, and finally washing the powder for a plurality of times by using the absolute ethyl alcohol after centrifuging to obtain the three-dimensional ordered mesoporous Au-Ag alloy nano particles.
7. The application of the three-dimensional ordered mesoporous noble metal nanoparticles prepared by the preparation method of any one of claims 1-6 in surface enhanced Raman scattering spectroscopy.
8. The application of the three-dimensional ordered mesoporous noble metal nanoparticles prepared by the preparation method of any one of claims 1-6 in the composite treatment of cancer photo-thermal and medicine.
9. The application of the three-dimensional ordered mesoporous noble metal nanoparticles prepared by the preparation method of any one of claims 1-6 in photoelectrochemical catalysis.
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