CN109437309B - Synthetic method of shuttle-shaped structure manganese carbonate nano material - Google Patents
Synthetic method of shuttle-shaped structure manganese carbonate nano material Download PDFInfo
- Publication number
- CN109437309B CN109437309B CN201811417697.7A CN201811417697A CN109437309B CN 109437309 B CN109437309 B CN 109437309B CN 201811417697 A CN201811417697 A CN 201811417697A CN 109437309 B CN109437309 B CN 109437309B
- Authority
- CN
- China
- Prior art keywords
- manganese carbonate
- shuttle
- solution
- kmno
- glucose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of nano material preparation, and provides a method for synthesizing a shuttle-shaped structure manganese carbonate nano material, which comprises the following steps: KMnO with a certain concentration is prepared4Solutions, PEG20000 solutions and glucose solutions; taking a certain volume of KMnO4Mixing the solution with PEG20000 solution to obtain KMnO4And PEG20000 in an amount of 0.01mol and 0.0261g, respectively, and stirring at 90 deg.C; adding a glucose solution into the mixed solution of S2, wherein the adding amount of glucose is 0.015-0.06 mol, and continuously stirring for 2-5 h at constant temperature; stopping stirring, cooling to room temperature, filtering, and drying the solid product to obtain the pure-phase manganese carbonate. The invention solves the technical problems that the manganese carbonate nano material only has rod and particle shapes and has single appearance in the prior art.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and relates to a synthetic method of a shuttle-shaped structure manganese carbonate nano material.
Background
The nanometer material has many peculiar properties different from the substances with larger particle size, has wide application potential in the aspects of materials, information, energy, environment, life, military and the like, and becomes an important strategic field occupying the high-tech and global economic competition of the century in all countries of the world, the oxide of the manganese is a multifunctional material and is concerned by people, the oxide of the nanometer manganese has surface effect, small-size effect, quantum size effect and the like, compared with the oxide of the manganese with the conventional size, the performance is more excellent, the shape of the oxide of the nanometer manganese is different, the performance is greatly changed, more application purposes and fields can be developed, the oxide of the manganese is generally obtained by the manganese carbonate under the condition of high-temperature calcination, the method is convenient, rapid and pollution-free, and the particle size of the prepared oxide of the manganese and the particle size of the manganese carbonate are basically kept unchanged, the original nanometer appearance of manganese carbonate can be kept, so that people are more urgent to search for manganese carbonate nanometer materials with more appearances, the existing manganese carbonate nanometer materials are in a particle type and a rod type, the manganese carbonate nanometer materials with the appearances are limited in application, no substantial progress is made in the research of preparing manganese carbonate nanometer materials with other appearances, the preparation process of common nanometer materials is complex, the synthesis temperature is high, and a plurality of organic solvents are used to pollute the environment.
In a preparation method of manganese-zinc-iron oxide nano powder in patent CN106365205B, the heat treatment temperature in the disclosed preparation method needs to reach 500-800 ℃, the energy consumption is large, the cost is high, the reaction process is complex, the prepared nano material is a powdery nano material, in a preparation method of a manganese carbonate nanorod in patent CN101805024B, a method for preparing a rod-shaped manganese carbonate nano material is disclosed, the preparation method is relatively simplified, but hydrogen peroxide is still used, the reaction temperature also needs to reach 180 ℃, and the time needs to reach 16-24 hours, so the problems in the prior art are as follows:
1. the time for preparing the nano material is long and the temperature is high;
2. the manganese carbonate nano material prepared is mostly rod-shaped and granular, and has single appearance
3. The reaction contains substances harmful to the environment, and waste liquid is not easy to treat.
Disclosure of Invention
The invention provides a method for synthesizing a shuttle-shaped structure manganese carbonate nano material, which solves the technical problem.
The technical scheme of the invention is realized as follows:
a method for synthesizing a shuttle-structure manganese carbonate nano material comprises the following steps: the method comprises the following steps:
s1, preparing KMnO with certain concentration4Solutions, PEG20000 solutions and glucose solutions;
s2, taking a certain volume of KMnO4Mixing the solution with PEG20000 solution to obtain KMnO4And PEG20000 in an amount of 0.01mol and 0.0261g, respectively, and stirring at 90 deg.C;
s3, adding the glucose solution into the mixed solution of S2, wherein the adding amount of glucose is 0.015-0.06 mol, and continuously stirring at constant temperature for 2-5 h;
and S4, stopping stirring, cooling to room temperature, filtering, and drying the solid product to obtain the pure-phase manganese carbonate.
