CN109926579B - Gold @ manganese dioxide super nanoparticle and preparation method thereof - Google Patents
Gold @ manganese dioxide super nanoparticle and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a gold @ manganese dioxide super nanoA rice grain and a preparation method thereof, comprising the following steps: (1) pretreating the gold nanoparticle stock solution to obtain gold nanoparticles; (2) dispersing gold nanoparticles into a sodium citrate solution, adding potassium permanganate in batches under a mixing condition, and reacting at 30-40 ℃. The method regulates and controls the surface environment of the gold nanoparticles by pretreating the gold nanoparticle stock solution, so that the manganese dioxide shells can be formed by in-situ self-assembly on the surfaces of the gold cores, the reaction conditions in the method are mild, the etching of potassium permanganate on the gold nanoparticle cores under the conditions of high temperature and strong acid can be avoided, and the diameters of the manganese dioxide core shells can be adjusted by adding the potassium permanganate in batches to obtain Au @ MnO shells of manganese dioxide shells with different diameters2A super nanoparticle.
Description
Technical Field
The invention relates to super nanoparticles, in particular to gold @ manganese dioxide super nanoparticles and a preparation method thereof.
Background
The gold nanoparticles have large extinction coefficient, shape, composition, SPR absorption sensitive to environment, and MnO2The nanosheet can be degraded into Mn with good nuclear magnetic resonance imaging characteristics in a cell microenvironment2+Thus Au @ MnO2Super nanometerThe particles can be applied to analysis and detection, nano-carriers, biological imaging and tumor diagnosis and treatment. At present, the core-shell structure Au @ MnO2The preparation of (A) is rarely reported, and several reported documents are in KMnO4Is a manganese source, and the synthesis is mainly completed under two conditions: alkaline high temperature and acidic normal temperature. KMnO under these two conditions4The oxidation property of the manganese dioxide is strong, the anisotropic gold nanorod or gold triangular plate inner core can be etched, the universality is not high, and the diameter of a manganese dioxide shell layer can not be regulated and controlled. Furthermore, in the preparation of Au @ MnO2In the process of nano particles, MnO is coated outside the gold nano rod2When the method is used, the phenomenon of Au nano particle agglomeration is easy to occur, manganese dioxide self-nucleates and cannot self-assemble in situ to generate AuNR @ MnO2A super nanoparticle.
Disclosure of Invention
The invention aims to provide gold @ manganese dioxide super nanoparticles and a preparation method thereof, the method regulates and controls the surface environment of gold nanoparticles by pretreating a gold nanoparticle stock solution to enable the gold nanoparticles to be self-assembled in situ on the surface of a gold core to form a manganese dioxide shell, the reaction conditions in the method are mild, the gold nanoparticle core can be prevented from being etched by potassium permanganate under the conditions of high temperature and strong acid, and the diameter of the manganese dioxide shell can be adjusted by adding the potassium permanganate in batches to obtain Au @ MnO shells with different diameters2A super nanoparticle. Moreover, the preparation method disclosed by the invention is simple to operate, mild in condition and universal, and is not only suitable for spherical gold nanoparticles, but also suitable for gold nanorods.
In order to realize the purpose, the invention provides a preparation method of gold @ manganese dioxide super nanoparticles, which comprises the following steps: (1) pretreating the gold nanoparticle stock solution to obtain gold nanoparticles; (2) dispersing gold nanoparticles into a sodium citrate solution, adding potassium permanganate in batches under a mixing condition, and reacting at 30-40 ℃.
The invention also provides Au @ MnO prepared by the preparation method2A super nanoparticle.
