CN111266103A - Synthesis method of nano silicon sphere reactor and application of nano silicon sphere reactor in organic dye wastewater - Google Patents
Synthesis method of nano silicon sphere reactor and application of nano silicon sphere reactor in organic dye wastewater Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J23/74—Iron group metals
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention relates to a synthesis method of a nano silicon sphere reactor and application of the nano silicon sphere reactor in organic dye wastewater. The invention uses a polymer L2Metal ions and a diblock polymer; the synthesis method comprises the following steps: first L2Complexing with metal ions through coordination to form a plurality of anion chains with negative charges;then the anion chain and the diblock polymer with positive charges are combined together through the charge action to form a micelle in a water phase; then depositing silicon dioxide, zirconium dioxide or titanium dioxide on the micelle as a template; finally, the mesoporous hollow nano silicon spheres containing metal or metal oxide are obtained through post-treatment. The invention not only has simple synthesis method, but also can be applied to various metals. The nano silicon ball material prepared by the synthesis method has the common advantages of the existing materials, namely, the nano silicon ball material contains metal, has mesoporous and hollow structures, and thus the application range of the material is expanded.
Description
Technical Field
The invention relates to synthesis of nano materials and organic catalytic oxidation, in particular to synthesis of metal-containing mesoporous hollow nanospheres and degradation of organic wastewater.
Background
At present, a reverse microemulsion method is mainly used for synthesizing mesoporous hollow nano silicon spheres, such as the documents [1] Z.Chen, Z.M.Cui, F.Niu, L.Jiang, W.G.Song, chem.Commun.2010,46, 6524-; [2] lu, A.Popa, S.ZHou, J.J.Zhu, A.C.S.Samia, chem.Commun.2013,49, 11436-; [3] a) D.Cassano, D.R.Martir, G.Signore, V.Piazza, V.Voliani, chem.Commun.2015,51, 9939-; b) G.D.Moon, U.Jeong, chem.Mater.2008,20, 3003-3007; and Micelle template methods, such as those described in [4] A. khanal, Y. Inoue, M.Yada, K.Nakashima.Synthesis of Silica Hollow nanoparticles with Core-Shell-Core Structure, J.Am.chem.Soc.2007,129, 1534-1535. Wherein: the reverse microemulsion method is mainly used for reducing metal ions into oleophilic nano metal in an aqueous solution. Amphoteric polymers such as tetradecyltrimethylammonium bromide (TTAB), references [5] H.Liu, H.Yu, Chun.Xiong, S.ZHOU.Architecture controlled PtNi @ mSiO2and Pt-NiO @ mSiO2 meso core-shell nanocations for enhancing p-chloronebenzene hydrogenation selection RSC adv.2015,5, 20238-20247 are then used to form micelles with the nano-metal particles. Next, using the micelle as a template, silica is deposited onto the template by adding Tetraethylorthosilicate (TEOS). Finally, a series of post-treatments such as centrifugation and roasting are carried out to obtain the metal-containing mesoporous nano silicon spheres. Although the synthesis method is mature, a plurality of disadvantages still exist. First, the most central step in the whole experimental process is the formation of micelles, but in the actual synthesis process, not every metal ion is reduced to form a stable micelle structure with the amphoteric polymer. For example, this method is not suitable for transition metals, and thus has a limitation in versatility. Second, this approach has great complexity in the synthesis process. Thirdly, only the metal-containing mesoporous nano silicon spheres can be obtained by the synthesis method, and no hollow region exists in the nano silicon spheres, so that the application field of the material is greatly limited, for example, the material cannot be applied to the aspect of medicine. Another micelle template method mainly utilizes self-assembled amphoteric polymers such as poly (styrene-2-vinylpyridine-b-ethylene oxide) (PS-PVP-PEO). The amphoteric polymer is self-assembled in the aqueous phase to form micelles by means of certain pretreatment such as dialysis and the like. Then, silica was deposited on the template by adding tetramethyl orthosilicate (TMOS) using the micelle as a template. Finally, a series of post-treatments such as centrifugation and roasting are carried out to obtain the mesoporous hollow nano silicon spheres. Although this synthesis method can deposit various materials, even metals, on the micelle template, it still has several disadvantages. First, there is still a great deal of complexity in the synthesis process. In the synthesis, formation of self-assembled micelles requires a series of pretreatment such as dialysis. This makes the synthesis process complicated throughout the experiment. Secondly, only mesoporous hollow nano-silicon spheres can be synthesized by the method, and no metal or metal oxide exists in the hollow area of the material. This structure also greatly limits the range of applications of the material, such as catalysis.
