CN106620702A - Preparation method of gold/nitrogen-doped hollow carbon nanosphere core-shell material - Google Patents
Preparation method of gold/nitrogen-doped hollow carbon nanosphere core-shell material Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
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- A—HUMAN NECESSITIES
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- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
- A61K9/5021—Organic macromolecular compounds
- A61K9/5031—Organic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, poly(lactide-co-glycolide)
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- A—HUMAN NECESSITIES
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5073—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals having two or more different coatings optionally including drug-containing subcoatings
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Abstract
The invention relates to a preparation method of a gold/nitrogen-doped hollow carbon nanosphere core-shell material, belonging to the field of biomedical materials. The preparation method comprises the steps of firstly, preparing gold sol by using a sol-gel method; secondly, coating the surfaces of gold particles with SiO2 by using an improved stober method, and then forming Au@SiO2@PDA spheres in a weak alkaline water-containing environment by means of auto polymerization of dopamine; finally, carrying out high-temperature calcination, and obtaining the gold/nitrogen-doped hollow carbon nanosphere core-shell material after NaOH is etched. The method is simple, mild and environment-friendly, and does not add additional toxicity; the prepared gold/nitrogen-doped hollow carbon nanosphere core-shell material has the particle size of about 165-175nm; as a near-infrared photothermal therapeutic agent for treating tumors, a product not only has good biocompatibility and light and heat stability, but also has the characteristic of having an internal hollow structure; after the gold/nitrogen-doped hollow carbon nanosphere core-shell material is used, the speed of particle exchange is accelerated, and the photothermal conversion efficiency is improved.
Description
Technical field
The invention belongs to field of biomedical materials, the photo-thermal therapy technology of more particularly to minimally invasive tumour.
Background technology
Cancer（Malignant tumour）Threat to human health is increasing, and its incidence of disease is annual all in increase, dead
Rate remains high.Although many diagnosis and treatment and treatment means are exploited for treating cancer, the survival rate of cancer patient is still
It is very low.Nowadays the clinical method for the treatment of cancer mainly passes through the methods such as operation, chemotherapy and radiation, yet with cancer metastasis
Property and infectivity, so in cancer of late stage, general surgery cannot cure cancer, chemotherapy and radiation is the feasible side of comparison
Method.But chemotherapy and radiation is to the specific poor of tumor tissues so that therapeutic effect is not good and has certain toxic and side effect.
Therefore the healing efficiency for improving cancer patient and the toxic and side effect for reducing anti-cancer therapies are in current cancer treatment procedure
Problem in the urgent need to address.
Photo-thermal therapy（Photothermal therapy, PTT）It is a kind of minimally invasive oncotherapy for developing in recent years
Technology, mainly by the way that the light of certain wavelength is shone directly into tumor locus so as to which tumor locus temperature raises to reach
To the purpose for killing tumour cell.Photo-thermal therapy can use long wavelength light, due to its energy it is relatively low, so to health tissues
It is smaller with the infringement of cell, also greatly reduce the toxicity of whole body system, therefore photo-thermal therapy becomes and have very much now latent
Power substitutes one of technology of operative treatment tumour.Therefore exploitation has good biocompatibility, and synthetic method is simple and has
Higher photo-thermal conversion efficiency and the photo-thermal therapy agent of photo and thermal stability is extremely important.
The material composition of the near-infrared photo-thermal therapy agent of existing treatment tumour is mainly noble metal nano particles, carbons material
Material, organic dyestuff material.Noble metal nano particles photo-thermal conversion efficiency is high, and near infrared region absorbability is strong, but expensive；
Material with carbon element photothermal deformation area is larger, and photo-thermal conversion efficiency is higher, although but near infrared region absorbability is general with low cost；
Therefore noble metal is compound not only with low cost with material with carbon element, and photo-thermal conversion efficiency is high, and near infrared absorption ability is stronger.
The absorption of golden nanometer particle and scattering strength are preferable so that they are latent with very big application in terms of photo-thermal therapy
Power.It is excellent that gold nano grain also has that biological safety is higher simultaneously, prepare that simple, surface nature is stable, optical property is adjustable etc.
