CN110405200B - Yolk-eggshell structure precious metal @ hollow carbon nanosphere composite material and preparation method and application thereof - Google Patents

Yolk-eggshell structure precious metal @ hollow carbon nanosphere composite material and preparation method and application thereof Download PDF

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CN110405200B
CN110405200B CN201910525824.3A CN201910525824A CN110405200B CN 110405200 B CN110405200 B CN 110405200B CN 201910525824 A CN201910525824 A CN 201910525824A CN 110405200 B CN110405200 B CN 110405200B
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梁业如
张伟财
杨晨
彭晶
刘应亮
郑明涛
肖勇
胡航
董汉武
雷炳富
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Abstract

The invention belongs to the technical field of materials, and discloses a noble metal @ hollow carbon nanosphere composite material with a yolk-eggshell structure and a preparation method and application thereof. The preparation method comprises the following steps: in the synthesis of noble metal @ SiO2Based on the core-shell nanospheres, the noble metal @ SiO with the multi-core-shell structure is prepared by surface modification and emulsion polymerization2According to the characteristic that self-crosslinking reaction can be carried out by using methylene of the polychloromethylstyrene, a rich micropore network structure can be built in the shell under the condition that a crosslinking agent is added randomly, and the composite material of the yolk-eggshell structure noble metal @ hollow carbon nanosphere is obtained by virtue of the rigid structure of the polychloromethylstyrene shell through high-temperature carbonization and HF etching treatment. The invention can be used as a high-activity p-nitrophenol reduction catalyst material, a high-capacity lithium-sulfur battery limited sulfur nano-carbon carrier material, a high-performance formaldehyde adsorption material and a biological antibacterial material.

Description

Yolk-eggshell structure precious metal @ hollow carbon nanosphere composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a noble metal @ hollow carbon nanosphere composite material with a yolk-eggshell structure and a preparation method and application thereof.
Background
The yolk-eggshell structure nanosphere is a spherical hollow cavity structure composite material formed by surrounding internal functional nanoparticles with a unique nanosheet layer, can exert the synergistic effect advantage of the hollow nanosphere and the functional nanoparticles, has wide application prospect in multiple fields, and is a popular research direction of the material subject. The carbon nanosphere composite material with the yolk-eggshell structure, in particular to the yolk-eggshell structure noble metal @ hollow carbon nanospheres, is an important advanced material. The nano carbon nano sphere and the nano hollow cavity thereof have unique nano carbon shell layers and noble metal nano particles loaded by the nano hollow cavity thereof, can exert the synergistic effect advantage of the hollow carbon nano sphere and the noble metal nano particles, have wide application prospect in the fields of catalysis, energy, biomedicine, environment, nano reactors and the like, and draw more and more attention in the field of material science.
Despite significant advances in the research of nanospheres of the yolk-eggshell structure, the design, synthesis and application of noble metal @ hollow polymer and its carbon nanospheres remain a serious challenge. The shell structure is an important component of the precious metal @ hollow carbon nanosphere composite material with the yolk-eggshell structure and is a key factor influencing the performance of the material. At present, the shell of the precious metal @ hollow carbon nanosphere composite material with the yolk-eggshell structure is generally (quasi-) nonporous, and the pore structure of the composite material is mainly derived from a small amount of micropores formed by removing non-carbon elements in the carbonization process, so that the porosity of a spherical carbon skeleton is low, the mass transfer resistance is high, and the performance improvement and the application expansion of the material are limited.
In recent years, people reform the shell structure design, and synthesize the noble metal @ hollow carbon nanosphere with the porous shell structure by using a hypercrosslinking method. Research shows that the reasonable porous structure constructed in the nano spherical shell layer can obviously improve the performance of the material. However, the following difficult disadvantages are commonly encountered in the construction of a large number of rigid microporous network structures in polymer shells: the need of using a large amount of cross-linking agent for cross-linking seriously hinders the process of industrial scale of the products prepared by the cross-linking agent. The main reasons are (1) the cross-linking agent (e.g. FDA methylal) is expensive; (2) the cross-linking agent (such as 1, 2-dichloroethane 1, 2-dichloromethane) seriously pollutes the environment; (3) after the cross-linking agent is added, the cross-linking agent needs to be removed from the reaction system, the process is complicated, and the experimental production cost is high; (4) the obtained carbon shell layer has low porosity and large mass transfer resistance, and is not beneficial to the function of the noble metal yolk core. These disadvantages have seriously hampered the fundamental research and industrialization progress of such nanocomposites.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a preparation method of a noble metal @ hollow carbon nanosphere composite material with a yolk-eggshell structure.
The invention also aims to provide the noble metal @ hollow carbon nanosphere composite material with the yolk-eggshell structure prepared by the preparation method.
The invention further aims to provide an application of the precious metal @ hollow carbon nanosphere composite material with the yolk-eggshell structure.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a noble metal @ hollow carbon nanosphere composite material with a yolk-eggshell structure comprises the following operation steps:
(1) reducing noble metal salt or acid by using a reducing agent to prepare nano noble metal hydrosol;
(2) adding ethanol and ammonia water into the nano noble metal hydrosol obtained in the step (1), and stirring and mixing the nano noble metal hydrosol with an ethanol solution of ethyl orthosilicate to obtain the noble metal @ SiO2A nanosphere solution;
(3) the noble metal @ SiO obtained in the step (2)2Adding ammonia water into the nanosphere solution, stirring and mixing with ethanol solution of gamma- (methacryloyloxy) propyl trimethoxy silane (KH570) for reaction to obtain noble metal @ SiO with amino double bonds on the nanosphere surface2Centrifuging and washing the nanosphere solution by using absolute ethyl alcohol, and concentrating the nanosphere solution into a nanosphere ethyl alcohol solution;
(4) introducing inert gas for protection, heating the mixed solution of water, sodium dodecyl benzene sulfonate and sodium bicarbonate under the stirring condition, adding the nanosphere ethanol solution obtained in the step (3), the organic monomer 4-chloromethyl styrene and divinylbenzene to obtain the polychloromethyl styrene coated noble metal @ SiO2Centrifuging, washing and drying the nanospheres by using absolute ethyl alcohol, and weighing the dry mass;
(5) placing the dried nanosphere body obtained in the step (4) into a reaction container, adding 1, 2-dichloroethane (1, 2-dichloroethane) as a solvent, swelling at room temperature, and adding anhydrous FeCl3As catalyst, heating and refluxing under stirring to perform Friedel-Crafts crosslinking reaction, centrifuging to obtain solid product, drying and post-treating to obtain crosslinked polychloromethylstyrene coated noble metal @ SiO2The nanosphere of (1);
(6) in N2Carbonizing the nanospheres obtained in the step (5) under the protection of atmosphere, and then treating with HF solution to remove SiO2And drying and then processing to obtain the noble metal @ hollow carbon nanosphere composite material with the yolk-eggshell structure.
