CN109926579A - Super nanoparticle of a kind of gold@manganese dioxide and preparation method thereof - Google Patents
Super nanoparticle of a kind of gold@manganese dioxide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses super nanoparticles of a kind of gold@manganese dioxide and preparation method thereof, comprising the following steps: (1) pre-processes gold nanoparticle stoste, obtain gold nanoparticle；(2) it disperses gold nanoparticle in sodium citrate solution, potassium permanganate is added portionwise under mixing condition, reacted in 30 DEG C~40 DEG C.This method regulates and controls the surface environment of gold nanoparticle by pre-processing to gold nanoparticle stoste, make it possible to be self-assembly of manganese dioxide shell in golden core surface in situ, reaction condition in the present invention is mild, potassium permanganate be can be avoided under high temperature and strong acid condition to the etching of gold nanoparticle core, and, by the way that potassium permanganate is added in batches, the diameter of manganese dioxide nucleocapsid can be adjusted, obtain the Au@MnO of different-diameter manganese dioxide shell2Super nanoparticle.
Description
Technical field
The present invention relates to super nanoparticles, and in particular, to a kind of super nanoparticle of gold@manganese dioxide and its preparation
Method.
Background technique
There is gold nanoparticle the SPR of big extinction coefficient and shape, composition, environment sensitive to absorb, and MnO2Nanometer sheet
The Mn with good Magnetic resonance imaging characteristic can be degraded under cell micro-environment2+, thus Au@MnO2Super nanoparticle energy
It is applied in analysis detection, nano-carrier, bio-imaging and tumour diagnosis and treatment.Currently, core-shell structure Au@MnO2Preparation rarely have
Report, reported several documents are with KMnO4For manganese source, synthesis is mainly completed under two conditions: first is that alkalinity is high
Temperature, second is that acidic normal temperature.KMnO under the conditions of both4Oxidisability it is very strong, anisotropic gold nanorods or gold can be etched
The kernel of triangular plate does not have universality, moreover, manganese dioxide shell diameter cannot regulate and control.Moreover, in preparation Au@
MnO2During nanoparticle, especially in gold nanorods outer cladding MnO2When, showing for the reunion of Au nanoparticle easily occurs
As, manganese dioxide spontaneous nucleation, and be unable to primary reconstruction and generate AuNR MnO2Super nanoparticle.
Summary of the invention
The object of the present invention is to provide super nanoparticles of a kind of gold@manganese dioxide and preparation method thereof, and this method passes through
Gold nanoparticle stoste is pre-processed to regulate and control the surface environment of gold nanoparticle, is made it possible in golden core surface in situ self assembly
Manganese dioxide shell is formed, the reaction condition in the present invention is mild, can be avoided under high temperature and strong acid condition, potassium permanganate is to Jenner
The etching of grain of rice daughter nucleus, moreover, can be adjusted, obtain to the diameter of manganese dioxide shell by the way that potassium permanganate is added in batches
To the Au@MnO of different-diameter manganese dioxide shell2Super nanoparticle.Moreover, preparation method of the invention it is easy to operate,
Mild condition and there is universality, is applicable not only to ball-type gold nanoparticle, and be suitable for gold nanorods.
To achieve the goals above, the present invention provides a kind of preparation method of the super nanoparticle of gold@manganese dioxide, packets
It includes following steps: (1) pre-processing gold nanoparticle stoste, obtain gold nanoparticle；(2) lemon is dispersed by gold nanoparticle
In acid sodium solution, potassium permanganate is added portionwise under mixing condition, is reacted in 30 DEG C~40 DEG C.
The present invention also provides a kind of Au@MnO being prepared according to previously described preparation method2Super nanoparticle.