Therefore, in order to make up for the defects of the existing synthesis method, a novel synthesis method is proposed. Compared with the existing synthesis method, the method is simpler and more universal. Meanwhile, the novel synthesis method not only makes up for the defects of the existing synthesis method, but also has the common advantages of the existing materials.
The material is then applied in the treatment of organic dye wastewater. The existing dye wastewater treatment technologies mainly include Wet air oxidation technology, Wet air catalytic oxidation technology, ozone oxidation technology, Fenton oxidation technology, photocatalytic oxidation technology, and electrocatalytic oxidation technology, etc., please refer to [6] F.Luck, Wet air oxidation: Past, present and future. Cat.today 1999,53, 81-91; [7] J.Levec, A.Pittar.catalytic wet-oxidation processes A.review.Catal.Total 2007, 124172-184; [8] K.El-sousy, A.Hussen, K.Hartani, H.El-Aila, Elimination of organic polutants using supported catalysts with hydrogen peroxide, Jordan J.chem.2007,2, 97-103; [9] sun, C.Chen, W.Ma, J.ZHao.Photodegradation of organic polutants catalyzed by proton semiconductors under visible light irradiation. Phys.chem.chem.Phys.2011,13, 1957-; [10] Y.Deng, J.D.Englehardt.treatment of landfilled leach by the Fenton process.Water Res.2006,40, 3683-3694; [11] bautista, A.F.Mohedano, J.A.Casas, J.A.Zazo, J.J.Rodriguez.an overview of the application of fendonoxidation to industrial waters waste stream, J.chem.Technol.Biotechnol.2008,83, 1323-Chi 1338; [12] (iii) S.J.Masten, S.H.R.Davies, The use of azo to degradable contaminants in waters Environ.Sci.Technol.1994,28,180A-185A; [13] Martinez-Huitee, E.Brillas, subtraction of water semiconductors synthetic organic means by electrochemical methods A general review. appl.Catal., B2009, 87, 105-145. However, the prior art has more or less disadvantages, so that the prior art cannot be widely applied to the treatment of organic wastewater. For example, wet air catalytic oxidation technology uses heterogeneous catalysts, but the reaction requires higher temperature and pressure, which greatly increases the cost of organic wastewater treatment and the difficulty of process operation. Secondly, part of active components in the heterogeneous catalyst can be lost along with the reaction, so that the service life of the catalyst can be reduced, and secondary pollution of organic wastewater can be caused. For another example, fenton oxidation technology is a commonly used technology in organic wastewater treatment at present, but has the disadvantages of high labor intensity, high operation difficulty, high cost and the like. Therefore, in the treatment of organic wastewater, a treatment technique which is easy to operate and safe is required.
In contrast, in the prior art documents [14] L.Zhou, W.Song, Z.Chen, G.yin.Degradation of organic polutants in Water by Bicarbonateactivated Hydrogen Peroxide with As-added Cobalt Catalyst, Environmental Science & Technology,2013, 3833-containing 3839, the use of sodium bicarbonate, Hydrogen Peroxide and a supported Cobalt oxide Catalyst system for treating organic Wastewater is mainly proposed. The main principle is that the catalyst is used for decomposing hydrogen peroxide to generate hydroxyl radicals to oxidize organic matters in the dye wastewater. The sodium bicarbonate is used for keeping the reaction solution in a weakly alkaline condition, so that the loss of active components of the catalyst and the content of cobalt ions in the organic wastewater along with the catalytic reaction are reduced, and the secondary pollution of the organic dye wastewater is avoided. Although the technology can solve the problems of the prior art, such as the use of the transition metal cobalt oxide as the catalyst, the cost can be reduced. By using the sodium bicarbonate and hydrogen peroxide system, the loss of active components in the catalyst can be reduced, and the cycle life of the catalyst can be prolonged. However, there are still some disadvantages to this technique. Firstly, the reaction rate is too slow in the treatment of organic dye wastewater, about 90% of methylene blue can be decomposed in about 80min, and about 5h is needed to reach more than 99%. Secondly, although the loss of the active components of the catalyst can be reduced by using a hydrogen peroxide and sodium bicarbonate system, the loss of the active components of the catalyst cannot be effectively prevented, so that the cycle number is reduced. Thirdly, although the content of cobalt ions in the organic wastewater can be reduced to 1ppm by using the supported catalyst, the content of cobalt ions in the waste liquid cannot be further reduced.