The specific steps of the step (1) are as follows: adding noble metal salt or acid into water, heating to fully dissolve the noble metal salt or acid to obtain a noble metal salt or acid solution, then adding a reducing agent solution to reduce the noble metal salt or acid solution, stirring for 12-36 h, centrifuging to obtain a solid, and dispersing the solid in 5-10 mL of deionized water to obtain a nano noble metal hydrosol; the noble metal salt or acid is more than one of chloroauric acid, chloroplatinic acid and silver nitrate; the reducing agent is sodium citrate or sodium borohydride.
The specific steps of the step (2) are as follows: dissolving the nano noble metal hydrosol obtained in the step (1) in 10-30 mL of absolute ethanol, stirring at room temperature, performing ultrasonic treatment for 10-30 min, adding ammonia water, stirring, dropwise adding an ethyl orthosilicate ethanol solution within 10-30 min, continuously stirring, and reacting for 10-20 h to obtain the noble metal @ SiO with amino double bonds on the surface of the nano sphere2A nanosphere solution; the ethyl orthosilicate ethanol solution is formed by dissolving 1.0-2.0 mL of ethyl orthosilicate in 10-20 mL of ethanol.
The specific steps of the step (3) are as follows: adding the noble metal @ SiO obtained in the step (2)2Adding 1-5 mL of ammonia water into the nanosphere solution, stirring for 10-30 min, then dropwise adding an ethanol solution of KH570 into the nanosphere solution within 4-8 h, and continuously stirring for reacting for 10-40 h to obtain the noble metal @ SiO2-KH570 nanosphere solution; the ethanol solution of the KH570 is formed by dissolving 1-3 mL of KH570 in 90-120 mL of ethanol.
The amount of water used in the step (4) is 80-150 mL, and the mass ratio of the sodium dodecyl benzene sulfonate to the sodium bicarbonate is 1: 5-1: 10, wherein the amount of the sodium bicarbonate is 0.19-0.36 g; the inert gas is nitrogen with the flow rate of 100-800 mL/min, the stirring is mechanical stirring at 150-300 rpm, and the heating temperature is 30-50 ℃; the volume ratio of the 4-chloromethylstyrene to the water in the system is 12:1: 60-36: 1:180, and the 4-chloromethylstyrene monomer needs to be subjected to an over-alkaline alumina column before use.
The specific steps of the step (5) are as follows: placing the nanosphere dry body in 1, 2-dichloroethane in a three-necked flask with a reflux condenser tube, stirring and swelling for 6-12 h at room temperature, then heating to 60-80 ℃, and rapidly adding anhydrous FeCl3Continuing to react for 12-36 h, adding a mixed solution of acetone and hydrochloric acid into a reaction system to stop the reaction, continuing to stir, centrifuging, washing and stirring with the mixed solution of acetone and hydrochloric acid, washing with ethanol for multiple times until the solution is neutral, and drying to obtain solid powder; the nanosphere dry body and FeCl3Carrying out super cross-linking with dichloroethane according to the mixture ratio of (0.5 g-1.5 g) to (0.6 g-1.7 g) to (50 mL-100 mL)Carrying out combined reaction; the volume ratio of acetone to hydrochloric acid in the acetone and hydrochloric acid mixed solution is 1: 1-5: 1.
In the carbonization step (6), the temperature is raised to 500-1000 ℃ at the temperature rise rate of 2-10 ℃/min in the nitrogen atmosphere with the flow rate of 100-800 mL/min, and the carbonization is carried out for 0.5-10 h; the treatment with the HF solution is to stir and dip the HF solution with the volume percentage concentration of 20-40% for 6-24 hours.
The yolk-eggshell structure precious metal @ hollow carbon nanosphere composite material prepared by the preparation method.
The shape of the noble metal @ hollow carbon nanosphere composite material with the yolk-eggshell structure is a regular nanosphere structure, the composite material is composed of internal noble metal nanoparticles and external hollow carbon nanosphere shells, and the BET specific surface area is 300-900 m2 g-1。
The yolk-eggshell structure noble metal @ hollow carbon nanosphere composite material is applied to a catalyst material for p-nitrophenol reduction, a lithium-sulfur battery limited sulfur nano carbon carrier material, a formaldehyde adsorption material or a biological antibacterial material.
The invention synthesizes noble metal @ SiO2Based on the core-shell nanospheres, the noble metal @ SiO with the multi-core-shell structure is prepared by surface modification and emulsion polymerization2According to the characteristics that self-crosslinking reaction can be carried out by using methylene of the polychloromethylstyrene, rich micropore network structures can be built in the shell without adding a crosslinking agent, and the composite material of the noble metal @ hollow carbon nanosphere with the yolk-eggshell structure can be obtained by virtue of the rigid structure of the polychloromethylstyrene shell after high-temperature carbonization and HF etching treatment.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention does not need any cross-linking agent, thus saving cost and reducing environmental pollution.
(2) The precious metal @ hollow carbon nanosphere composite material with the yolk-eggshell structure contains 5-12% of precious metal, the size of a precious metal nanoparticle is 10-20 nm, the outer diameter is 200-350 nm, the diameter of an inner cavity is 100-160 nm, the size of a micropore duct of a shell layer is 0.6-1.2 nm, and the size and the appearance are uniform, stable and controllable.
(3) The yolk-eggshell structure noble metal @ hollow carbon nanosphere composite material disclosed by the invention combines the synergistic effect advantages of the hollow nanospheres and the functional nanoparticles, so that the composite material has potential application prospects in the aspects of active substance carriers, organic pollutant adsorption, catalysis, biological antibiosis and the like, and can be used as a high-activity p-nitrophenol reduction catalyst material, a high-capacity lithium-sulfur battery limited sulfur nano carbon carrier material, a high-performance formaldehyde adsorption material and a biological antibiosis material.
Drawings
Fig. 1 is a scanning electron microscope photograph and a transmission electron microscope photograph of the yolk-eggshell structure Au @ hollow carbon nanosphere composite prepared in example 1, wherein a and b are scanning electron microscope photographs, and c is a transmission electron microscope photograph.
Fig. 2 is a pore size distribution curve of the yolk-eggshell structure Au @ hollow carbon nanosphere composite prepared in example 1.
Fig. 3 is an XRD pattern of the yolk-eggshell structure Au @ hollow carbon nanosphere composite prepared in example 1.
Fig. 4 is a uv-vis spectrum of the yolk-eggshell structure Au @ hollow carbon nanosphere composite material prepared in example 1 for catalytic reduction of p-nitrophenol.
Fig. 5 is a graph comparing the performance of the lithium-sulfur battery at 0.1C for the yolk-eggshell structure Au @ hollow carbon nanosphere composite prepared in example 1 and the yolk-eggshell structure hollow @ carbon nanosphere electrode prepared in comparative example 1.