Point.Biocompatible carbon material preferably, also shows certain application potential in terms of photo-thermal therapy, therefore by material with carbon element and gold
Nano-particle combines, and plays their cooperative effect, is expected to set up the multifunctional light heat cure platform for working well.
The content of the invention
To solve the above problems, present invention aim at proposition is a kind of can be used as the near-infrared photo-thermal therapy agent for the treatment of tumour
Gold/N doping hollow Nano carbon balls core-shell material preparation method.
The present invention is comprised the following steps：
1）By the water and HAuCl of boiling4The aqueous solution, trisodium citrate aqueous solution mixing, after being stirred at reflux cool down, then again with
The mixing of the PVP aqueous solution carries out modification reaction, and reaction is centrifuged after terminating, and takes solid phase dispersion in water, obtains final product aurosol；
2）By aurosol, ethanol, deionized water, ammoniacal liquor mix after, in mixed solution be added dropwise TEOS be stirred at room temperature after from
The heart, takes solid matter with water and alcohol washing post-drying, obtains Au@SiO2Ball；
3）By Au@SiO2Ball be dissolved in concentration for 0.01～0.02 M,pH values are in 8.0～8.5 Tris aqueous solution, after ultrasound
The Dopamine hydrochloride aqueous solution is added, Jing centrifugations after being stirred at room temperature take solid phase washing, drying, obtain Au SiO2@PDA ball solid powder
End；
4）In N2Under protection, by Au@SiO2@PDA ball pressed powders are placed in tube furnace and calcine, and obtain carbide；Again will charing
Thing is placed in the NaOH aqueous solution that concentration is 1 M and soaks, Jing centrifugations, obtains solid phase and washs to neutrality, drying, obtains golden/N doping
Hollow Nano carbon balls core-shell material (Au@N-HCNs).
The present invention first aurosol is prepared by sol-gal process, secondly by improved stober methods gold particle table
Bread wraps up in SiO2, then Au@SiO are formed by the auto polymerization of dopamine under alkalescent aqueous environment2@PDA balls, most after Jing high temperature
Calcining, obtains the hollow Nano carbon balls core-shell material of gold/N doping after NaOH etchings.
Particularly the present invention adopt concentration for 0.01～0.02 M,pH values for 8.0～8.5 the Tris aqueous solution, this environment
Be conducive to the polymerization of dopamine, dopamine equably can attach to Au@SiO by autohemagglutination2Ball surface.
Not only method for designing is simple, gentle for the present invention, environmental protection, will not also increase additional toxicity.Gold/nitrogen prepared by the present invention
The hollow Nano carbon balls core-shell material particle diameter of doping is about 165～175 nm, near-infrared of the product of the present invention as treatment tumour
Photo-thermal therapy agent not only has good biocompatibility and photo and thermal stability, and with the internal spy for hollow-core construction
Point, increases the speed of exchange of particles, improves photo-thermal conversion efficiency.
Further, step 1 of the present invention）In, HAuCl4AuCl in the aqueous solution3, citric acid three in trisodium citrate aqueous solution
The mixing mol ratio of PVP is 1: 6: 2 in sodium and the PVP aqueous solution.Strict control HAuCl4It is 1 with the mol ratio of trisodium citrate:
6, drip sodium citrate can significantly see solution colour by yellow to colourless to black to purple, eventually become claret.
So the particle diameter of gold particle is about 15 nm after the reduction of gold chloride Jing trisodium citrates.Treat that solution is cooled down after reaction half an hour
To room temperature, it is stirred overnight with PVP modifications, the mol ratio of trisodium citrate and PVP is 3: 1.It is centrifuged after the completion of reaction, by what is obtained
The aurosol modified with PVP is dissolved in H2In O, it is easy to later stage coated Si O2Use.
Step 1 of the present invention）In, the mixing speed is 600～700 r/min, the Jenner formed under the rotating speed
Rice corpuscles is than more uniform.