By the technical scheme, the gold nanoparticle stock solution is pretreated to obtain gold nanoparticles, the gold nanoparticles are dispersed in a sodium citrate solution, potassium permanganate is added in batches under the mixing condition, and the reaction is carried out at 30-40 ℃ to prepare Au @ MnO2A super nanoparticle. The surface environment of the gold nanoparticles is regulated and controlled by pretreating the gold nanoparticle stock solution, so that manganese dioxide shells can be formed on the surfaces of the gold cores in an in-situ self-assembly manner, and Au @ MnO with regular appearance and good monodispersity is obtained2The super nanoparticle of (1). In addition, the reaction conditions in the invention are mild, the etching of the potassium permanganate on the gold nanoparticle core can be avoided under the conditions of high temperature and strong acid, and the diameter of the manganese dioxide core shell can be adjusted by adding the potassium permanganate in batches to obtain Au @ MnO of manganese dioxide shells with different diameters2A super nanoparticle. Moreover, the preparation method disclosed by the invention is simple to operate, mild in condition and universal, and is not only suitable for spherical gold nanoparticles, but also suitable for gold nanorods.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a diagram of AuNP @ MnO synthesized in examples 1-42An absorption spectrogram of the super nanoparticles;
FIG. 2 is AuNP @ MnO obtained in examples 1-42Transmission electron microscopy of the super nanoparticles;
FIG. 3 is a diagram of AuNP @ MnO obtained in example 42High resolution transmission electron microscopy images of the super nanoparticles;
FIG. 4 is a transmission electron micrograph of the nanoparticles of example 1, example 5, example 6 and example 7.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of gold @ manganese dioxide super nanoparticles, which comprises the following steps: (1) pretreating the gold nanoparticle stock solution to obtain gold nanoparticles; (2) dispersing gold nanoparticles into a sodium citrate solution, adding potassium permanganate in batches under a mixing condition, and reacting at 30-40 ℃.
By the technical scheme, the gold nanoparticle stock solution is pretreated to obtain gold nanoparticles, the gold nanoparticles are dispersed in a sodium citrate solution, potassium permanganate is added in batches under the mixing condition, and the reaction is carried out at 30-40 ℃ to prepare Au @ MnO2A super nanoparticle. The surface environment of the gold nanoparticles is regulated and controlled by pretreating the gold nanoparticle stock solution, so that manganese dioxide shells can be formed on the surfaces of the gold cores in an in-situ self-assembly manner, and Au @ MnO with regular appearance and good monodispersity is obtained2The super nanoparticle of (1). Moreover, the reaction conditions in the method are mild, the etching of potassium permanganate on the gold nanoparticle cores under the conditions of high temperature and strong acid can be avoided, and the diameter of the manganese dioxide shell can be regulated and controlled by adding the potassium permanganate in batches to obtain Au @ MnO of manganese dioxide shells with different diameters2A super nanoparticle. Moreover, the preparation method disclosed by the invention is simple to operate, mild in condition and universal, and is not only suitable for spherical gold nanoparticles, but also suitable for gold nanorods.
In a preferred embodiment of the present invention, in order to avoid etching of the gold nanoparticle core and to control the diameter of the manganese dioxide shell, potassium permanganate is preferably added in an amount of 8 to 12mmol per batch.
In a more preferred embodiment of the present invention, in order to avoid etching the gold nanoparticle core and to adjust the diameter of the manganese dioxide core shell, preferably, after the potassium permanganate is added in batches, the concentration of the potassium permanganate in the reaction system is 0.1-0.6 mmol/L.
The reaction time can be adjusted within a wide range, and is preferably 4 to 24 hours.
Wherein the concentration of the sodium citrate solution can be adjusted within a wide range in order to obtain Au @ MnO of manganese dioxide shells with different diameters2The concentration of the super nano particle, preferably the sodium citrate solution is 5-10 mmol/L.
To obtain Au @ MnO of manganese dioxide shells with different diameters2The concentration of the super nanoparticles, preferably the gold nanoparticles in step (2), is 3-5 × 10 as calculated by Lambert beer's law-10mol/L。
According to the method, Au @ MnO of manganese dioxide shells with different diameters can be obtained2According to a preferred embodiment of the invention, after the potassium permanganate is added in batches, the concentration of the potassium permanganate in the reaction system is 0.1mmol/L, the reaction time is 4-6 h, and Au @ MnO with the diameter of a manganese dioxide shell layer of 65-85nm can be obtained2A super nanoparticle.
In a preferred embodiment of the invention, after the potassium permanganate is added in batches, the concentration of the potassium permanganate in the reaction system is 0.2mmol/L, the reaction time is 8-10 h, and Au @ MnO with the shell diameter of the manganese dioxide of 100-2A super nanoparticle.
In a preferred embodiment of the invention, after the potassium permanganate is added in batches, the concentration of the potassium permanganate in the reaction system is 0.4mmol/L, the reaction time is 12-15 h, and Au @ MnO with the manganese dioxide shell diameter of 140-2A super nanoparticle.
In a preferred embodiment of the invention, after the potassium permanganate is added in batches, the concentration of the potassium permanganate in the reaction system is 0.6mmol/L, the reaction time is 18-20 h, and the reaction time can be adjusted toObtaining Au @ MnO with the diameter of the manganese dioxide shell of 200-2A super nanoparticle.