Fig. 6 is a scanning electron micrograph of the hollow @ carbon nanosphere of the yolk-eggshell structure prepared in comparative example 1.
Fig. 7 is a uv-vis spectrum of the hollow @ carbon nanosphere of yolk-eggshell structure prepared in comparative example 1 on p-nitrophenol.
Fig. 8 is a transmission electron microscope photograph of the Ag @ hollow carbon nanosphere composite of the yolk-eggshell structure prepared in example 4.
Fig. 9 is a graph comparing the total amount of formaldehyde adsorbed by the yolk-eggshell structure Ag @ hollow carbon nanosphere composite prepared in example 4 with that of commercial activated carbon.
Fig. 10 is a graph of the antibacterial effect of (a) the yolk-eggshell structure hollow @ carbon nanosphere prepared in comparative example 1 and (b) the yolk-eggshell structure Ag @ hollow carbon nanosphere composite prepared in example 4.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of an Au @ hollow carbon nanosphere composite material with a yolk-eggshell structure comprises the following steps:
(1) preparing Au nano particles: 0.0216g of HAuCl was weighed4Dissolving in 237.5mL deionized water, adding into 500mL three-neck flask equipped with aqueduct, reflux condenser, vacuum plug and magneton, stirring vigorously with magneton, heating for reflux, and heating to boil; weighing 0.125g of sodium citrate, dissolving in 12.5mL of deionized water, quickly adding into the solution at one time, continuously heating and refluxing for 30min, and cooling to room temperature; after cooling, 0.0042g of PVP is weighed and dissolved in 1mL of deionized water, and then the solution is added into the cooled solution and stirred for 24 hours at room temperature; and centrifuging the obtained nano-gold solution by using a centrifugal machine (rotating speed 11800rpm, time 20min), removing supernatant liquid, and dispersing obtained solid in 6mL of water to obtain a nano-gold aqueous solution.
(2)Au@SiO2Preparing and modifying nanospheres: adding 19mL of ethanol and 6mL of nano-gold aqueous solution into a 100mL three-neck flask with a magnetic stirring and vacuum plug, performing ultrasonic treatment for 30min, adding 0.8mL of ammonia water, stirring the magnetic particles for 10min, adding an ethanol solution (19mL) of tetraethoxysilane (1.6mL) in 20min by using a microsyringe, and continuing stirring at room temperature for 12 h; the Au @ SiO obtained in the above way2Adding 1.4mL of ammonia water into the nanosphere solution, stirring with magnetons for 10min, adding KH570(2mL) ethanol solution (100mL) with a microsyringe for 8h, and stirring at room temperature for 36h to obtain Au @ SiO2-KH570, followed by centrifugation with absolute ethanol, washing 3 times, and dispersion into 10mL nanosphere ethanol solution.
(3)Au@SiO2@ preparation of polychloromethylstyrene composite nanospheres: 100mL of deionized water was poured into a 250mL four-necked round-bottomed flask equipped with an air duct, reflux condenser, mechanical stirrer, and vacuum stopper, mechanically stirred, and then purged with nitrogen to remove oxygen for 10 min. 0.03g of SDBS and 0.24g of NaHCO were added3Fully stirring until the system is uniform, continuously introducing nitrogen to remove oxygen for 10min, and then adding ultrasonically dispersed Au @ SiO2-KH570 in ethanol, stirred until the system is homogeneous; then adding 4.8mL of chloromethyl styrene (CMS, over-alkaline alumina column) and 0.2mL of Divinylbenzene (DVB), and stirring and reacting for 36h at the temperature of 30 ℃; after the reaction was completed, the nanospheres were centrifuged, washed with THF and EtOH, centrifuged 3 times each, and then dried at 60 ℃ for 6 hours to obtain nanosphere solid powder, which was weighed and recorded as Au @ SiO2@PCMS。
(4)Au@SiO2@ Friedel-Crafts hypercrosslinking reaction of polychlorostyrene composite nanospheres: according to Au @ SiO2@ PCMS nanosphere solid FeCl 31, 2-dichloroethane, 1(g), 1.1(g), and 80(mL) in the following ratio: in a single-neck bottle provided with a reflux condenser tube, a certain amount of Au @ SiO2@ PCMS is placed in 1, 2-dichloroethane for swelling for 12h, then the temperature is raised to 80 ℃, and anhydrous FeCl is rapidly added3And reacting for 24 hours. After the reaction was complete, acetone was added: terminating the reaction by using the acetone-hydrochloric acid mixed solvent with the volume ratio of 3:1, continuously keeping the temperature of 80 ℃ for 30min, filtering and washing, centrifuging to obtain a solid, washing and stirring the solid by using the acetone-hydrochloric acid mixed solution with the same concentration for 6h, washing the solid by using EtOH for multiple times to be neutral, and drying the solid in a vacuum oven at 60 ℃ to obtain a product, namely Au @ SiO2@xPCMS。
(5) Preparation of Au @ hollow microporous carbon nanospheres: 0.5g of Au @ SiO was taken2The product of the @ xPCMS nanosphere is carbonized in a carbonization furnace in a porcelain boat with the flow of N of 400mL/min2Raising the temperature to 900 ℃ at the temperature raising rate of 5 ℃/min under the atmosphere protection, keeping the temperature for 3h, and naturally cooling. Then removing SiO with 40% HF solution2And marking the obtained product as Au @ xPCMS-C to obtain the Au @ hollow carbon nanosphere composite material with the yolk-eggshell structure.
Using Micromeritic USAThe BET specific surface area of the prepared Au @ xPCMS-C is 315m by testing with an ASAP 2020 adsorber nitrogen adsorption method produced by s company2Per g, pore volume of 0.21cm3(ii) in terms of/g. As shown in FIG. 1, the microstructure of the obtained Au @ xPCMS-C is a regular nano spherical structure, a huge cavity is formed inside the nano sphere to form a yolk-eggshell structure, and the volume of the cavity is the original SiO2Volume of the nanospheres, and the gold nanoparticles are wrapped inside the cavity. The pore diameter is tested and analyzed, and the pore diameter is distributed in a hierarchical pore distribution (figure 2). XRD testing was performed on Au @ xPCMS-C, and the results are shown in FIG. 3. As can be seen from the figure, obvious diffraction peaks can be observed at 38 degrees, 44 degrees, 65 degrees and 78 degrees, which correspond to the crystal planes of the gold face-centered cubic structures 111, 200, 220 and 311 respectively, and the particle size of the gold nanoparticles is about 15nm and is consistent with the observation result of a transmission electron microscope after the crystal plane of the gold nanoparticles 111 is calculated by using the Sherrer formula.