As a further technical scheme, KMnO prepared in S14The concentrations of the solution and the glucose solution were 0.1mol/L and 0.2mol/L, respectively.
As a further technical proposal, the adding amount of the glucose in S3 is preferably 0.02 mol.
As a further technical proposal, the time for continuing the reaction in S3 is specifically 3 h.
As a further technical scheme, the drying temperature in the step S4 is 60 ℃.
As a further technical scheme, the solid product is washed 3-5 times by distilled water during filtration in S4.
As a further technical scheme, the pure-phase manganese carbonate obtained in S4 is in a shuttle-shaped MnCO shape assembled by nano rods3。
Compared with the prior art, the invention has the working principle and the beneficial effects that:
1. in the invention, long-chain PEG20000 is used as a template to promote MnCO3The nano-rods are formed and assembled, in the reaction, reactants and products are harmless to the environment, the waste liquid is easy to treat, and the KMnO is realized under the conditions of low temperature and short time4Synthesis of MnCO by reaction with glucose3And preparing MnCO with shuttle-shaped morphology3The nano-materials are assembled by nano-rods, so the invention makes substantial progress in preparing manganese carbonate nano-materials with other morphologies.
2. In the invention, the polyethylene glycol has a straight chain structure, and the chain length is different according to the difference of the molecular weight of the polyethylene glycol, in the experiment, PEG20000 with longer chain length is used as a template, when MnCO3 is formed, under the influence of hydrogen bonds at two ends of the polyethylene glycol, MnCO3 can grow along the straight chain, so that nanorods are formed, meanwhile, the nanorods are connected together, and finally assembled into a shuttle-shaped structure, and when PEG6000 is used, the chain length is greatly shortened. It can also be seen from the SEM image of the product that the final morphology is also spindle-shaped, but the rod-like structure cannot be clearly seen, so that it can be shown that the chain length of PEG has a great influence on the formation of the morphological structure of the sample.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is an XRD pattern of a sample obtained in example two of the present invention;
FIG. 2 is an SEM photograph of a sample obtained in example two of the present invention;
FIG. 3 is an SEM image of a sample obtained in example III of the present invention;
FIG. 4 is an XRD pattern of samples obtained in examples one and four of the present invention;
FIG. 5 is an SEM image of samples obtained in examples one and four of the present invention;
FIG. 6 is an XRD pattern of a sample obtained in comparative example one of the present invention;
FIG. 7 is an SEM image of a sample obtained in comparative example one of the present invention;
FIG. 8 is an SEM image of a sample obtained by a comparative example of the present invention;
FIG. 9 is an SEM image of a sample obtained in comparative example III of the present invention;
FIG. 10 is an SEM photograph of a sample obtained in comparative example four of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in FIGS. 1 to 10, the present invention provides a method for synthesizing manganese carbonate nanomaterial with shuttle structure,
the first embodiment is as follows: placing the neck flask in a constant temperature water bath at 90 ℃, and adding KMnO4Adding the solution (0.1mol/L, 100mL) and polyethylene glycol 20000(PEG20000) solution (0.0261g, 10mL) into a three-necked flask, adding a magnetic stirrer, and stirring continuously; then adding the prepared glucose solution (0.15mol/L, 100mL) into the solution, and continuing to react for 2 h; then connecting the three necksThe flask is taken out of the water bath, placed and cooled to room temperature, the obtained precipitate is subjected to suction filtration, and is washed with distilled water for a plurality of times, and then the precipitate is dried in an oven at 60 ℃.