Disclosure of Invention
The invention aims to solve the defects of the existing synthesis method of nano silicon spheres and provides a synthesis method of hollow nano silicon spheres containing metal, which not only has a simple synthesis process, but also can be suitable for various metals. Meanwhile, the nano silicon ball material prepared by the synthesis method disclosed by the invention has the common advantages of the existing materials, namely, the nano silicon ball material contains metal, has a mesoporous and hollow structure, and thus the application range of the material is expanded.
The specific technical scheme of the invention is as follows:
the synthesis method of nano silicon ball reactor adopts polymer L2Metal ions and diblock polymer poly (N-met)hyl-2-vinyl-pyridiniumiodide)-b-poly(ethyleneoxide)(P2MVP128-b-PEO477) Three raw materials, wherein L2And P2MVP128-b-PEO477The specific structural formula is shown as formula 1 and formula 2:
the synthesis method comprises the following steps: first L2Complexing with metal ions through coordination to form a plurality of anion chains with negative charges; followed by the anionic chains and the positively charged diblock polymer P2MVP128-b-PEO477The polymer is combined together through the charge effect to form micelles in the water phase; then depositing silicon dioxide, zirconium dioxide or titanium dioxide on the micelle as a template; finally, the mesoporous hollow nano silicon spheres containing metal or metal oxide are obtained through post-treatment.
Further, the metal or its metal oxide means cobalt, nickel, iron, copper, zinc, manganese, palladium, platinum, gold or its metal oxide.
Furthermore, the loading amount of the metal and the metal oxide accounts for 2 per mill-10% of the total mass.
The process of the flow chart for synthesizing the mesoporous hollow nano silicon spheres containing the transition metal oxide is shown in figure 2. The formation process of the micelle is specifically illustrated by taking divalent cobalt ions as an example. The divalent cobalt ions are tetra-coordinated so that each cobalt ion can be associated with two L2Coordinate to form a negatively charged M-L2An anionic chain. Simultaneously utilizing positively charged P2MVP128-b-PEO477Diblock polymers, by charge reaction of M-L2And P2MVP128-b-PEO477The two are combined together to form a micelle. And then using the template to deposit materials such as silicon dioxide and the like. Finally, the mesoporous hollow nano silicon sphere material containing the transition metal oxide is obtained through post-treatment such as roasting.
Compared with the prior art, the synthesis method has the technical effects that: firstly, in the process of forming the micelle, the synthesis method of the invention is only used for adding three raw materials into a water phase according to a certain proportion, and then the micelle containing metal ions can be formed after the PH is adjusted to a certain range, thereby greatly simplifying the whole synthesis process. Secondly, the method of the invention has good universality in the universality. Not only suitable for transition metals, but also suitable for noble metals. Thirdly, in the synthesized material structure, the synthesized material structure of the invention takes into account all the advantages of the synthesized material by the existing method, and the material not only contains metal, but also has mesoporous and hollow structures. Therefore, the synthesized material can be applied to wider fields.
Furthermore, the mesoporous hollow nano-silica sphere catalyst containing cobalt oxide prepared by the synthesis method of the invention replaces the supported catalyst used in the existing method to carry out organic wastewater treatment and application.