The obtained Au @ xPCMS-C was used for the catalytic reduction of 4-nitrophenol (4-NP): after adding NaBH4After the solution, 4-NP showed a distinct UV absorption peak at 400nm (as shown in FIG. 4), and Au @ xPCMS-C was added, and as the reaction proceeded, the reactant absorption peak at 400nm gradually decreased until it nearly disappeared at 60min, while a new absorption peak at 305nm appeared and increased with time, thus demonstrating the reduction of 4-NP to 4-aminophenol (4-AP).
The obtained Au @ xPCMS-C is used as an electrode material of a lithium sulfur battery, the performance of the electrode material is tested, and a figure 5 shows the discharge specific capacity of the first 25 circles under the current density of 0.1C. As can be seen from the figure, the first discharge specific capacities were 1385mAh g, respectively-1Based on the theoretical specific discharge capacity of sulfur of 1675mAh g-1Calculated, the utilization rate of the corresponding sulfur is 82.7 percent; specific capacity after 25 cycles was 712mAh g-1The specific discharge capacity retention rate was 51.4%. Therefore, the electrode prepared from Au @ xPCMS-C has high specific discharge capacity, high sulfur utilization rate and high specific capacity retention rate.
Comparative example 1
A preparation method of a hollow @ carbon nanosphere with a yolk-eggshell structure comprises the following steps:
(1)SiO2preparing and modifying nanospheres: adding 19mL of ethanol and 6mL of deionized water into a 100mL three-neck flask with a magnetic stirring and vacuum plug, adding 0.8mL of ammonia water, stirring for 10min by using a magnetic stirring device, adding an ethanol solution (19mL) of tetraethoxysilane (1.6mL) within 20min by using a microsyringe, and continuing stirring at room temperature for 12 h; the obtained SiO2Adding 1.4mL ammonia water into the nanosphere solution, stirring with magnetons for 10min, adding KH570(2mL) ethanol solution (100mL) with a microsyringe for 8h, and stirring at room temperature for 36h to obtain SiO2-KH570, followed by centrifugation with absolute ethanol, washing 3 times, and dispersion into 10mL nanosphere ethanol solution.
(2)SiO2@ preparation of polychloromethylstyrene composite nanospheres: pouring 100mL of deionized water into a 250mL four-neck round-bottom bottle provided with an air duct, a reflux condenser tube, a mechanical stirring rod and a vacuum plug, starting mechanical stirring, and introducing nitrogen to remove oxygen for 10 min; adding 0.03g of SDBS and 0.24g of NaHCO3, fully stirring until the system is uniform, continuously introducing nitrogen to remove oxygen for 10min, then adding ethanol dispersion of SiO2-KH570 dispersed by ultrasonic, and stirring until the system is uniform; then, 4.8mL of chloromethylstyrene (CMS, over-basic alumina column) and 0.2mL of Divinylbenzene (DVB) were added and the reaction was stirred at 30 ℃ for 36 hours. After the reaction was completed, centrifugation was performed, and washed with THF and EtOH, centrifuged 3 times each, and then dried at 60 ℃ for 6 hours to obtain nanosphere solid powder and weighed. We will denote it as SiO2@PCMS。
(3)SiO2@ Friedel-Crafts hypercrosslinking reaction of polychlorostyrene composite nanospheres: according to SiO2The preparation ratio of @ PCMS nanosphere solid FeCl3:1, 2-dichloroethane ═ 1(g):1.1(g):80(mL) is adopted for the hypercrosslinking reaction: in a single-neck bottle with reflux condenser tube, a certain amount of SiO2@ PCMS is placed in 1, 2-dichloroethane for swelling for 12h, then the temperature is raised to 80 ℃, anhydrous FeCl3 is rapidly added, and the reaction is carried out for 24 h. After the reaction was complete, acetone was added: terminating the reaction by acetone-hydrochloric acid mixed solvent with the volume ratio of 3:1, keeping the temperature of 80 ℃ for 30min, filtering and washing, centrifuging to obtain solid, washing and stirring the solid by the acetone-hydrochloric acid mixed solution with the same concentration for 6h, and washing with EtOHThen drying the mixture in a vacuum oven at 60 ℃ until the mixture is neutral to obtain a product named as SiO2@xPCMS。
(4) Preparation of hollow @ carbon nanospheres: take 0.5g SiO2The product of the @ xPCMS nanosphere is carbonized in a carbonization furnace in a porcelain boat with the flow of N of 400mL/min2Raising the temperature to 900 ℃ at the temperature rise rate of 5 ℃/min under the atmosphere protection, keeping the temperature for 3 hours, and naturally cooling; then removing SiO with 40% HF solution2And marking the obtained product as hollow @ xPCMS-C to obtain the hollow @ microporous carbon nanosphere with the yolk-eggshell structure.
The BET specific surface area of the prepared hollow @ xPCMS-C is 321m by using an ASAP 2020 adsorber nitrogen adsorption method produced by Micromeritics of America2Per g, pore volume of 0.23cm3The pore diameter is in hierarchical pore distribution. As shown in fig. 6, the microstructure of the resulting hollow @ xPCMS-C is a regular nanosphere structure, the internal hollow structure of the nanosphere. XRD testing was performed on hollow @ xPCMS-C, and the results are shown in FIG. 7, which is a peak pattern of amorphous carbon.
As can be seen from FIG. 7, when the hollow @ xPCMS-C carbon nanospheres catalyze and reduce p-nitrophenol, the absorption peak at 400nm is the same as that at 0min at 30min and 60min without changing and weakening along with time due to the absence of the gold nanoparticles, and no new absorption peak appears at 300nm, which indicates that the hollow @ xPCMS-C has no effect of catalyzing and reducing p-nitrophenol.
The obtained hollow @ xPCMS-C is used as an electrode material of a lithium-sulfur battery, and the performance of the hollow @ xPCMS-C is tested. Specific capacity after 25 cycles of 591mAh g-1。
Example 2
A preparation method of an Au @ hollow carbon nanosphere composite material with a yolk-eggshell structure comprises the following steps:
(1) preparing Au nano particles: 0.0216g of HAuCl was weighed4Dissolved in 237.5mL of deionized water, and the resulting solution was charged into a 500mL three-necked flask equipped with a water guide, reflux condenser, vacuum stopper and magneton, vigorously stirred with the magneton, heated to reflux, and heated to boiling. 0.125g of sodium citrate is weighed and dissolved in 12.5mL of deionized water, and is quickly added into the upper solution in one time,heating and refluxing for 30min, and cooling to room temperature. After cooling, 0.0042g of PVP was weighed and dissolved in 1mL of deionized water, and then added to the above cooled solution, and stirred at room temperature for 24 h. The resulting nanogold solution was centrifuged (11800 rpm for 20min) using a centrifuge, and the supernatant was removed to obtain a solid dispersed in 6mL of water.