Step 1 of the present invention）In, the centrifugal rotational speed is 11800 r/min, can be reduced to greatest extent under the rotating speed
The loss of gold particle.The damaged situation of centrifuge tube occurs if rotating speed is too big；Rotating speed is too little then gold particle will to lose too many.
Centrifugation 1～2 time, if centrifugation number of times is too many, golden nanometer particle is easier to reunite.
Step 2 of the present invention）In, the mixed volume ratio of the TEOS, ammoniacal liquor, aurosol, deionized water and ethanol is 1: 2: 4
: 12: 20, the SiO of golden nanometer particle load under the ratio2Particle diameter is than more uniform.
The step 2）In, the speed being stirred at room temperature is 600～700 r/min, and the centrifugal rotational speed is 10000
r/min.The Au@SiO formed with this2Than more uniform, in 150 nm or so, so not only yield is more for particle diameter, and granule for ball
The sample in footpath is more suitable for photothermal deformation.
The step 3）In, the Au@SiO2Ball is 1: 1～3 with the mixing quality ratio of Dopamine hydrochloride, is wrapped under the ratio
The poly-dopamine wrapped up in is than more uniform, and photo-thermal effect is preferable.Ultrasonic power is 80 W, and ultrasonic time is 0.5 h.If during ultrasound
Between it is too short, sample can be made to disperse uneven in the Tris aqueous solution, affect poly-dopamine cladding；Such as cross overlong time, although
Sample dispersion is uniform, but time consumption and energy consumption.It is described that speed is stirred at room temperature for 600～700 r/min；The centrifugal rotational speed is
10000 r/min.Under the reaction conditions, the attachment of poly-dopamine layer is uniform, and thickness is moderate.
The step 4）In, 2 h are kept after being warming up to 800 DEG C with the heating rate of 5 DEG C/min during the calcining.This
It is bright temperature be 800 DEG C under the conditions of calcine when, degree of carbonization is best.Carbonization temperature is too high, and carbon and nitrogen loss can be made tight
Weight；Carbonization temperature is too low, and more impurity is had in material with carbon element, and degree of carbonization is low, causes degree of graphitization relatively low.With 5 DEG C/
When min is heating rate, both can guarantee that poly-dopamine polycondensation and carbonization in pyrolytic process generated material with carbon element, while can also reduce
The loss amount of material with carbon element in pyrolysis.
The step 4）In, the soaking temperature is 75 DEG C, and the time is 3 h.The addition of NaOH is removed for etching
SiO2, the NaOH solution of low concentration.Improving temperature can shorten etch period, and 75 DEG C of temperature are more suitable.Reaction time is
3 h are to guarantee SiO2Removed by etching completely.
The step 4）In, the centrifugal rotational speed is 10000 r/min.If centrifugal rotational speed is too little, sample has too much
Loss；If centrifugal rotational speed is too big, time consumption and energy consumption.
Description of the drawings
Fig. 1 is Au@SiO prepared by the present invention2The TEM figures of ball.
Fig. 2 is Au@SiO prepared by the present invention2The TEM figures of@PDA balls.
Fig. 3 is Au@SiO prepared by the present invention2The TEM figures of@N-CNs.
Fig. 4 is the TEM figures of Au@N-HCNs core-shell materials prepared by the present invention.
Fig. 5 is the x-ray diffraction pattern of Au@N-HCNs core-shell materials prepared by the present invention.
Fig. 6 is the Raman spectrogram of Au@N-HCNs core-shell materials prepared by the present invention.
Fig. 7 is heating curve figure of the Au@N-HCNs core-shell materials of present invention preparation under near-infrared irradiation.
Fig. 8 is the cycling rate of heating curve under near-infrared irradiation of Au@N-HCNs core-shell materials prepared by the present invention.
Specific embodiment
First, preparation technology：
1st, embodiment 1：
（1）PVP modifies the preparation of aurosol：Take 30 mL water be placed in 100mL single necked round bottom flask be heated to boiling, respectively plus
Enter the HAuCl of 150 mM4The μ L of trisodium citrate aqueous solution 74 of the μ L of the aqueous solution 100 and 34 mM, in the stirring of 700 r/min
Flow back 0.5 h under speed.Treat that solution is cooled to room temperature, add the mL of the PVP aqueous solution 5.86 of 1.28 mM, be stirred overnight.