Through the above technical solutions, gold nanoparticle stoste is pre-processed, gold nanoparticle is obtained, then by gold nanoparticle
It is scattered in sodium citrate solution, potassium permanganate is added portionwise under mixing condition, react, can prepare in 30 DEG C~40 DEG C
Au@MnO2Super nanoparticle.Regulate and control the surface environment of gold nanoparticle by pre-processing gold nanoparticle stoste, so that
It can be self-assembly of manganese dioxide shell in golden core surface in situ, obtain shape rule, the good Au@MnO of monodispersity2It is super
Grade nanoparticle.In addition, the reaction condition in the present invention is mild, can be avoided under high temperature and strong acid condition, potassium permanganate is to gold
The etching of nanoparticle core, moreover, can be adjusted to the diameter of manganese dioxide nucleocapsid by the way that potassium permanganate is added in batches
It is whole, obtain the Au@MnO of different-diameter manganese dioxide shell2Super nanoparticle.Moreover, preparation method of the invention operation
Simply, mild condition and there is universality, is applicable not only to ball-type gold nanoparticle, and be suitable for gold nanorods.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the AuNP@MnO synthesized in embodiment 1-42The abosrption spectrogram of super nanoparticle；
Fig. 2 is AuNP@MnO obtained in embodiment 1-42The transmission electron microscope picture of super nanoparticle；
Fig. 3 is that AuNP@MnO is obtained in embodiment 42The high-resolution-ration transmission electric-lens figure of super nanoparticle；
Fig. 4 is the transmission electron microscope picture of the super nanoparticle in embodiment 1, embodiment 5, embodiment 6 and embodiment 7.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation methods of the super nanoparticle of gold@manganese dioxide, comprising the following steps: (1) will
The pretreatment of gold nanoparticle stoste, obtains gold nanoparticle；(2) it disperses gold nanoparticle in sodium citrate solution, mixed
Potassium permanganate is added portionwise under the conditions of conjunction, is reacted in 30 DEG C~40 DEG C.
Through the above technical solutions, gold nanoparticle stoste is pre-processed, gold nanoparticle is obtained, then by gold nanoparticle
It is scattered in sodium citrate solution, potassium permanganate is added portionwise under mixing condition, react, can prepare in 30 DEG C~40 DEG C
Au@MnO2Super nanoparticle.Regulate and control the surface environment of gold nanoparticle by pre-processing gold nanoparticle stoste, so that
It can be self-assembly of manganese dioxide shell in golden core surface in situ, obtain shape rule, the good Au@MnO of monodispersity2It is super
Grade nanoparticle.Moreover, the reaction condition in the present invention is mild, can be avoided under high temperature and strong acid condition, potassium permanganate
To the etching of gold nanoparticle core, moreover, can be adjusted to the diameter of manganese dioxide shell by the way that potassium permanganate is added in batches
Control, obtains the Au@MnO of different-diameter manganese dioxide shell2Super nanoparticle.Moreover, preparation method of the invention operation
Simply, mild condition and there is universality, is applicable not only to ball-type gold nanoparticle, and be suitable for gold nanorods.
In a kind of preferred embodiment of the present invention, in order to avoid the etching and regulation titanium dioxide to gold nanoparticle core
The diameter of manganese shell, it is preferable that the amount that potassium permanganate is added in each batch is 8-12mmol.
In a kind of preferred embodiment of the present invention, in order to avoid the etching and regulation dioxy to gold nanoparticle core
Change the diameter of manganese nucleocapsid, it is preferable that after potassium permanganate is added portionwise, potassium permanganate concentration is 0.1- in reaction system
0.6mmol/L。
Wherein, it for the time of reaction, can be adjusted in a wider range, it is preferable that reaction time 4-24h.
Wherein, the concentration of sodium citrate solution can be adjusted in a wider range, in order to obtain different-diameter two
The Au@MnO of manganese oxide shell2Super nanoparticle, it is preferable that the concentration of sodium citrate solution is 5-10mmol/L.