Example two: placing the neck flask in a constant temperature water bath at 90 ℃, and adding KMnO4Adding the solution (0.1mol/L, 100mL) and polyethylene glycol 20000(PEG20000) solution (0.0261g, 10mL) into a three-necked flask, adding a magnetic stirrer, and stirring continuously; then adding the prepared glucose solution (0.2mol/L, 100mL) into the solution, and continuing to react for 3 h; and taking the three-neck flask out of the water bath, standing, cooling to room temperature, carrying out suction filtration on the obtained precipitate, washing with distilled water for a plurality of times, and drying the precipitate in an oven at 60 ℃.
Example three: placing the neck flask in a constant temperature water bath at 90 ℃, and adding KMnO4Adding the solution (0.1mol/L, 100mL) and polyethylene glycol 20000(PEG20000) solution (0.0261g, 10mL) into a three-necked flask, adding a magnetic stirrer, and stirring continuously; then adding the prepared glucose solution (0.2mol/L, 100mL) into the solution, and continuing to react for 5 h; and taking the three-neck flask out of the water bath, standing, cooling to room temperature, carrying out suction filtration on the obtained precipitate, washing with distilled water for a plurality of times, and drying the precipitate in an oven at 60 ℃.
Example four: placing the neck flask in a constant temperature water bath at 90 ℃, and adding KMnO4Adding the solution (0.1mol/L, 100mL) and polyethylene glycol 20000(PEG20000) solution (0.0261g, 10mL) into a three-necked flask, adding a magnetic stirrer, and stirring continuously; then adding the prepared glucose solution (0.6mol/L, 100mL) into the solution, and continuing to react for 3 h; and taking the three-neck flask out of the water bath, standing, cooling to room temperature, carrying out suction filtration on the obtained precipitate, washing with distilled water for a plurality of times, and drying the precipitate in an oven at 60 ℃.
Comparative example one: placing the neck flask in a constant temperature water bath at 90 ℃, and adding KMnO4Adding the solution (0.1mol/L, 100mL) and polyethylene glycol 20000(PEG20000) solution (0.0261g, 10mL) into a three-necked flask, adding a magnetic stirrer, and stirring continuously; then adding the prepared glucose solution (0.2mol/L, 100mL) into the solution, and continuing to react for 1 h; then taking the three-neck flask out of the water bath kettle and placing the three-neck flask in a cold stateCooling to room temperature, suction filtering the obtained precipitate, washing with distilled water for several times, and drying the precipitate in a 60 ℃ oven.
Comparative example two: placing the neck flask in a constant temperature water bath at 90 ℃, and adding KMnO4Adding the solution (0.1mol/L, 100mL) and polyethylene glycol 20000(PEG6000) solution (0.0261g, 10mL) into a three-necked flask, adding a magnetic stirrer, and stirring continuously; then adding the prepared glucose solution (0.2mol/L, 100mL) into the solution, and continuing to react for 3 h; and taking the three-neck flask out of the water bath, standing, cooling to room temperature, carrying out suction filtration on the obtained precipitate, washing with distilled water for a plurality of times, and drying the precipitate in an oven at 60 ℃.
Comparative example three: placing the neck flask in a constant temperature water bath at 90 ℃, and adding KMnO4Adding the solution (0.1mol/L, 100mL) and polyoxyethylene ether solution (0.0261g, 10mL) into a three-neck flask, adding a magnetic stirrer, and stirring continuously, wherein the molecular weight of the polyoxyethylene ether is similar to that of PEG20000 in the example; then adding the prepared glucose solution (0.2mol/L, 100mL) into the solution, and continuing to react for 3 h; and taking the three-neck flask out of the water bath, standing, cooling to room temperature, carrying out suction filtration on the obtained precipitate, washing with distilled water for a plurality of times, and drying the precipitate in an oven at 60 ℃.
Comparative example four: the polyoxyethylene ether in the comparative example was replaced with polyvinylpyrrolidone or cetyltrimethylammonium bromide.
TABLE 1 comparison table of parameter changes in examples and comparative examples
It can be seen from FIG. 1 that the sample obtained in example two of the present invention is pure-phase MnCO3And the scanning electron microscope image of fig. 2 shows that the obtained sample is in a shuttle-shaped structure assembled by nanorods, three of the images are display images of a scale which is gradually enlarged, so that the overall nano morphology is in the shuttle-shaped structure, and each shuttle-shaped structure is assembled by the nanorods after further enlargement, therefore, the embodiment obtains the nano-material with the shuttle-shaped structureNovel nano-shaped MnCO3The nano material has the advantages of simple synthesis steps, low temperature, short time, no addition of substances harmful to the environment in the process, and easy treatment of waste liquid.