(2)Au@SiO2Preparing and modifying nanospheres: adding 19mL of ethanol and 6mL of nano-gold aqueous solution into a 100mL three-neck flask with a magnetic stirring and vacuum plug, performing ultrasonic treatment for 30min, adding 0.8mL of ammonia water, stirring for 10min by a magnetic stirring, adding an ethanol solution (19mL) of tetraethoxysilane (1.6mL) within 20min by using a microsyringe, and continuing stirring at room temperature for 12h after the addition. The Au @ SiO obtained in the above way2Adding 1.4mL of ammonia water into the nanosphere solution, stirring with magnetons for 10min, adding KH570(2mL) ethanol solution (100mL) with a microsyringe for 8h, and stirring at room temperature for 36h to obtain Au @ SiO2-KH570, followed by centrifugation with absolute ethanol, washing 3 times, and dispersion into 10mL nanosphere ethanol solution.
(3)Au@SiO2@ preparation of polychloromethylstyrene composite nanospheres: 100mL of deionized water was poured into a 250mL four-necked round-bottomed flask equipped with an air duct, reflux condenser, mechanical stirrer, and vacuum stopper, mechanically stirred, and then purged with nitrogen to remove oxygen for 10 min. 0.03g of SDBS and 0.24g of NaHCO were added3Fully stirring until the system is uniform, continuously introducing nitrogen to remove oxygen for 10min, and then adding ultrasonically dispersed Au @ SiO2-KH570 in ethanol, stirred until the system is homogeneous. Then, 4.8mL of chloromethylstyrene (CMS, over-basic alumina column) and 0.2mL of Divinylbenzene (DVB) were added and the reaction was stirred at 30 ℃ for 36 hours. After the reaction was completed, centrifugation was performed, and washed with THF and EtOH, centrifuged 3 times each, and then dried at 60 ℃ for 6 hours to obtain nanosphere solid powder and weighed. We will note it as Au @ SiO2@PCMS。
(4)Au@SiO2@ Friedel-Crafts hypercrosslinking reaction of polychlorostyrene composite nanospheres: according to Au @ SiO2The material of the @ PCMS nanosphere solid FeCl3:1, 2-dichloroethane ═ 1(g):1.1(g):80(mL) is subjected to a hypercrosslinking reaction. In a single-neck flask with reflux condenserPlacing a certain amount of Au @ SiO2@ PCMS in 1, 2-dichloroethane for swelling for 12h, then heating to 80 ℃, and rapidly adding anhydrous FeCl3And reacting for 24 hours. After the reaction was complete, acetone was added: terminating the reaction by using the acetone-hydrochloric acid mixed solvent with the volume ratio of 3:1, continuously keeping the temperature of 80 ℃ for 30min, filtering and washing, centrifuging to obtain a solid, washing and stirring the solid by using the acetone-hydrochloric acid mixed solution with the same concentration for 6h, washing the solid by using EtOH for multiple times to be neutral, and drying the solid in a vacuum oven at 60 ℃ to obtain a product, namely Au @ SiO2@xPCMS。
(5) Preparation of Au @ hollow microporous carbon nanospheres: 0.5g of Au @ SiO was taken2The product of the @ xPCMS nanosphere is carbonized in a carbonization furnace in a porcelain boat with the flow of N of 400mL/min2Raising the temperature to 900 ℃ at the temperature raising rate of 5 ℃/min under the atmosphere protection, keeping the temperature for 1h, and naturally cooling. Then removing SiO with 40% HF solution2And marking the obtained product as Au @ xPCMS-C-2 to obtain the Au @ hollow carbon nanosphere composite material with the yolk-eggshell structure.
The BET specific surface area of the prepared Au @ xPCMS-C-2 is 305m when tested by an ASAP 2020 adsorber nitrogen adsorption method of Micromeritics corporation in USA2Per g, pore volume of 0.19cm3/g。
The obtained Au @ xPCMS-C-2 is used for carrying out catalytic reaction on 4-nitrophenol, and shows better catalytic activity.
The obtained Au @ xPCMS-C-2 is used as an electrode material of a lithium-sulfur battery, the performance of the electrode material is tested, and the specific capacity after 25 circles is 710mAh g-1。
Example 3
A preparation method of an Au @ hollow carbon nanosphere composite material with a yolk-eggshell structure comprises the following steps:
(1) preparing Au nano particles: 0.0216g of HAuCl was weighed4Dissolved in 237.5mL of deionized water, and the resulting solution was charged into a 500mL three-necked flask equipped with a water guide, reflux condenser, vacuum stopper and magneton, vigorously stirred with the magneton, heated to reflux, and heated to boiling. 0.125g of sodium citrate is weighed and dissolved in 12.5mL of deionized water, and is quickly added into the solution in one step, and the solution is continuously heated and refluxed for 30min and cooled to room temperature. After cooling, call0.0042g of PVP was dissolved in 1mL of deionized water, and added to the above cooled solution, and stirred at room temperature for 24 h. The resulting nanogold solution was centrifuged (11800 rpm for 20min) using a centrifuge, and the supernatant was removed to obtain a solid dispersed in 6mL of water.
(2)Au@SiO2Preparing and modifying nanospheres: adding 19mL of ethanol and 6mL of nano-gold aqueous solution into a 100mL three-neck flask with a magnetic stirring and vacuum plug, performing ultrasonic treatment for 30min, adding 0.8mL of ammonia water, stirring for 10min by a magnetic stirring, adding an ethanol solution (19mL) of tetraethoxysilane (1.6mL) within 20min by using a microsyringe, and continuing stirring at room temperature for 12h after the addition. The Au @ SiO obtained in the above way2Adding 1.4mL of ammonia water into the nanosphere solution, stirring with magnetons for 10min, adding KH570(2mL) ethanol solution (100mL) with a microsyringe for 8h, and stirring at room temperature for 36h to obtain Au @ SiO2-KH570, followed by centrifugation with absolute ethanol, washing 3 times, and dispersion into 10mL nanosphere ethanol solution.