The Au@MnO of different-diameter manganese dioxide shell in order to obtain2Super nanoparticle, it is preferable that Jenner in step (2)
The concentration of rice corpuscles is calculated as 3-5 × 10 by langbobier law-10mol/L。
According to the method described above, the Au@MnO of different-diameter manganese dioxide shell can be obtained2Super nanoparticle, in the present invention one
In kind preferred embodiment, after potassium permanganate is added portionwise, potassium permanganate concentration is 0.1mmol/ in reaction system
L, reaction time are 4~6h, and the Au@MnO that manganese dioxide shell diameter is 65-85nm can be obtained2Super nanoparticle.
In a kind of preferred embodiment of the present invention, after potassium permanganate is added portionwise, Gao Meng in reaction system
Sour potassium concn is 0.2mmol/L, and the reaction time is 8~10h, and the Au@that manganese dioxide shell diameter is 100-115nm can be obtained
MnO2Super nanoparticle.
In a kind of preferred embodiment of the present invention, after potassium permanganate is added portionwise, Gao Meng in reaction system
Sour potassium concn is 0.4mmol/L, and the reaction time is 12~15h, and the Au@that manganese dioxide shell diameter is 140-155nm can be obtained
MnO2Super nanoparticle.
In a kind of preferred embodiment of the present invention, after potassium permanganate is added portionwise, Gao Meng in reaction system
Sour potassium concn is 0.6mmol/L, and the reaction time is 18~20h, and the Au@that manganese dioxide shell diameter is 200-240nm can be obtained
MnO2Super nanoparticle.
In a kind of preferred embodiment of the present invention, in order to avoid gold nanoparticle is reunited in the solution, thus
So that manganese dioxide nucleocapsid is smoothly coated on gold nanoparticle core, it is preferable that the pretreated step includes: by gold nano
Particle stoste be centrifuged to obtain precipitating, by precipitating be dispersed in 6-15h in the kayexalate solution of 0.1-0.2wt%, again from
The heart.Inventor speculates, when preparing gold nanoparticle, the surface aggregation of gold nanoparticle in obtained gold nanoparticle stoste
Therefore a large amount of positive charge such as directly disperses gold nanoparticle in sodium citrate solution, citrate can neutralize Jenner
The positive charge on rice corpuscles surface, gold nanoparticle will be assembled before ligand exchange, the reaction of subsequent packet manganese dioxide
It cannot complete.Specifically, crystal seed growth method is method that is the most frequently used, most preparing golden stick extensively, when being related to using gold nanorods
Use CTAB as surfactant.The a large amount of CTAB of the modification on golden stick surface.Use PSS can will be golden as mild scavenger
The CTAB on stick surface is removed, and is adsorbed on golden stick surface by weak interaction, keeps golden stick surface negatively charged.Then lemon
Acid group falls PSS by ligand exchange, and entire ligand exchange processes gold stick surface is negatively charged, and the dispersion liquid of golden stick is more stable, does not have
Have and assembles.And it can directly pass through regulation sodium citrate and KMnO4Concentration regulate and control the big of manganese dioxide nano-plates
It is small.If citrate to be directly added to the Jin Bangzhong of CTAB modification, citrate can neutralize CTAB layers of positive charge, ligand exchange
Golden stick will be assembled before, and the reaction of subsequent packet manganese dioxide cannot be completed.
Gold nanoparticle stoste can be obtained using a variety of methods, can use prior art preparation gold nanoparticle, and
General gold nanoparticle is then stored directly in liquid, referred to as gold nanoparticle stoste, is contained in the gold nanoparticle stoste
There are one of gold chloride, silver nitrate, sodium citrate, sodium borohydride, cetyl trimethylammonium bromide, ascorbic acid and hydrochloric acid
Or it is a variety of.In the present invention, gold nanoparticle stoste is gold nanosphere stoste and/or gold nanorods stoste.
Gold nanosphere stoste is directly stored in reaction system after reaction after referring to synthesis gold nanosphere.At this
In invention, gold nano grain is prepared using following methods.