Completely reacted solution is placed in centrifuge tube and is centrifuged 1～2 time with 11800 r/min, upper liquid is taken out with dropper,
Remaining solid phase aurosol is dispersed in 8 mL deionized waters, obtains aurosol, standby.
（2）Au@SiO2The preparation of ball：Take 2 mL aurosols ultrasonically treated 3～5 min under conditions of power is 80 W
It is placed in 50 mL single necked round bottom flask, with 700 r/min under room temperature with 1 mL ammoniacal liquor, 6 mL deionized waters, 10 mL ethanol afterwards
Stir 0.5 h.0.5 mL TEOS are eventually adding, 6 h are stirred with 700 r/min under room temperature, then the r/min centrifuging and takings of Jing 1000 are obtained
Solid phase, to wash, alcohol is washed each 3 times, is placed in 60 DEG C of baking oven and is dried, and obtains Au@SiO2Ball.
（3）Au@SiO2The preparation of@PDA balls：Weigh Au@SiO2The mg of ball 50 is added to the 100 mL Tris aqueous solution（pH=
8.5,0.01 M）In, then ultrasonically treated 0.5 h under conditions of power is 80 W is adding 50 mg Dopamine hydrochlorides, room
10h is stirred with 700 r/min under temperature, then the r/min centrifuging and takings of Jing 1000 obtain solid phase, to wash, alcohol is washed each 3 times, is placed in 60 DEG C
Baking oven in dry, obtain Au@SiO2@PDA ball pressed powders.
（4）The preparation of Au@N-HCNs：By Au@SiO2@PDA ball pressed powders are placed in tube furnace, it is passed through 10 in advance～
The N of 20 min2Air in drain quartz ampoule, then with the heating rate of 5 DEG C/min rise to 800 DEG C charing 2 h obtain charcoal
Compound Au@SiO2@N-CNs.Carbide is placed in into water-bath immersion 3 h, the r/ of Jing 1000 in the NaOH aqueous solution of 75 DEG C of 0.1 M
Min is centrifuged, and takes solid phase deionized water and is washed till neutrality, is placed in 60 DEG C of baking oven and dries, and the hollow carbon for obtaining golden/N doping is received
Rice ball shell material Au@N-HCNs.
2nd, embodiment 2：
（1）PVP modifies the preparation of aurosol：Take 30 mL water be placed in 100mL single necked round bottom flask be heated to boiling, respectively plus
Enter the HAuCl of 150 mM4The μ L of trisodium citrate aqueous solution 74 of the μ L of the aqueous solution 100 and 34 mM, in the stirring of 700 r/min
Flow back 0.5 h under speed.Treat that solution is cooled to room temperature, add the mL of the PVP aqueous solution 5.86 of 1.28 mM, be stirred overnight.
Completely reacted solution is placed in centrifuge tube and is centrifuged 1 ~ 2 time with 11800 r/min, upper liquid is taken out with dropper,
Remaining solid phase aurosol is dispersed in 8 mL deionized waters, obtains aurosol, standby.
（2）Au@SiO2The preparation of ball：Take 2 mL aurosols under conditions of the W of power 80 after ultrasonically treated 3～5 min and
1 mL ammoniacal liquor, 6 mL deionized waters, 10 mL ethanol are placed in 50 mL single necked round bottom flask, with 700 r/min stirrings under room temperature
0.5 h.0.5 mL TEOS are eventually adding, 6 h are stirred with 700 r/min under room temperature, then the r/min centrifuging and takings of Jing 1000 must be consolidated
Phase, to wash, alcohol is washed each 3 times, is placed in 60 DEG C of baking oven and is dried, and obtains Au@SiO2Ball.