In a preferred embodiment of the present invention, in order to prevent gold nanoparticles from agglomerating in a solution, thereby allowing manganese dioxide core shells to be smoothly coated on the gold nanoparticle cores, preferably, the pretreatment step includes: centrifuging the gold nanoparticle stock solution to obtain a precipitate, dispersing the precipitate in 0.1-0.2wt% of sodium polystyrene sulfonate solution for 6-15h, and centrifuging again. The inventors speculate that, when preparing gold nanoparticles, a large amount of positive charges are accumulated on the surfaces of the gold nanoparticles in the obtained gold nanoparticle stock solution, so that, if the gold nanoparticles are directly dispersed in a sodium citrate solution, the citrate can neutralize the positive charges on the surfaces of the gold nanoparticles, the gold nanoparticles are accumulated before ligand exchange, and the subsequent reaction of wrapping manganese dioxide cannot be completed. In particular, when gold nanorods are used, the seed crystal growth method is the most common and widely used method for preparing the gold nanorods, and CTAB is used as a surfactant. The surface of the gold rod is modified with a large amount of CTAB. The PSS is used as a mild scavenging agent to scavenge CTAB on the surface of the gold rod, and the CTAB is adsorbed on the surface of the gold rod through weak interaction, so that the surface of the gold rod is negatively charged. Then, the PSS is removed through ligand exchange by the citrate, the surface of the gold rod is negatively charged in the whole ligand exchange process, the dispersion liquid of the gold rod is stable, and aggregation does not occur. And can directly regulate and control sodium citrate and KMnO4The size of the manganese dioxide nano-sheet is regulated and controlled by the concentration of the manganese dioxide nano-sheet. If the citrate is directly added into the CTAB modified gold rod, the citrate can neutralize the positive charge of the CTAB layer, the gold rod can be gathered before ligand exchange, and the subsequent reaction of coating manganese dioxide can not be completed.
The gold nanoparticle stock solution can be obtained by various methods, can be used for preparing gold nanoparticles by adopting the prior art, is directly stored in the liquid and is called as gold nanoparticle stock solution, and contains one or more of chloroauric acid, silver nitrate, sodium citrate, sodium borohydride, hexadecyl trimethyl ammonium bromide, ascorbic acid and hydrochloric acid. In the invention, the gold nanoparticle stock solution is a gold nanosphere stock solution and/or a gold nanorod stock solution.
The gold nanosphere stock solution refers to that the gold nanospheres are directly stored in a reaction system after the reaction is finished after the synthesis of the gold nanospheres. In the present invention, gold nanoparticles were prepared using the following method.
Preparing gold nanospheres with the diameter of 14 nm: adding 99mL of ultrapure water into a 250mL three-necked bottle, adding 2.5mL of 0.01M chloroauric acid, magnetically stirring and heating to boil, adding 875 μ L of 0.1M trisodium citrate into the bottle by one gun, continuously boiling for 30min, stopping heating, and naturally cooling to room temperature to obtain the gold nanosphere stock solution.
Preparing gold nanospheres with the diameter of 50 nm: 1.815mL of ultrapure water was added to a 10mL round-bottomed flask, and 2.5mL of 0.01M chloroauric acid and 0.085mL of 5.88X 10 were sequentially added under magnetic stirring-3Mixing M silver nitrate and 0.6mL of 0.034M sodium citrate for 2.5min, rapidly injecting into 95mL of boiling water (within 30 s) under vigorous stirring, continuously boiling for 30min, stopping heating, and naturally cooling to room temperature to obtain gold nanosphere stock solution.
Preparing gold nanospheres with the diameter of 80 nm: synthesized by adopting a seed growth method. Adding 150mL of 0.0022M sodium citrate into a 250mL three-necked bottle, magnetically stirring and heating to boil, adding 1mL of 0.025M chloroauric acid, continuously boiling for 30min, and cooling to 90 ℃ to obtain a solution 1. Taking the solution 1 as a gold seed, adding 1mL of 0.025M chloroauric acid into the gold seed for reaction for 30min, repeatedly adding the chloroauric acid twice, reacting for 30min respectively to obtain a solution 2, stopping heating, and naturally cooling to room temperature. And (3) adding 53mL of ultrapure water and 2mL of 0.06M sodium citrate into 55mL of the solution 2 to obtain a solution 3, and repeating the above process twice by using the solution 3 as a gold seed to obtain a gold nanosphere stock solution.