The preparation of diameter 14nm gold nanosphere: being added 99mL ultrapure water in 250mL three-necked bottle, and 2.5mL 0.01M chlorine is added
Auric acid, after magnetic agitation is heated to boiling, 875 μ L 0.1M trisodium citrates are added in a rifle, stop adding after continuing boiling 30min
Heat, cooled to room temperature obtain gold nanosphere stoste.
Prepared by diameter 50nm gold nanosphere: the addition 1.815mL ultrapure water in 10mL round-bottomed flask, under magnetic agitation successively
2.5mL 0.01M gold chloride, 0.085mL 5.88 × 10 is added-3M silver nitrate, 0.6mL 0.034M sodium citrate mixing 2.5min
Afterwards, it is vigorously stirred in lower quick (in 30s) injection 95mL boiling water, stops heating after continuing boiling 30min, naturally cool to room
Temperature obtains gold nanosphere stoste.
Diameter 80nm gold nanosphere preparation: using seed mediated growth method synthesis.150mL is added in 250mL three-necked bottle
0.0022M sodium citrate, after magnetic agitation is heated to boiling, be added 1mL 0.025M gold chloride, continue boil 30min after will be warm
Degree is down to 90 DEG C, obtains solution 1.It is gold kind with solution 1,1mL 0.025M gold chloride is then added thereto and reacts 30min, then
Repetition plus twice gold chloride react 30min respectively and obtain solution 2, stop heating, cooled to room temperature.55mL solution 2 is taken to add
53mL ultrapure water and 2mL 0.06M sodium citrate obtain solution 3, are gold kind with solution 3, after repeating the above process twice, obtain golden
Nanosphere stoste.
Gold nanorods are synthesized according to reported seed mediated growth method.Seed solution is prepared first, weighs 0.3645g
CTAB (cetyl trimethylammonium bromide) is added the dissolution of 10mL ultrapure water, adds 250 μ L 0.01M in 50mL conical flask
HAuCl4It shakes uniformly, is eventually adding the NaBH that 600 μ L ice water are now prepared4, Quick shaking is uniform, after 2min, places it in 30 DEG C of constant temperature
2h is incubated in water-bath.Growth-promoting media is followed by prepared, weighs 5.4675g CTAB in 250mL volumetric flask, is added 150mL bis- times
After water dissolution, 7.5mL 0.01M HAuCl is added4, 1.2mL 0.01M AgNO is added after shaking uniformly3, 3mL is added after shaking uniformly
1.2mL 0.1M AA (ascorbic acid) is added after shaking uniformly in 1M HCl.After mixing shakes up growth-promoting media, take 210 μ L seed liquors quick
It injects wherein and shakes up and be placed on 12h in 30 DEG C of thermostat water baths, it is cooling, obtain gold nanorods stoste.
In the above-mentioned technical solutions, described when gold nanoparticle stoste is gold nanosphere stoste in order to save preparation step
Pretreated step is replaced with following steps: gold nanoparticle stoste is directly centrifuged to obtain precipitating.
The present invention also provides a kind of Au@MnO being prepared according to previously described preparation method2Super nanoparticle.
Through the above technical solutions, gold nanoparticle stoste is pre-processed, gold nanoparticle is obtained, then by gold nanoparticle
It is scattered in sodium citrate solution, potassium permanganate is added portionwise under mixing condition, react, can prepare in 30 DEG C~40 DEG C
Au@MnO2Super nanoparticle.Regulate and control the surface environment of gold nanoparticle by pre-processing gold nanoparticle stoste, so that
It can be self-assembly of manganese dioxide shell in golden core surface in situ, obtain shape rule, the good Au@MnO of monodispersity2It is super
Grade nanoparticle.In addition, the reaction temperature in the present invention is mild, routine can be reduced under high temperature and strong acid or basic conditions,
Potassium permanganate is added moreover, passing through to the etching phenomenon of gold nanoparticle core in potassium permanganate in batches, can be to manganese dioxide shell
Diameter be adjusted, obtain the Au@MnO of different-diameter manganese dioxide shell2Super nanoparticle.Moreover, of the invention
Preparation method is easy to operate, mild condition and has universality, is applicable not only to ball-type gold nanoparticle, and be suitable for Jenner
Rice stick.