（3）Au@SiO2The preparation of@PDA balls：Weigh Au@SiO2The mg of ball 50 is added to the 100 mL Tris aqueous solution（pH=
8.5,0.01 M）In, then ultrasonically treated 0.5 h under conditions of power is 80 W is adding 100mg Dopamine hydrochlorides, room
10h is stirred with 700 r/min under temperature, then the r/min centrifuging and takings of Jing 1000 obtain solid phase, to wash, alcohol is washed each 3 times, is placed in 60 DEG C
Baking oven in dry, obtain Au@SiO2@PDA ball pressed powders.
（4）The preparation of Au@N-HCNs：By Au@SiO2@PDA ball pressed powders are placed in tube furnace, it is passed through 10 in advance～
The N of 20 min2Air in drain quartz ampoule, then with the heating rate of 5 DEG C/min rise to 800 DEG C charing 2 h obtain charcoal
Compound Au@SiO2@N-CNs.Carbide is placed in water-bath immersion 3 h, the r/ of Jing 1000 in the NaOH aqueous solution of 75 DEG C of 0.1M
Min is centrifuged, and takes solid phase deionized water and is washed till neutrality, is placed in 60 DEG C of baking oven and dries, and the hollow carbon for obtaining golden/N doping is received
Rice ball shell material Au@N-HCNs.
3rd, embodiment 3：
（1）PVP modifies the preparation of aurosol：Take 30 mL water be placed in 100mL single necked round bottom flask be heated to boiling, respectively plus
Enter the HAuCl of 150 mM4The μ L of trisodium citrate aqueous solution 74 of the μ L of the aqueous solution 100 and 34 mM, in the stirring of 600 r/min
Flow back 0.5 h under speed.Treat that solution is cooled to room temperature, add the mL of the PVP aqueous solution 5.86 of 1.28 mM, be stirred overnight.
Completely reacted solution is placed in centrifuge tube and is centrifuged 1 ~ 2 time with 11800 r/min, upper liquid is taken out with dropper,
Remaining solid phase aurosol is dispersed in 8 mL deionized waters, obtains aurosol, standby.
（2）Au@SiO2The preparation of ball：2 mL aurosols are taken under conditions of power is 80 W after ultrasonically treated 3～5 min
It is placed in 50 mL single necked round bottom flask with 1 mL ammoniacal liquor, 6 mL deionized waters, 10 mL ethanol, is stirred with 600 r/min under room temperature
Mix 0.5 h.0.5 mL TEOS are eventually adding, 6 h are stirred with 700 r/min under room temperature, then the r/min centrifuging and takings of Jing 1000 must be consolidated
Phase, to wash, alcohol is washed each 3 times, is placed in 60 DEG C of baking oven and is dried, and obtains Au@SiO2Ball.
（3）Au@SiO2The preparation of@PDA balls：Weigh Au@SiO2The mg of ball 50 is added to the 100 mL Tris aqueous solution（pH=
8.5,0.01 M）In, then ultrasonically treated 0.5 h under conditions of power is 80 W is adding 150 mg Dopamine hydrochlorides, room
10 h are stirred with 600 r/min under temperature, then the r/min centrifuging and takings of Jing 1000 obtain solid phase, to wash, alcohol is washed each 3 times, is placed in 60 DEG C
Baking oven in dry, obtain Au@SiO2@PDA ball pressed powders.
（4）The preparation of Au@N-HCNs：By Au@SiO2@PDA ball pressed powders are placed in tube furnace, it is passed through 10 in advance～
The N of 20 min2Air in drain quartz ampoule, then with the heating rate of 5 DEG C/min rise to 800 DEG C charing 2 h obtain charcoal
Compound Au@SiO2@N-CNs.Carbide is placed in into water-bath immersion 3 h, the r/ of Jing 1000 in the NaOH aqueous solution of 75 DEG C of 0.1 M
Min is centrifuged, and takes solid phase deionized water and is washed till neutrality, is placed in 60 DEG C of baking oven and dries, and the hollow carbon for obtaining golden/N doping is received
Rice ball shell material Au@N-HCNs.