Gold nanorods were synthesized according to the reported seed growth method. Firstly, prepare seed solution, weigh 0.3645g CTAB (cetyl trimethyl ammonium bromide) in 50mL conical flask, add 10mL ultrapure water to dissolve, then add 250 μ L0.01M HAuCl4Shaking uniformly, and finally adding 600 mu L of ice water to prepare NaBH4Quickly and uniformly shaking, and after 2min, putting the mixture into a constant-temperature water bath kettle at the temperature of 30 ℃ for incubation for 2 h. Secondly, preparing the growth liquid, weighing 5.4675g CTAB in a 250mL volumetric flask, adding 150mL secondary water for dissolving, adding 7.5mL 0.01M HAuCl4All shakingAfter homogenizing, 1.2mL of 0.01M AgNO was added3After shaking uniformly, 3mL of 1M HCl was added, and after shaking uniformly, 1.2mL of 0.1M AA (ascorbic acid) was added. And mixing and shaking the growth solution uniformly, quickly injecting 210 mu L of seed solution into the growth solution, shaking uniformly, placing the seed solution in a constant-temperature water bath kettle at the temperature of 30 ℃ for 12 hours, and cooling to obtain the gold nanorod stock solution.
In the above technical scheme, in order to save the preparation steps, when the gold nanoparticle stock solution is a gold nanosphere stock solution, the pretreatment step is replaced by the following steps: directly centrifuging the gold nanoparticle stock solution to obtain a precipitate.
The invention also provides Au @ MnO prepared by the preparation method2A super nanoparticle.
By the technical scheme, the gold nanoparticle stock solution is pretreated to obtain gold nanoparticles, the gold nanoparticles are dispersed in a sodium citrate solution, potassium permanganate is added in batches under the mixing condition, and the reaction is carried out at 30-40 ℃ to prepare Au @ MnO2A super nanoparticle. The surface environment of the gold nanoparticles is regulated and controlled by pretreating the gold nanoparticle stock solution, so that manganese dioxide shells can be formed on the surfaces of the gold cores in an in-situ self-assembly manner, and Au @ MnO with regular appearance and good monodispersity is obtained2The super nanoparticle of (1). In addition, the reaction temperature in the invention is mild, the phenomenon that the potassium permanganate etches the gold nanoparticle core under the conditions of high temperature and strong acid or strong alkali can be reduced, and the diameter of the manganese dioxide shell can be adjusted by adding the potassium permanganate in batches to obtain Au @ MnO of manganese dioxide shells with different diameters2A super nanoparticle. Moreover, the preparation method disclosed by the invention is simple to operate, mild in condition and universal, and is not only suitable for spherical gold nanoparticles, but also suitable for gold nanorods.
In a preferred embodiment of the invention, the Au @ MnO2The thickness of the manganese dioxide shell layer in the super nano particle is 65-240 nm.
The present invention will be described in detail below by way of examples.
Preparation example 1
Preparing gold nanospheres with the diameter of 50 nm: 1.8 was added to a 10mL round bottom flask15mL of ultrapure water, 2.5mL of 0.01M chloroauric acid, 0.085mL of 5.88X 10 were added in this order under magnetic stirring-3Mixing M silver nitrate and 0.6mL of 0.034M sodium citrate for 2.5min, rapidly injecting into 95mL of boiling water (within 30 s) under vigorous stirring, continuously boiling for 30min, stopping heating, and naturally cooling to room temperature to obtain gold nanoparticle stock solution with the diameter of 50 nm.
Preparation example 2
Preparing gold nanorods: 0.3645g CTAB was weighed into a 50mL Erlenmeyer flask, dissolved in 10mL ultrapure water, and 250. mu.L of 0.01M HAuCl was added4Shaking uniformly, and finally adding 600 mu L of ice water to prepare NaBH4Quickly and uniformly shaking, and after 2min, putting the mixture into a constant-temperature water bath kettle at the temperature of 30 ℃ for incubation for 2 h. Secondly, preparing the growth liquid, weighing 5.4675g CTAB in a 250mL volumetric flask, adding 150mL secondary water for dissolving, adding 7.5mL 0.01M HAuCl4After shaking uniformly, 1.2mL of 0.01M AgNO was added3After shaking uniformly, 3mL of 1M HCl was added, and after shaking uniformly, 1.2mL of 0.1M AA was added. After mixing and shaking the growth solution uniformly, 210 mu L of seed solution is quickly injected into the growth solution, and the growth solution is shaken uniformly and placed in a constant temperature water bath kettle at 30 ℃ for 12h to obtain the gold nanorod stock solution.