In a kind of preferred embodiment of the present invention, Au@MnO2Manganese dioxide shell thickness is in super nanoparticle
65-240nm。
The present invention will be described in detail by way of examples below.
Preparation example 1
Prepared by diameter 50nm gold nanosphere: the addition 1.815mL ultrapure water in 10mL round-bottomed flask, under magnetic agitation successively
2.5mL 0.01M gold chloride, 0.085mL 5.88 × 10 is added-3M silver nitrate, 0.6mL 0.034M sodium citrate mixing 2.5min
Afterwards, it is vigorously stirred in lower quick (in 30s) injection 95mL boiling water, stops heating after continuing boiling 30min, naturally cool to room
Temperature obtains diameter 50nm gold nanosphere stoste.
Preparation example 2
The preparation of gold nanorods: weighing 0.3645g CTAB in 50mL conical flask, and 10mL ultrapure water is added and dissolves, then plus
Enter 250 μ L 0.01M HAuCl4It shakes uniformly, is eventually adding the NaBH that 600 μ L ice water are now prepared4, Quick shaking is uniform, will after 2min
It is placed in 30 DEG C of thermostat water baths and is incubated for 2h.Growth-promoting media is followed by prepared, weighs 5.4675g CTAB in 250mL volumetric flask
In, after the dissolution of 150mL secondary water is added, 7.5mL 0.01M HAuCl is added4, 1.2mL 0.01M AgNO is added after shaking uniformly3,
3mL 1M HCl is added after shaking uniformly, 1.2mL 0.1M AA is added after shaking uniformly.After mixing shakes up growth-promoting media, 210 μ L seeds are taken
Liquid, which is rapidly injected wherein and shakes up, is placed on 12h in 30 DEG C of thermostat water baths, obtains gold nanorods stoste.
Preparation example 3
The preparation of diameter 14nm gold nanosphere: being added 99mL ultrapure water in 250mL three-necked bottle, and 2.5mL 0.01M chlorine is added
Auric acid, after magnetic agitation is heated to boiling, 875 μ L 0.1M trisodium citrates are added in a rifle, stop adding after continuing boiling 30min
Heat, cooled to room temperature obtain diameter 14nm gold nanosphere stoste.
Preparation example 4
The preparation of diameter 80nm gold nanosphere: being added 150mL 0.0022M sodium citrate in 250mL three-necked bottle, and magnetic force stirs
It mixes after being heated to boiling, 1mL 0.025M gold chloride is added, cool the temperature to 90 DEG C after continuing boiling 30min, obtain solution 1.
It is gold kind with solution 1,1mL 0.025M gold chloride is then added thereto and reacts 30min, repeats plus gold chloride is distinguished twice
Reaction 30min obtains solution 2, stops heating, cooled to room temperature.Take 55mL solution 2 plus 53mL ultrapure water and 2mL 0.06M
Sodium citrate obtains solution 3, is gold kind with solution 3, after repeating the above process twice, obtains diameter 80nm gold nanosphere stoste.
Embodiment 1
The gold nanosphere stoste in preparation example 1 is taken directly to be centrifuged to obtain precipitating, it is molten with being obtained after the dispersion of 10mL 5mM sodium citrate
(gold particle concentration calculates about 3.0 × 10 by langbobier law to liquid 1-10M), 10mM permanganic acid is added portionwise under magnetic agitation
Potassium, when potassium permanganate concentration is 0.1mM in reaction system, 35 DEG C of oil bath heatings flow back 4h, and cooled to room temperature obtains
AuNP@MnO2Super nanoparticle SPs-67.