2nd, product property：
Au@SiO prepared by the step of various embodiments above 22The TEM of ball is schemed as shown in figure 1, significantly finding out goldc grains from Fig. 1
The particle diameter of son is in 15 nm or so, and Au@SiO2Particle diameter in 145～155 nm.
Au@SiO prepared by the step of various embodiments above 32The TEM of@PDA balls is schemed as shown in Fig. 2 can from Fig. 2
Go out PDA and be uniformly coated on Au@SiO2The surface of ball, Au@SiO2The nm of particle diameter about 165～175 of@PDA balls.
Au@SiO prepared by the step of various embodiments above 42The TEM of@N-CNs balls is schemed as shown in figure 3, can be with bright from Fig. 3
Aobvious finds out that the material particle size after charing has reduced, and this explanation PDA has shunk when being carbonized, Au@SiO2@N-CNs balls
Particle diameter is in 160～170 nm.
Au@SiO prepared by the step of various embodiments above 42The TEM figures of@N-HCNs balls are as shown in figure 4, can be with from Fig. 4
Clearly find out SiO2It is divided, carbon layers having thicknesses are in 10～15 nm.
The x-ray diffraction pattern of Au@N-HCNs core-shell materials prepared by the step of various embodiments above 4 is as shown in Figure 5.Root
Understand according to X-ray diffraction result,（111）、（200）、（220）、（311）Crystallographic plane diffraction peak coincide substantially with Au standard diffractions peak,
(002)、（110）Crystallographic plane diffraction peak coincide substantially with the amorphous diffraction maximum of C.The Au@N-HCNs nucleocapsids that the present invention is prepared
Material, substantially conforms to standard card contrast, and the composition and structure of resulting materials is demonstrated substantially.
The step of various embodiments above 4）The Raman spectrogram of the Au@N-HCNs core-shell materials of preparation is as shown in Figure 6.From figure
In it can be seen that the ratio at D peaks and G peaks is ID/IG=0.916, illustrate that Au@N-HCNs core-shell materials have preferable graphitization journey
Degree.
The step of various embodiments above 4）Heating curve figure of the Au@N-HCNs core-shell materials of preparation under near-infrared irradiation
As shown in Figure 7.Incident wavelength is 808 nm, and laser intensity is 2 W/cm2 .Because human temperature is at 37 DEG C or so, cancer cell exists
At a high temperature of 45-50 DEG C, 40 min are adhered to, it is possible to block the synthesis of cancer cell DNA, cause cancer cell-apoptosis.Can from figure
To find out heating curve of the material of variable concentrations after illumination, containing 50 μ g/mL, 100 μ g/mL, 150 μ g/mL,
The suspension of the Au@N-HCNs core-shell materials of 200 μ g/mL after the laser of 808 nm irradiates 10 min, distinguish by the temperature of suspension
Improve 9.5 DEG C, 15.2 DEG C, 15.9 DEG C, 17.2 DEG C.The result explanation Au@N-HCNs core-shell materials are relatively effective
For treating the near-infrared photo-thermal therapy agent of tumour.
Each embodiment step 4）The cycling rate of heating curve of the Au@N-HCNs core-shell materials of preparation under near-infrared irradiation
As shown in Figure 8.As can be seen from the figure the temperature of the intensification of the suspension of 150 μ g/mL three times has been respectively increased 15.9 DEG C, and 15.2
DEG C, 14.5 DEG C, be due to suspension remains stationary, Au@N-HCNs core-shell materials in measurement process the reason for temperature decreases
Can settle so that particle encounter speed decreases.But as a whole, Au@N-HCNs core-shell materials are more stable
For treating the near-infrared photo-thermal therapy agent of tumour.