Compared with the prior art, the application of the synthetic material has the technical effects that: first, cobalt oxide, which is an active component of the catalyst using the synthetic material of the present invention, is highly dispersed, and the sites where the catalytic reaction proceeds are in the hollow regions of the material, as compared to the supported catalyst. Therefore, the concentration of reactants and the probability of reactant contact should be much greater compared to supported catalysts. Second, the amount of cobalt ions dissolved in the organic wastewater is further reduced. Under the same conditions, although the dissolution of cobalt ions is still unavoidable with the catalysts of the invention, even if cobalt ions dissolve, they must come out of the catalyst if they are to be put into solution. Therefore, the content of cobalt ions in the organic wastewater tends to be lower than that of the supported catalyst. Thirdly, the synthetic material of the invention has fast adsorption rate and good adsorption capacity when being used as a catalyst. Fourth, the loading of the catalyst with the synthetic material of the invention as the active component of the catalyst was 1.4 wt%, whereas the loading in the literature was 2.5 wt%. It is clear that the present invention will use relatively less active component than the supported catalyst. Fifthly, the synthetic material of the invention is used as a catalyst and has good recycling performance in the wastewater degradation of methylene blue. Here, methylene blue degradation experiments were carried out using a methylene blue solution as a representative of organic wastewater, using the present invention as a catalyst under the same conditions as in reference [1] Z.Chen, Z.M.Cui, F.Niu, L.Jiang, W.G.Song, chem.Commun.2010,46, 6524-. The degradation rate and the degradation degree of methylene blue are determined by ultraviolet spectrum. The content of cobalt ions in the reacted liquid was determined by plasma spectrometer (ICP). Finally, the catalyst of the invention is used for degrading other various dyes, such as acid red, cresol red, methyl orange, rhodamine 6G and the like, and has excellent degradation rate and degradation effect, which is enough to prove that the synthetic material of the invention can be applied to various acidic, neutral and basic dyes by being used as the catalyst.
Drawings
FIG. 1 is a flow chart of a method for synthesizing mesoporous hollow nano silicon spheres containing transition metal oxides;
FIG. 2 transmission electron micrograph a), MnxOy@h-silica；b),ZnO@h-silica；c),CoxOy@h-silica；d),NixOy@h-silica；e),CuO@h-silica；f),FexOy@ h-silica; h) -l) respectively corresponding high power electron micrographs;
FIG. 3 degradation of methylene blue UV spectrum: mesoporous hollow nano silicon spheres containing cobalt oxide (every 5 min/time);
FIG. 4 degradation of methylene blue UV spectrum: loading cobalt oxide catalyst (every 5 min/time);
FIG. 5 is a graph showing the ultraviolet spectrum measurement of the degradation reaction of methylene blue by the synthesized catalyst;
FIG. 6 test chart of catalyst cycle;
FIG. 7 is a graph of methylene blue adsorbed solution of the catalyst;
FIG. 8 is a schematic diagram of the degradation of various fuels by mesoporous hollow nano-silica sphere catalysts containing cobalt oxide;
fig. 9 is a schematic diagram of the degradation of various fuels by the mesoporous hollow nano-silica sphere catalyst containing cobalt oxide.
Detailed Description
Synthesis of nano silicon ball reactorMethod using polymer L2Metal ions and a diblock polymer poly (N-methyl-2-vinyl-pyridine) b-poly (ethylene oxide) (P2 MVP)128-b-PEO477) Three raw materials, wherein L2And P2MVP128-b-PEO477The specific structural formula is shown as formula 1 and formula 2:
the synthesis method comprises the following steps: first L2Complexing with metal ions through coordination to form a plurality of anion chains with negative charges; followed by the anionic chains and the positively charged diblock polymer P2MVP128-b-PEO477The polymer is combined together through the charge effect to form micelles in the water phase; then depositing silicon dioxide on the surface by using the micelle as a template; and finally, carrying out post-treatment to obtain the mesoporous hollow nano silicon spheres containing the transition metal oxide.
The process of the flow chart for synthesizing the mesoporous hollow nano silicon spheres containing the transition metal oxide is shown in figure 2. The formation process of the micelle is specifically illustrated by taking divalent cobalt ions as an example. The divalent cobalt ions are tetra-coordinated so that each cobalt ion can be associated with two L2Coordinate to form a negatively charged M-L2An anionic chain. Simultaneously utilizing positively charged P2MVP128-b-PEO477Diblock polymers, by charge reaction of M-L2And P2MVP128-b-PEO477The two are combined together to form a micelle. And then using the template to deposit materials such as silicon dioxide and the like. Finally, the mesoporous hollow nano silicon sphere material containing the transition metal oxide is obtained through post-treatment such as roasting.