(3)Au@SiO2@ preparation of polychloromethylstyrene composite nanospheres: 100mL of deionized water was poured into a 250mL four-necked round-bottomed flask equipped with an air duct, reflux condenser, mechanical stirrer, and vacuum stopper, mechanically stirred, and then purged with nitrogen to remove oxygen for 10 min. 0.03g of SDBS and 0.24g of NaHCO were added3Fully stirring until the system is uniform, continuously introducing nitrogen to remove oxygen for 10min, and then adding ultrasonically dispersed Au @ SiO2-KH570 in ethanol, stirred until the system is homogeneous. Then, 4.8mL of chloromethylstyrene (CMS, over-basic alumina column) and 0.2mL of Divinylbenzene (DVB) were added and the reaction was stirred at 30 ℃ for 36 hours. After the reaction was completed, centrifugation was performed, and washed with THF and EtOH, centrifuged 3 times each, and then dried at 60 ℃ for 6 hours to obtain nanosphere solid powder and weighed. We will note it as Au @ SiO2@PCMS。
(4)Au@SiO2@ Friedel-Crafts hypercrosslinking reaction of polychlorostyrene composite nanospheres: according to Au @ SiO2The material of the @ PCMS nanosphere solid FeCl3:1, 2-dichloroethane ═ 1(g):1.1(g):80(mL) is subjected to a hypercrosslinking reaction. In a single-neck bottle provided with a reflux condenser, a certain amount of Au @ SiO2@ PCMS is dissolved in 1, 2-dichloroethaneExpanding for 12h, then heating to 80 ℃, and rapidly adding anhydrous FeCl3And reacting for 24 hours. After the reaction was complete, acetone was added: terminating the reaction by using the acetone-hydrochloric acid mixed solvent with the volume ratio of 3:1, continuously keeping the temperature of 80 ℃ for 30min, filtering and washing, centrifuging to obtain a solid, washing and stirring the solid by using the acetone-hydrochloric acid mixed solution with the same concentration for 6h, washing the solid by using EtOH for multiple times to be neutral, and drying the solid in a vacuum oven at 60 ℃ to obtain a product, namely Au @ SiO2@xPCMS。
(5) Preparation of Au @ hollow microporous carbon nanospheres: 0.5g of Au @ SiO was taken2The product of the @ xPCMS nanosphere is carbonized in a carbonization furnace in a porcelain boat with the flow of N of 400mL/min2Raising the temperature to 900 ℃ at the temperature raising rate of 5 ℃/min under the atmosphere protection, keeping the temperature for 6 hours, and naturally cooling. Then removing SiO with 40% HF solution2And marking the obtained product as Au @ xPCMS-C-3 to obtain the Au @ hollow carbon nanosphere composite material with the yolk-eggshell structure.
The BET specific surface area of the prepared Au @ xPCMS-C-3 is 331m by using an ASAP 2020 adsorber nitrogen adsorption method of Micromeritics corporation in America2Per g, pore volume of 0.26cm3/g。
The obtained Au @ xPCMS-C-3 is used for carrying out catalytic reaction on 4-nitrophenol, and shows better catalytic activity.
The obtained Au @ xPCMS-C-3 is used as an electrode material of a lithium-sulfur battery, the performance of the electrode material is tested, and the specific capacity after 25 circles is 708mAh g-1。
Example 4
A preparation method of an Ag @ hollow carbon nanosphere composite material with a yolk-eggshell structure comprises the following steps:
(1) preparing Ag nano particles: 50g of PVP is weighed and added into a 500mL three-necked flask, 375mL of ethylene glycol is weighed and added, and mechanical stirring is carried out under an oil bath at the temperature of 80 ℃ until complete dissolution is achieved, so that colorless transparent liquid is obtained. Weighing 2g of AgNO3The solid is added into the colorless solution at one time, and is mechanically stirred in the dark until the solid is completely dissolved to form light yellow. Then the temperature is increased to 115 ℃ for reaction for 1 h. After the reaction is finished, the green-brown nano silver sol is moved into a 2L beaker for natural cooling, and a large amount of acetone (about)1800mL), stirring for 1min by a glass rod, standing and precipitating for 7-8 h until the supernatant is colorless. And removing colorless supernatant, diluting with 500mL of ethanol, centrifuging (rotating speed of 11500rpm, 15min), separating out nano silver at the bottom of the centrifuge tube, continuously centrifuging the upper layer of nano silver-containing solution, and repeating for 3 times. After the centrifugation is completed, the obtained nano silver-containing solution is washed by ethanol centrifugation for 3 times (rotation speed 11500rpm, 15min), and finally the silver is dispersed in 10mL of water.
(2)Ag@SiO2Preparing and modifying nanospheres: adding 19mL of ethanol and 6mL of nano-silver aqueous solution into a 100mL three-neck flask with a magnetic stirring and vacuum plug, performing ultrasonic treatment for 30min, adding 0.8mL of ammonia water, stirring for 10min by a magnetic stirring, adding an ethanol solution (19mL) of tetraethoxysilane (1.6mL) within 20min by using a microsyringe, and continuing stirring at room temperature for 12h after the addition. The Au @ SiO obtained in the above way2Adding 1.4mL ammonia water into the nanosphere solution, stirring with magnetons for 10min, adding KH570(2mL) ethanol solution (100mL) with a microsyringe for 8h, and stirring at room temperature for 36h to obtain Ag @ SiO2-KH570, followed by centrifugation with absolute ethanol, washing 3 times, and dispersion into 10mL nanosphere ethanol solution.
(3)Ag@SiO2@ preparation of polychloromethylstyrene composite nanospheres: 100mL of deionized water was poured into a 250mL four-necked round-bottomed flask equipped with an air duct, reflux condenser, mechanical stirrer, and vacuum stopper, mechanically stirred, and then purged with nitrogen to remove oxygen for 10 min. 0.03g of SDBS and 0.24g of NaHCO were added3Fully stirring until the system is uniform, continuously introducing nitrogen to remove oxygen for 10min, and then adding ultrasonically dispersed Au @ SiO2-KH570 in ethanol, stirred until the system is homogeneous. Then, 4.8mL of chloromethylstyrene (CMS, over-basic alumina column) and 0.2mL of Divinylbenzene (DVB) were added and the reaction was stirred at 30 ℃ for 36 hours. After the reaction was completed, centrifugation was performed, and washed with THF and EtOH, centrifuged 3 times each, and then dried at 60 ℃ for 6 hours to obtain nanosphere solid powder and weighed. We will note it as Ag @ SiO2@PCMS。
(4)Ag@SiO2@ Friedel-Crafts hypercrosslinking reaction of polychlorostyrene composite nanospheres: according to Ag @ SiO2@ PCMS nanosphere solid FeCl3:1, 2-dichloroethane ═ 1(g):1.1(g) 80(mL) in the above ratio. In a single-neck bottle provided with a reflux condenser tube, a certain amount of Au @ SiO2@ PCMS is placed in 1, 2-dichloroethane for swelling for 12h, then the temperature is raised to 80 ℃, and anhydrous FeCl is rapidly added3And reacting for 24 hours. After the reaction was complete, acetone was added: terminating the reaction by using the acetone-hydrochloric acid mixed solvent with the volume ratio of 3:1, continuously keeping the temperature of 80 ℃ for 30min, filtering and washing, centrifuging to obtain a solid, washing and stirring the solid by using the acetone-hydrochloric acid mixed solution with the same concentration for 6h, washing the solid by using EtOH for multiple times to be neutral, and drying the solid in a vacuum oven at 60 ℃ to obtain a product named as Ag @ SiO2@xPCMS。
(5) Preparing Ag @ hollow microporous carbon nanospheres: 0.5g of Ag @ SiO is taken2The product of the @ xPCMS nanosphere is carbonized in a carbonization furnace in a porcelain boat with the flow of N of 400mL/min2Raising the temperature to 900 ℃ at the temperature raising rate of 5 ℃/min under the atmosphere protection, keeping the temperature for 3h, and naturally cooling. Then removing SiO with 40% HF solution2And marking the obtained product as Ag @ xPCMS-C to obtain the Ag @ hollow carbon nanosphere composite material with the yolk-eggshell structure.