Claims (10)
1. a kind of preparation method of the hollow Nano carbon balls core-shell material of gold/N doping, it is characterised in that comprise the following steps：
1）By the water and HAuCl of boiling4The aqueous solution, trisodium citrate aqueous solution mixing, after being stirred at reflux cool down, then again with PVP
Aqueous solution mixing carries out modification reaction, and reaction is centrifuged after terminating, and takes solid phase dispersion in water, obtains final product aurosol；
2）By aurosol, ethanol, deionized water, ammoniacal liquor mix after, in mixed solution be added dropwise TEOS be stirred at room temperature after from
The heart, takes solid matter with water and alcohol washing post-drying, obtains Au@SiO2Ball；
3）By Au@SiO2Ball be dissolved in concentration for 0.01～0.02 M,pH values are in 8.0～8.5 Tris aqueous solution, to add after ultrasound
Enter the Dopamine hydrochloride aqueous solution, Jing centrifugations after being stirred at room temperature take solid phase washing, drying, obtain Au SiO2@PDA ball pressed powders；
4）In N2Under protection, by Au@SiO2@PDA ball pressed powders are placed in tube furnace and calcine, and obtain carbide；Again by carbide
It is placed in the NaOH aqueous solution that concentration is 1 M and soaks, Jing centrifugations obtains solid phase and wash to neutrality, drying, obtain golden/N doping
Hollow Nano carbon balls core-shell material.
2. preparation method according to claim 1, it is characterised in that the step 1）In, HAuCl4AuCl in the aqueous solution3、
The mixing mol ratio of PVP is 1: 6: 2 in trisodium citrate and the PVP aqueous solution in trisodium citrate aqueous solution.
3. preparation method according to claim 2, it is characterised in that the step 1）In, the mixing speed is 600
～700 r/min, the centrifugal rotational speed is 11800 r/min, is centrifuged 1～2 time.
4. preparation method according to claim 1, it is characterised in that the step 2）In, the TEOS, ammoniacal liquor, Jin Rong
The mixed volume ratio of glue, deionized water and ethanol is 1: 2: 4: 12: 20.
5. preparation method according to claim 4, it is characterised in that the step 2）In, the speed that is stirred at room temperature is
600～700 r/min, the centrifugal rotational speed is 10000 r/min.
6. preparation method according to claim 1, it is characterised in that the step 3）In, the Au@SiO2Ball is more with hydrochloric acid
The mixing quality ratio of bar amine is 1: 1～3, and ultrasonic power is 80 W, and ultrasonic time is 0.5 h.
7. preparation method according to claim 6, it is characterised in that the step 3）In, the speed that is stirred at room temperature is
600～700 r/min；The centrifugal rotational speed is 10000 r/min.
8. preparation method according to claim 1, it is characterised in that the step 4）In, with 5 DEG C/min during the calcining
Heating rate be warming up to 800 DEG C after keep 2 h.
9. the preparation method according to claim 1 or 8, it is characterised in that the step 4）In, the soaking temperature is 75
DEG C, the time is 3 h.
10. preparation method according to claim 1, it is characterised in that the step 4）In, the centrifugal rotational speed is 10000
r/min。
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| CN107195462A (en) * | 2017-06-02 | 2017-09-22 | 扬州大学 | A kind of preparation method and applications of photosensitizer nano composite material |
| CN107216882A (en) * | 2017-07-21 | 2017-09-29 | 安徽师范大学 | A kind of preparation and application of AgNPs@PDA CdSe quantum dot Nanoscale assemblies |
| CN107481827A (en) * | 2017-08-31 | 2017-12-15 | 扬州大学 | The preparation method of internal confinement growth MOFs hollow magnetic Nano carbon balls |
| CN108539163A (en) * | 2018-04-08 | 2018-09-14 | 齐鲁工业大学 | A kind of preparation method of mesoporous hollow nitrogen-doped carbon nanosphere/manganese dioxide Zinc ion battery positive electrode |