The preparation process is described in detail by taking the preparation of the mesoporous hollow nano silicon spheres containing nickel oxide as an example. Mainly, a certain amount of L3, P2MVP128-b-PEO477 and Ni (NO)3 solution are added into deionized water and stirred to be fully mixed. And then adjusting the pH value to 4-5, and stirring for a certain time. Tetramethyl orthosilicate is added. Stirring for two days at normal temperature, standing for four days to fully hydrolyze and polymerize the tetramethyl orthosilicate. And (3) centrifugally separating the obtained substance, washing with water and ethanol, and drying and roasting to obtain the mesoporous hollow nano material containing nickel oxide.
Furthermore, the mesoporous hollow nano-silica sphere catalyst containing cobalt oxide prepared by the synthesis method of the invention replaces the supported catalyst used in the existing method to carry out organic wastewater treatment and application. The method is mainly represented by a methylene blue solution, and the specific test process refers to the existing literature and carries out certain improvement on the literature process. Firstly, the catalyst and deionized water are put together and stirred, then the hydrogen peroxide, the sodium bicarbonate and the methylene blue are added into the catalyst aqueous solution together, and the stirring and the timing are carried out. Then, 1ml of the reaction solution was taken every 5min to measure the ultraviolet absorption spectrum. The degradation rate of the organic matter is judged by the change of the height of the absorption peak in the ultraviolet spectrum. The specific degree of decomposition is then determined by plotting a standard curve.
In the recycling of the catalyst, the experimental conditions were the same as in the above experimental procedure, and the only difference was that the catalyst after each reaction was not taken out, but the catalyst was allowed to continuously react. After 1 hour of each reaction, 244ul of the stock solution was taken out and diluted 20-fold to determine the extent of reaction progress. Then, methylene blue and hydrogen peroxide are added to ensure that the volume of reaction liquid, the amount of treated methylene blue and the amount of added hydrogen peroxide are kept unchanged to determine the recycling performance of the catalyst.
The method for synthesizing the metal-containing mesoporous hollow nano silicon spheres overcomes the defects of the existing method, such as complex preparation process, no universality of the method and the like. And the prepared material has a plurality of advantages of the existing material. Namely, the mesoporous hollow material contains metal. FIG. 2 transmission electron micrograph a), MnxOy@h-silica；b),ZnO@h-silica；c),CoxOy@h-silica；d),NixOy@h-silica；e),CuO@h-silica；f),FexOy@ h-silica; h) l) high power electron micrographs corresponding to each. Therefore, the application range of the material of the invention is enlarged.
The degradation experiment of methylene blue was performed using the synthesized catalyst. Under the same experimental conditions as the literature, the catalyst can be degraded by about 90% in about 5min, while about 40min is needed for the supported catalyst to reach about 90% in the literature, and the ultraviolet spectrum of the reaction is shown in fig. 3 and 4. Thus, the rate of degradation of methylene blue is significantly faster with this catalyst. Meanwhile, in order to prove that the catalyst not only acts on the dye wastewater, but also performs experiments on the degradation of the carmine wastewater, a good degradation rate is also found. And the cobalt ion content in the solution after the reaction was also determined. The cobalt ion content of the solution after the catalytic reaction was found to be about 0.2ppm, which is much less than the 1ppm given in the literature, by ICP measurement. Therefore, the catalyst can effectively reduce the dissolution of active components in the catalyst into organic wastewater.