Embodiment 2
According to the method in embodiment 1, when potassium permanganate concentration is 0.2mM, 30 DEG C of oil bath heating reflux in reaction system
8h, cooled to room temperature, centrifugal purification obtain AuNP@MnO2Super nanoparticle SPs-108.
Embodiment 3
According to the method in embodiment 1, when potassium permanganate concentration is 0.4mM, 40 DEG C of oil bath heating reflux in reaction system
15h, cooled to room temperature, centrifugal purification obtain AuNP@MnO2Super nanoparticle SPs-151。
Embodiment 4
According to the method in embodiment 1, when potassium permanganate concentration is 0.6mM, 35 DEG C of oil bath heating reflux in reaction system
18h, cooled to room temperature, centrifugal purification obtain AuNP@MnO2Super nanoparticle SPs-230.
Embodiment 5
After taking the gold nanorods stoste 8000r/min in 10mL preparation example 2 to be centrifuged 10min, precipitating is dispersed in
12h in 0.15wt%PSS (kayexalate), centrifugation be dispersed in 5mM sodium citrate obtain solution 2 (golden stick
Concentration calculates about 5.0 × 10 by langbobier law-10M), 10mM permanganic acid is added portionwise under magnetic stirring in solution 2
Potassium, the reflux of 35 DEG C of oil bath heatings for 24 hours, when potassium permanganate concentration is 0.6mM in end reaction system, cooled to room temperature, from
The heart purifies to obtain AuNR@MnO2Super nanoparticle.
Embodiment 6
AuNR@MnO is prepared according to the method for embodiment 12Super nanoparticle, unlike, using straight in preparation example 3
Diameter 14nm gold nanosphere stoste replaces the gold nanosphere stoste in preparation example 1.
Embodiment 7
AuNR@MnO is prepared according to the method for embodiment 12Super nanoparticle, unlike, using straight in preparation example 4
Diameter 80nm gold nanosphere stoste replaces the gold nanosphere stoste in preparation example 1.
Detect example 1
The AuNP@MnO that will be synthesized in embodiment 1-42Stoste be diluted with water 4 times after in UV, visible light sub-ray spectrometer (U-
2910) it is measured on.The result is shown in Figure 1.As seen from Figure 1, with the increase of manganese dioxide shell, the refractive index around gold particle increases
Greatly, the corresponding peak SPR red shift, while the intensity of manganese dioxide characteristic absorption peak is gradually increased.AuNP@MnO obtained2It is super to receive
The diameter of its manganese dioxide nano-plates of rice corpuscles is successively 67nm, 108nm, 151nm, 230nm, successively referred to as SPs-67,
SPs-108, SPs-151, SPs-230.
Fig. 2 is the different AuNP@MnO of manganese dioxide shell diameter obtained in embodiment 1-42Super nanoparticle it is saturating
Penetrate electron microscope.A corresponding is SPs-67, and B corresponding is SPs-108, and C corresponding is SPs-151, and D corresponding is SPs-230,
As it can be seen that AuNP@MnO2Super nanoparticle is similar to the pattern of fried egg, and center is gold nanoparticle core, and the shell of core is coated with
The extension that manganese dioxide nano-plates are formed, and method of the invention can be used to be adjusted for the diameter of extension, and make in embodiment 1-4
The AuNP@MnO obtained2The diameter of super its manganese dioxide nano-plates of nanoparticle is successively 67nm, 108nm, 151nm, 230nm,
Successively it is referred to as SPs-67, SPs-108, SPs-151, SPs-230, it is seen that can be consistent with the testing result of Fig. 1.
Fig. 3 is that the AuNP@MnO that manganese dioxide shell diameter is 230nm is obtained in embodiment 42The height of super nanoparticle
Resolved transmittance electron microscope；Obtain it is manganese dioxide from the lattice of shell.