The BET specific surface area of the prepared Ag @ xPCMS-C is 321m by using an ASAP 2020 adsorber nitrogen adsorption method produced by Micromeritics of America2Per g, pore volume of 0.23cm3(ii) in terms of/g. As shown in FIG. 8, the microstructure of the obtained Ag @ xPCMS-C is a regular nano spherical structure, a huge cavity is formed inside the nano sphere to form a yolk-eggshell structure, and the volume of the cavity is the original SiO2The volume of the nanosphere is larger, and the nano silver particles are wrapped inside the cavity.
The formaldehyde adsorption performance of Ag @ xPCMS-C is studied by using a TTPS-1602H type formaldehyde detection demonstration instrument of titanium Tang nanotechnology Co., Ltd (figure 9), and the total formaldehyde adsorption amount of Ag @ xPCMS-C is 75mg/m after adsorbing for 24H3Much higher than that of commercial activated carbon by 5mg/m3And after 48 hours, the concentration reaches 87mg/m3Showing outstanding formaldehyde removal capability.
Ag @ xPCMS-C was used for the biological antibacterial property study, and the results are shown in FIG. 10. After 24 hours of culture in the incubator, the pure nano silver particles have powerful bacteriostatic effect and bacteriostatic ringIs obvious. Although the nano silver in the Ag @ xPCMS-C carbon nanosphere is blocked by a thick carbon shell layer outside, the free Ag+The filter paper can quickly pass through the shell layer with rich pores and is distributed around the filter paper, so that a good bacteriostatic effect is achieved.
Example 5
A preparation method of a yolk-eggshell structure Pt @ hollow carbon nanosphere composite material comprises the following steps:
(1) preparing Pt nano particles: 50mL of deionized water, 4mL of 7.723X 10 was placed in a 150mL three-necked flask- 3mol L-1H2PtCl6Adding 51.4mg PVP into the aqueous solution, stirring with magneton, mixing, heating to 50 deg.C, and weighing 35.2mg NaBH4Dissolved in 30mL of ice-deionized water, slowly added dropwise to the reactor with stirring, and the solution gradually turned dark brown in color with a large amount of bubbles. And after the dropwise addition is finished, continuously stirring for 15 hours to obtain the Pt nano particles. Followed by centrifugation at 14000rpm and 3000rpm for 15min each, respectively, and storage in 6mL of deionized water.
(2)Pt@SiO2Preparing and modifying nanospheres: adding 19mL of ethanol and 6mL of nano platinum aqueous solution into a 100mL three-neck flask with a magnetic stirring and vacuum plug, performing ultrasonic treatment for 30min, adding 0.8mL of ammonia water, stirring the magnetic particles for 10min, adding an ethanol solution (19mL) of tetraethoxysilane (1.6mL) in 20min by using a microsyringe, and continuing stirring at room temperature for 12 h. The Pt @ SiO obtained in the above way2Adding 1.4mL of ammonia water into the nanosphere solution, stirring with magnetons for 10min, adding KH570(2mL) ethanol solution (100mL) with a microsyringe for 8h, and stirring at room temperature for 36h to obtain Pt @ SiO2-KH570, followed by centrifugation with absolute ethanol, washing 3 times, and dispersion into 10mL nanosphere ethanol solution.
(3)Pt@SiO2@ preparation of polychloromethylstyrene composite nanospheres: 100mL of deionized water was poured into a 250mL four-necked round-bottomed flask equipped with an air duct, reflux condenser, mechanical stirrer, and vacuum stopper, mechanically stirred, and then purged with nitrogen to remove oxygen for 10 min. 0.03g of SDBS and 0.24g of NaHCO were added3Fully stirring until the system is uniformHomogenizing, introducing nitrogen gas continuously to remove oxygen for 10min, and adding ultrasonically dispersed Pt @ SiO2-KH570 in ethanol, stirred until the system is homogeneous. Then, 4.8mL of chloromethylstyrene (CMS, over-basic alumina column) and 0.2mL of Divinylbenzene (DVB) were added and the reaction was stirred at 30 ℃ for 36 hours. After the reaction was completed, centrifugation was performed, and washed with THF and EtOH, centrifuged 3 times each, and then dried at 60 ℃ for 6 hours to obtain nanosphere solid powder and weighed. We will note it as Pt @ SiO2@PCMS。
(4)Pt@SiO2@ Friedel-Crafts hypercrosslinking reaction of polychlorostyrene composite nanospheres: according to Pt @ SiO2@ PCMS nanosphere solid FeCl3The hypercrosslinking reaction was carried out in a ratio of 1, 2-dichloroethane to 1(g) to 1.1(g) to 80 (mL). In a single-neck bottle provided with a reflux condenser tube, a certain amount of Pt @ SiO2@ PCMS is placed in 1, 2-dichloroethane for swelling for 12h, then the temperature is raised to 80 ℃, and anhydrous FeCl is rapidly added3And reacting for 24 hours. After the reaction was complete, acetone was added: terminating the reaction by using the acetone-hydrochloric acid mixed solvent with the volume ratio of 3:1, continuously keeping the temperature of 80 ℃ for 30min, filtering and washing, centrifuging to obtain a solid, washing and stirring the solid by using the acetone-hydrochloric acid mixed solution with the same concentration for 6h, washing the solid by using EtOH for multiple times to be neutral, and drying the solid in a vacuum oven at 60 ℃ to obtain a product, namely Pt @ SiO2@xPCMS。
(5) Preparation of Pt @ hollow carbon nanospheres: 0.5g of Pt @ SiO was taken2The product of the @ xPCMS nanosphere is carbonized in a carbonization furnace in a porcelain boat with the flow of N of 400mL/min2Raising the temperature to 900 ℃ at the temperature raising rate of 5 ℃/min under the atmosphere protection, keeping the temperature for 3h, and naturally cooling. Then removing SiO with 40% HF solution2And marking the obtained product as Pt @ xPCMS-C to obtain the Pt @ hollow carbon nanosphere composite material with the yolk-eggshell structure.