Meanwhile, the experiment of the catalyst cycle performance is also carried out, and the catalyst cycle performance is tested by carrying out the degradation reaction of methylene blue by using the synthesized catalyst under the same reaction conditions as the literature. The catalyst is not removed after each reaction but is allowed to react continuously. Under the condition of ensuring that the total solution volume, the methylene blue treatment amount and the hydrogen peroxide adding amount of each reaction are not changed, the ultraviolet spectrum is measured after each reaction is carried out for 1 hour. Through the above tests of catalyst cycle, the decomposition degree of 4 times of methylene blue is above 95%, and the specific results are shown in fig. 4 and fig. 5. This can prove that the catalyst has good recycling performance. Then, the content of cobalt ions in the solution after 5 cycles of reaction was measured, and the content of cobalt ions was about 1 ppm. This is the same as the reference which utilizes a supported cobalt oxide catalyst system to carry out a single treatment of the methylene waste water and then the cobalt ion content in the solution. This indicates that this catalyst has a relatively better ability to limit the loss of active component.
In addition, in order to exclude the decrease of the absorption peak of methylene blue in the ultraviolet ray, the decrease is caused only by the adsorption of the catalyst, and the adsorption performance of the material is also measured. Similarly, the adsorption performance of the catalyst was tested under the same experimental conditions as in the literature but without adding hydrogen peroxide, and the results are shown in fig. 7. As can be seen, this material has a very fast adsorption rate. The adsorption balance can be reached in about 20 min. And the adsorption rate is the fastest in the first 5min, and about 40% of the adsorption can be probably realized. This demonstrates that this catalyst has a good adsorption capacity. Meanwhile, the good reaction rate of the catalyst is related to the good adsorption performance of the catalyst, and the existing mass transfer resistance is small.
Then, degradation reaction is carried out on other kinds of dyes by using the same method, and good degradation effect is found, which proves that the catalyst has good catalytic activity on acid, alkaline and neutral dyes. The specific results are shown in fig. 8 and 9.
Claims (5)
1. The synthesis method of the nano silicon ball reactor is characterized by adopting three raw materials of polymer L2, metal ions and diblock polymer poly (N-methyl-2-vinyl-pyridinium-iodide) -b-poly (ethylene oxide) (P2MVP128-b-PEO477), wherein the specific structural formulas of L2 and P2MVP128-b-PEO477 are shown as formula 1 and formula 2:
the synthesis method comprises the following steps: firstly, L2 and metal ions are complexed together through coordination to form a plurality of anion chains with negative charges; then the anionic chains and the diblock polymer P2MVP128-b-PEO477 with positive charges are combined together through the charge action to form micelles in the water phase; then depositing silicon dioxide, zirconium dioxide or titanium dioxide on the micelle as a template; finally, the mesoporous hollow nano silicon spheres containing metal or metal oxide are obtained through post-treatment.
2. The method as claimed in claim 1, wherein the metal or metal oxide thereof is cobalt, nickel, iron, copper, zinc, manganese, palladium, platinum, gold or metal oxide thereof.
3. The synthesis method of the nano silicon sphere reactor according to claim 1 or 2, wherein the loading amount of the metal and the metal oxide is 2% o to 10% of the total mass.
4. The mesoporous hollow nano-silicon spheres containing metal or metal oxide prepared by the synthesis method of claim 1.
5. The application of the mesoporous hollow nano-silica spheres containing metal or metal oxide prepared by the synthesis method of claim 1 as a catalyst for organic wastewater treatment.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104646033A (en) * | 2015-02-17 | 2015-05-27 | 浙江工业大学 | Sulfonic functionalized mesoporous silicon dioxide microsphere loaded metal oxide catalyst and preparation method and application of catalyst |
| CN106984261A (en) * | 2017-05-16 | 2017-07-28 | 浙江工业大学 | A kind of CoFe2O4/ N/C hollow nano-spheres and its preparation and application |
| CN109701538A (en) * | 2018-12-28 | 2019-05-03 | 华东理工大学 | A kind of synthetic method and its application of nano silicon spheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104646033A (en) * | 2015-02-17 | 2015-05-27 | 浙江工业大学 | Sulfonic functionalized mesoporous silicon dioxide microsphere loaded metal oxide catalyst and preparation method and application of catalyst |
| CN106984261A (en) * | 2017-05-16 | 2017-07-28 | 浙江工业大学 | A kind of CoFe2O4/ N/C hollow nano-spheres and its preparation and application |
| CN109701538A (en) * | 2018-12-28 | 2019-05-03 | 华东理工大学 | A kind of synthetic method and its application of nano silicon spheres |
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