Preparation example 3
Preparing gold nanospheres with the diameter of 14 nm: adding 99mL of ultrapure water into a 250mL three-necked bottle, adding 2.5mL of 0.01M chloroauric acid, magnetically stirring and heating to boil, adding 875 μ L of 0.1M trisodium citrate into the bottle by one gun, continuously boiling for 30min, stopping heating, and naturally cooling to room temperature to obtain the gold nanosphere stock solution with the diameter of 14 nm.
Preparation example 4
Preparing gold nanospheres with the diameter of 80 nm: adding 150mL of 0.0022M sodium citrate into a 250mL three-necked bottle, magnetically stirring and heating to boil, adding 1mL of 0.025M chloroauric acid, continuously boiling for 30min, and cooling to 90 ℃ to obtain a solution 1. Taking the solution 1 as a gold seed, adding 1mL of 0.025M chloroauric acid into the gold seed for reaction for 30min, repeatedly adding the chloroauric acid twice, reacting for 30min respectively to obtain a solution 2, stopping heating, and naturally cooling to room temperature. And (3) adding 53mL of ultrapure water and 2mL of 0.06M sodium citrate into 55mL of the solution 2 to obtain a solution 3, and repeating the above process twice by using the solution 3 as a gold seed to obtain a gold nanosphere stock solution with the diameter of 80 nm.
Example 1
The gold nanosphere stock solution of preparation example 1 was centrifuged directly to obtain a precipitate, which was dispersed with 10mL of 5mM sodium citrate to obtain solution 1 (the concentration of gold particles was about 3.0X 10 as calculated by Lambert beer's law)-10M) and adding 10mM potassium permanganate into the mixture in batches under magnetic stirring, heating and refluxing the mixture in an oil bath at 35 ℃ for 4 hours when the concentration of the potassium permanganate in the reaction system is 0.1mM, and naturally cooling the mixture to room temperature to obtain AuNP @ MnO2The super nanoparticles SPs-67.
Example 2
According to the method in example 1, when the potassium permanganate concentration in the reaction system is 0.2mM, the reaction system is heated and refluxed in an oil bath at 30 ℃ for 8 hours, naturally cooled to room temperature, and centrifugally purified to obtain AuNP @ MnO2The super nanoparticles SPs-108.
Example 3
According to the method in example 1, when the potassium permanganate concentration in the reaction system is 0.4mM, the reaction system is heated and refluxed in an oil bath at 40 ℃ for 15 hours, naturally cooled to room temperature, and centrifugally purified to obtain AuNP @ MnO2Super nanoparticle SPs-151。
Example 4
According to the method in example 1, when the potassium permanganate concentration in the reaction system is 0.6mM, the reaction system is heated and refluxed in an oil bath at 35 ℃ for 18 hours, naturally cooled to room temperature, and centrifugally purified to obtain AuNP @ MnO2The super nanoparticles SPs-230.
Example 5
10mL of the stock solution of gold nanorods of preparation example 2 was centrifuged at 8000r/min for 10min, and the precipitate was dispersed in 0.15 wt% PSS (sodium polystyrene sulfonate) for 12h, and the centrifuged precipitate was dispersed in 5mM sodium citrate to obtain solution 2 (the concentration of gold rods was about 5.0X 10 as calculated by Lambert beer's law)-10M) is added into the solution 2 in batches under magnetic stirring, 10mM potassium permanganate is added into the solution in batches under the condition of magnetic stirring, oil bath heating at 35 ℃ is carried out for reflux for 24 hours, when the concentration of the potassium permanganate in a final reaction system is 0.6mM, the solution is naturally cooled to room temperature, and centrifugal purification is carried out to obtain AuNR @ MnO2A super nanoparticle.
Example 6
AuNR @ MnO preparation according to example 12Super nanoparticles except that stock solution of gold nanosphere with diameter of 14nm as in preparation example 3 was used instead ofThe stock solution of gold nanospheres of example 1 was prepared.
Example 7
AuNR @ MnO preparation according to example 12Super nanoparticles except that the gold nanosphere stock solution of preparation example 1 was replaced with the gold nanosphere stock solution of preparation example 4 having a diameter of 80 nm.