The BET specific surface area of the prepared Pt @ xPCMS-C is 332m when tested by an ASAP 2020 adsorber nitrogen adsorption method of Micromeritics corporation in USA2Per g, pore volume of 0.25cm3(ii) in terms of/g. The microstructure of the Pt @ xPCMS-C is in a regular nano spherical structure, a huge cavity is arranged inside the nanosphere to form a yolk-eggshell structure, and the volume of the cavity is the original SiO2Volume of nanospheres, with nano-platinum particles wrapped inside the cavity.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a noble metal @ hollow carbon nanosphere composite material with a yolk-eggshell structure is characterized by comprising the following operation steps of:
(1) reducing noble metal salt or acid by using a reducing agent to prepare nano noble metal hydrosol;
(2) adding ethanol and ammonia water into the nano noble metal hydrosol obtained in the step (1), and stirring and mixing the nano noble metal hydrosol with an ethanol solution of ethyl orthosilicate to obtain the noble metal @ SiO2A nanosphere solution;
(3) the noble metal @ SiO obtained in the step (2)2Continuously adding ammonia water into the nanosphere solution, stirring and mixing the solution by using an ethanol solution of gamma-methacryloxypropyltrimethoxysilane to react to obtain the noble metal @ SiO with amino double bonds on the surfaces of the nanospheres2Centrifuging and washing the nanosphere solution by using absolute ethyl alcohol, and concentrating the nanosphere solution into a nanosphere ethyl alcohol solution;
(4) introducing inert gas for protection, heating the mixed solution of water, sodium dodecyl benzene sulfonate and sodium bicarbonate under the stirring condition, adding the nanosphere ethanol solution obtained in the step (3), the organic monomer 4-chloromethyl styrene and divinylbenzene to obtain the polychloromethyl styrene coated noble metal @ SiO2Centrifuging, washing and drying the nanospheres by using absolute ethyl alcohol, and weighing the dry mass;
(5) placing the dried nanospheres obtained in the step (4) into a reaction container, adding 1, 2-dichloroethane as a solvent, swelling at room temperature, and adding anhydrous FeCl3As catalyst, heating and refluxing under stirring to perform Friedel-Crafts crosslinking reaction, centrifuging to obtain solid product, drying and post-treating to obtain crosslinked polychloromethylstyrene coated noble metal @ SiO2The nanosphere of (1);
(6) in N2Carbonizing the nanospheres obtained in the step (5) under the protection of atmosphere, and then treating with HF solution to remove SiO2And drying and then processing to obtain the noble metal @ hollow carbon nanosphere composite material with the yolk-eggshell structure.
2. The method of claim 1, wherein: the specific steps of the step (1) are as follows: adding noble metal salt or acid into water, heating to fully dissolve the noble metal salt or acid to obtain a noble metal salt or acid solution, then adding a reducing agent solution to reduce the noble metal salt or acid solution, stirring for 12-36 h, centrifuging to obtain a solid, and dispersing the solid in 5-10 mL of deionized water to obtain a nano noble metal hydrosol; the noble metal salt or acid is more than one of chloroauric acid, chloroplatinic acid and silver nitrate; the reducing agent is sodium citrate or sodium borohydride.
3. The method of claim 1, wherein: the specific steps of the step (2) are as follows: dissolving the nano noble metal hydrosol obtained in the step (1) in 10-30 mL of absolute ethanol, stirring at room temperature, performing ultrasonic treatment for 10-30 min, adding ammonia water, stirring, dropwise adding an ethyl orthosilicate ethanol solution within 10-30 min, continuously stirring, and reacting for 10-20 h to obtain the noble metal @ SiO2A nanosphere solution; the ethyl orthosilicate ethanol solution is formed by dissolving 1.0-2.0 mL of ethyl orthosilicate in 10-20 mL of ethanol.
4. The method of claim 1, wherein: the specific steps of the step (3) are as follows: adding the noble metal @ SiO obtained in the step (2)2Adding 1-5 mL of ammonia water into the nanosphere solution, stirring for 10-30 min, then dropwise adding an ethanol solution of gamma-methacryloxypropyltrimethoxysilane within 4-8 h, and continuously stirring for reacting for 10-40 h to obtain the precious metal @ SiO with amino double bonds on the nanosphere surface2A nanosphere solution; the ethanol solution of the gamma-methacryloxypropyltrimethoxysilane is prepared by dissolving 1-3 mL of gamma-methacryloxypropyltrimethoxysilane in 90-120 mL of ethanolThe resulting solution.
5. The method of claim 1, wherein: the amount of water used in the step (4) is 80-150 mL, and the mass ratio of the sodium dodecyl benzene sulfonate to the sodium bicarbonate is 1: 5-1: 10, wherein the amount of the sodium bicarbonate is 0.19-0.36 g; the inert gas is nitrogen with the flow rate of 100-800 mL/min, the stirring is mechanical stirring at 150-300 rpm, and the heating temperature is 30-50 ℃; the volume ratio of the 4-chloromethylstyrene to the water in the system is 12:1: 60-36: 1:180, and the 4-chloromethylstyrene monomer needs to be subjected to an over-alkaline alumina column before use.
6. The method of claim 1, wherein: the specific steps of the step (5) are as follows: placing the nanosphere dry body in 1, 2-dichloroethane in a three-necked flask with a reflux condenser tube, stirring and swelling for 6-12 h at room temperature, then heating to 60-80 ℃, and rapidly adding anhydrous FeCl3Continuing to react for 12-36 h, adding a mixed solution of acetone and hydrochloric acid into a reaction system to stop the reaction, continuing to stir, centrifuging, washing and stirring with the mixed solution of acetone and hydrochloric acid, washing with ethanol for multiple times until the solution is neutral, and drying to obtain solid powder; the nanosphere dry body and FeCl3Carrying out Friedel-Crafts crosslinking reaction with dichloroethane according to the mixture ratio of (0.5 g-1.5 g) to (0.6 g-1.7 g) to (50 mL-100 mL); the volume ratio of acetone to hydrochloric acid in the acetone and hydrochloric acid mixed solution is 1: 1-5: 1.
7. The method of claim 1, wherein: in the carbonization step (6), the temperature is raised to 500-1000 ℃ at the temperature rise rate of 2-10 ℃/min in the nitrogen atmosphere with the flow rate of 100-800 mL/min, and the carbonization is carried out for 0.5-10 h; the treatment with the HF solution is to stir and dip the HF solution with the volume percentage concentration of 20-40% for 6-24 hours.
8. The noble metal @ hollow carbon nanosphere composite material with the yolk-eggshell structure prepared by the preparation method of any one of claims 1 to 7.
9. The yolk-eggshell structure noble metal @ hollow carbon nanosphere composite of claim 8 wherein: the shape of the noble metal @ hollow carbon nanosphere composite material with the yolk-eggshell structure is a regular nanosphere structure, the composite material is composed of internal noble metal nanoparticles and external hollow carbon nanosphere shells, and the BET specific surface area is 300-900 m2 g-1。
10. The use of the yolk-eggshell structure noble metal @ hollow carbon nanosphere composite material of claim 9 in a catalyst material for p-nitrophenol reduction, a lithium-sulfur battery limited sulfur nanocarbon support material, a formaldehyde adsorption material or a biological antibacterial material.
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