| CN109200059A (en) * | 2017-07-07 | 2019-01-15 | 中科新蕴生物科技（北京）有限公司 | The SOD like activity and application thereof of nitrogen-doped nanometer carbon ball |
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| CN111054416A (en) * | 2019-12-09 | 2020-04-24 | 华南理工大学 | Nitrogen-doped carbon material supported alloy catalyst and preparation method and application thereof |
| CN112022837A (en) * | 2020-09-14 | 2020-12-04 | 安徽理工大学 | Nano delivery system and preparation method and application thereof |
| CN113415798A (en) * | 2021-05-12 | 2021-09-21 | 江西农业大学 | Preparation method of phosphorus-doped microporous, mesoporous and macroporous coexisting grade pore structure nano carbon spheres |
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| CN116446192A (en) * | 2023-05-06 | 2023-07-18 | 广州市得易服饰有限公司 | Heating and warming fabric and preparation method thereof |
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| CN107195462A (en) * | 2017-06-02 | 2017-09-22 | 扬州大学 | A kind of preparation method and applications of photosensitizer nano composite material |
| CN107195462B (en) * | 2017-06-02 | 2019-03-29 | 扬州大学 | A kind of preparation method and applications of photosensitizer nanocomposite |
| CN109200059A (en) * | 2017-07-07 | 2019-01-15 | 中科新蕴生物科技（北京）有限公司 | The SOD like activity and application thereof of nitrogen-doped nanometer carbon ball |
| CN109200059B (en) * | 2017-07-07 | 2021-03-30 | 昆山新蕴达生物科技有限公司 | Superoxide dismutase-like activity of nitrogen-doped carbon nanospheres and application thereof |
| CN107216882B (en) * | 2017-07-21 | 2020-01-10 | 安徽师范大学 | Preparation and application of AgNPs @ PDA-CdSe quantum dot nano assembly |
| CN107216882A (en) * | 2017-07-21 | 2017-09-29 | 安徽师范大学 | A kind of preparation and application of AgNPs@PDA CdSe quantum dot Nanoscale assemblies |
| CN107481827A (en) * | 2017-08-31 | 2017-12-15 | 扬州大学 | The preparation method of internal confinement growth MOFs hollow magnetic Nano carbon balls |
| CN107481827B (en) * | 2017-08-31 | 2019-04-19 | 扬州大学 | The preparation method of the hollow magnetic Nano carbon balls of internal confinement growth MOFs |
| CN108539163A (en) * | 2018-04-08 | 2018-09-14 | 齐鲁工业大学 | A kind of preparation method of mesoporous hollow nitrogen-doped carbon nanosphere/manganese dioxide Zinc ion battery positive electrode |
| CN110280290A (en) * | 2019-07-08 | 2019-09-27 | 华南理工大学 | One kind having flower-shaped type nitrogen-doped carbon-spinel-type microspherical catalyst of high-specific surface area and the preparation method and application thereof |
| CN110280290B (en) * | 2019-07-08 | 2021-10-26 | 华南理工大学 | Flower-shaped nitrogen-doped carbon-spinel microsphere catalyst with high specific surface area and preparation method and application thereof |
| CN111054416A (en) * | 2019-12-09 | 2020-04-24 | 华南理工大学 | Nitrogen-doped carbon material supported alloy catalyst and preparation method and application thereof |
| CN111054416B (en) * | 2019-12-09 | 2021-12-21 | 华南理工大学 | Nitrogen-doped carbon material supported alloy catalyst and preparation method and application thereof |
| CN112022837A (en) * | 2020-09-14 | 2020-12-04 | 安徽理工大学 | Nano delivery system and preparation method and application thereof |
| CN113415798A (en) * | 2021-05-12 | 2021-09-21 | 江西农业大学 | Preparation method of phosphorus-doped microporous, mesoporous and macroporous coexisting grade pore structure nano carbon spheres |
| CN113415798B (en) * | 2021-05-12 | 2023-02-24 | 江西农业大学 | Preparation method of phosphorus-doped microporous, mesoporous and macroporous coexisting grade pore structure carbon nanospheres |
| CN113578359A (en) * | 2021-05-31 | 2021-11-02 | 中国科学院金属研究所 | Hollow nitrogen-doped nano carbon sphere loaded high-dispersion palladium-based catalyst, preparation method thereof and application thereof in ethylbenzene dehydrogenation |
| CN116446192A (en) * | 2023-05-06 | 2023-07-18 | 广州市得易服饰有限公司 | Heating and warming fabric and preparation method thereof |
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