Detection example 1
AuNP @ MnO synthesized in examples 1-42The stock solution was diluted 4 times with water and measured on a UV-Vis spectrometer (U-2910). The results are shown in FIG. 1. As can be seen from fig. 1, as the shell of manganese dioxide is increased, the refractive index around the gold particles is increased, and the corresponding SPR peak is red-shifted, while the intensity of the characteristic absorption peak of manganese dioxide is gradually increased. Prepared AuNP @ MnO2The diameters of manganese dioxide nano-sheets of the super nano-particles are 67nm, 108nm, 151nm and 230nm in sequence, and are called as SPs-67, SPs-108, SPs-151 and SPs-230 for short in sequence.
FIG. 2 is a graph of AuNP @ MnO diameters of manganese dioxide shell layers different from those of examples 1-42Transmission electron microscopy of the super nanoparticles. A corresponds to SPs-67, B corresponds to SPs-108, C corresponds to SPs-151, D corresponds to SPs-230, and AuNP @ MnO2The super nanoparticles have a shape similar to that of fried egg, the core is gold nanoparticle core, the shell of the core is coated with an extension formed by manganese dioxide nanosheets, the diameter of the extension can be adjusted by using the method of the invention, and AuNP @ MnO prepared in examples 1-42The diameters of manganese dioxide nano-sheets of the super nanoparticles are 67nm, 108nm, 151nm and 230nm in sequence, and are called as SPs-67, SPs-108, SPs-151 and SPs-230 in sequence for short, and the diameters can be consistent with the detection result shown in the figure 1.
FIG. 3 is a graph of AuNP @ MnO with a manganese dioxide shell diameter of 230nm obtained in example 42High resolution transmission electron microscopy images of the super nanoparticles; manganese dioxide is derived from the crystal lattice of the outer shell.
FIG. 4 is a transmission electron micrograph of the nanoparticles of example 1, example 5, example 6 and example 7. A is Au @ MnO of 14nm gold particle2Super nanoparticles, B is Au @ MnO of 50nm gold particles2Super nanoparticles, C being 80nm gold particlesAu@MnO2Super nanoparticles, D is Au @ MnO of gold rod2A super nanoparticle. As can be seen from FIG. 4, the gold nanospheres and gold nanorods with different sizes can obtain the super nanoparticles with gold core and manganese dioxide shell with good monodispersity by adopting the method, and the phenomenon of etching the gold nanoparticle core does not occur, so that the in-situ self-assembly method has good universality.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (2)
1. A preparation method of gold @ manganese dioxide super nanoparticles is characterized by comprising the following steps:
(1) pretreating the gold nanoparticle stock solution to obtain gold nanoparticles; the step of pre-treating comprises: centrifuging the gold nanoparticle stock solution to obtain a precipitate, dispersing the precipitate in 0.1-0.2wt% of sodium polystyrene sulfonate solution for 6-15h, and centrifuging again;
(2) dispersing gold nanoparticles into a sodium citrate solution, adding potassium permanganate in batches under a mixing condition, and reacting at 30-40 ℃;
wherein the gold nanoparticle stock solution is a gold nanosphere stock solution and/or a gold nanorod stock solution; wherein the amount of potassium permanganate added in each batch is 8-12 mmol;
wherein, after the potassium permanganate is added in batches, the reactantThe concentration of potassium permanganate in the system is 0.1mmol/L, the reaction time is 4-6 h, and Au @ MnO with the diameter of a manganese dioxide shell layer of 65-85nm can be obtained2A super nanoparticle;
when the potassium permanganate is added in batches, the concentration of the potassium permanganate in the reaction system is 0.2mmol/L, the reaction time is 8-10 h, and Au @ MnO with the shell diameter of the manganese dioxide of 100-2A super nanoparticle;
when the potassium permanganate is added in batches, the concentration of the potassium permanganate in the reaction system is 0.4mmol/L, the reaction time is 12-15 h, and Au @ MnO with the shell diameter of the manganese dioxide of 140-2A super nanoparticle;
when the potassium permanganate is added in batches, the concentration of the potassium permanganate in the reaction system is 0.6mmol/L, the reaction time is 18-20 h, and Au @ MnO with the shell diameter of the manganese dioxide of 200-2A super nanoparticle.
2. The preparation method according to claim 1, wherein the concentration of the sodium citrate solution is 5 to 10 mmol/L;
and/or the concentration of the gold nanoparticles in the step (2) is 3-5 x 10 calculated according to the Lambert beer law-10mol/L。
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