Fig. 4 is the super nanoparticle transmission electron microscope picture in embodiment 1, embodiment 5, embodiment 6 and embodiment 7.A is
The Au@MnO of 14nm gold particle2Super nanoparticle, B are the Au@MnO of 50nm gold particle2Super nanoparticle, C are 80nm gold
The Au@MnO of grain2Super nanoparticle, D are the Au@MnO of golden stick2Super nanoparticle.From fig. 4, it can be seen that various sizes of Jenner
Rice ball and gold nanorods can obtain the super nanoparticle of monodispersity golden core manganese dioxide shell well using this method, and
There is not the etching phenomenon to gold nanoparticle core, the method for the primary reconstruction has good universality.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of the super nanoparticle of gold@manganese dioxide, which comprises the following steps:
(1) gold nanoparticle stoste is pre-processed, obtains gold nanoparticle；
(2) disperse gold nanoparticle in sodium citrate solution, potassium permanganate be added portionwise under mixing condition, in 30 DEG C~
40 DEG C of reactions.
2. preparation method according to claim 1, wherein the amount that potassium permanganate is added in each batch is 8-12mmol.
3. preparation method according to claim 2, wherein after potassium permanganate is added portionwise, Gao Meng in reaction system
Sour potassium concn is 0.1-0.6mmol/L；
And/or reaction time 4-24h；
And/or the concentration of sodium citrate solution is 5-10mmol/L；
And/or the concentration of gold nanoparticle is calculated as 3-5 × 10 by langbobier law in step (2)-10mol/L。
4. preparation method according to claim 3, wherein high in reaction system after potassium permanganate is added portionwise
Mangaic acid potassium concn is 0.1mmol/L, and the reaction time is 4~6h, and the Au that manganese dioxide shell diameter is 65-85nm can be obtained
MnO2Super nanoparticle；
After potassium permanganate is added portionwise, in reaction system potassium permanganate concentration be 0.2mmol/L, the reaction time be 8~
The Au@MnO that manganese dioxide shell diameter is 100-115nm can be obtained in 10h2Super nanoparticle；
After potassium permanganate is added portionwise, in reaction system potassium permanganate concentration be 0.4mmol/L, the reaction time be 12~
The Au@MnO that manganese dioxide shell diameter is 140-155nm can be obtained in 15h2Super nanoparticle；
After potassium permanganate is added portionwise, in reaction system potassium permanganate concentration be 0.6mmol/L, the reaction time be 18~
The Au@MnO that manganese dioxide shell diameter is 200-240nm can be obtained in 20h2Super nanoparticle.
5. preparation method according to claim 1-4, wherein the pretreated step includes: by gold nano
Particle stoste be centrifuged to obtain precipitating, by precipitating be dispersed in 6-15h in the kayexalate solution of 0.1-0.2wt%, again from
The heart.
6. preparation method according to claim 1-4, wherein gold nanoparticle stoste is gold nanosphere stoste
And/or gold nanorods stoste.
7. preparation method according to claim 6, wherein described pre- when gold nanoparticle stoste is gold nanosphere stoste
The step of processing, is replaced with following steps: gold nanoparticle stoste is directly centrifuged to obtain precipitating.
8. preparation method according to claim 6, wherein in the gold nanoparticle stoste containing gold chloride, silver nitrate,
One of sodium citrate, sodium borohydride, cetyl trimethylammonium bromide, ascorbic acid and hydrochloric acid are a variety of.
9. the golden super nanoparticle of@manganese dioxide that preparation method according to claim 1-8 is prepared.
10. the super nanoparticle of gold@manganese dioxide according to claim 9, wherein manganese dioxide shell diameter is 65-
240nm。
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| CN110976851A (en) * | 2019-12-10 | 2020-04-10 | 上海大学 | Preparation method of gold/manganese dioxide composite nano material with core-shell structure |
| CN112375545A (en) * | 2020-11-16 | 2021-02-19 | 桂林电子科技大学 | Manganese dioxide-melamine formaldehyde resin double-shell composite phase change material and preparation method thereof |
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