As can be seen from FIG. 3, in the third example, when the reaction time is prolonged to 5 hours, the morphology of the obtained sample is still shuttle-shaped, which is substantially the same as that of the second example.
As can be seen from FIGS. 4 and 5, in examples one and four, the reaction time was shortened or the amount of glucose was increased, and the resulting material was also pure-phase MnCO3And the morphology of the sample is still shuttle-like or may also be referred to as peanut-like.
As can be seen from FIGS. 6 and 7, the sample obtained in the first comparative example is pure-phase birnessite-type manganese dioxide and is in the form of nanoparticles with non-smooth surfaces, which indicates that the influence factor of the reaction time is large, and MnCO cannot be formed in the reaction time of 1h3The shuttle-type nanostructure of (1).
Fig. 8 shows that, in the comparative example, after PEG20000 is changed to PEG6000, the obtained sample still has a spindle structure as a whole, but the spindle structure is not assembled from rods, but is composed of nanoparticles.
As can be seen from FIGS. 9 to 10, the samples obtained by replacing PEG with other surfactants in the third and fourth comparative examples did not form a spindle-shaped structure assembled in a rod shape and did not form a regular shape, indicating that PEG20000 does not function as a surfactant alone but as a structural template, and MnCO is used as MnCO3Will grow along the linear chain to form nanorods and also connect the nanorods together to finally assemble into a spindle-shaped structure, besides the chain length of PEG plays a decisive role.
The principle presumed from the experimental results in the experimental process is: the polyethylene glycol has a linear chain structure, the chain length is different according to the difference of the molecular weight, when PEG20000 with longer chain length is adopted as a template, and when MnCO3 is formed, under the influence of hydrogen bonds at two ends of the polyethylene glycol, MnCO3Will grow along a linear chain, thereby formingAnd (3) a shuttle-shaped structure assembled by nano rods.
In conclusion, the invention synthesizes the rod-shaped assembled MnCO on the premise of simple steps, short reaction time and low temperature3The spindle-shaped nano structure makes substantial progress in preparing manganese carbonate nano materials with other shapes, and can develop more MnCO in the future3The application of the nano material and the whole contract process are more environment-friendly and pollution-free, and the waste liquid is easy to treat.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A synthetic method of a shuttle-shaped structure manganese carbonate nano material is characterized by comprising the following steps:
s1, preparing KMnO with certain concentration4Solutions, PEG20000 solutions and glucose solutions;
s2, taking a certain volume of KMnO4Mixing the solution with PEG20000 solution to obtain KMnO4And PEG20000 in an amount of 0.01mol and 0.0261g, respectively, and stirring at 90 deg.C;
s3, adding the glucose solution into the mixed solution of S2, wherein the adding amount of glucose is 0.015-0.06 mol, and continuously stirring at constant temperature for 2-5 h;
and S4, stopping stirring, cooling to room temperature, filtering, and drying the solid product to obtain the pure-phase manganese carbonate.
2. The method for synthesizing manganese carbonate nanomaterial with shuttle-type structure as claimed in claim 1, wherein KMnO formulated in S14The concentrations of the solution and the glucose solution were 0.1mol/L and 0.2mol/L, respectively.
3. The method for synthesizing the shuttle-structured manganese carbonate nanomaterial according to claim 1, wherein the addition amount of glucose in S3 is preferably 0.02 mol.
4. The method for synthesizing manganese carbonate nanomaterial with shuttle-type structure according to claim 1, wherein the reaction time in S3 is 3 h.
5. The method for synthesizing manganese carbonate nanomaterial with shuttle-type structure according to claim 1, wherein the drying temperature in S4 is 60 ℃.
6. The method for synthesizing the shuttle-structured manganese carbonate nanomaterial according to claim 1, wherein the solid product is washed 3 to 5 times with distilled water during filtration in S4.
7. The method for synthesizing manganese carbonate nanomaterial with shuttle-shaped structure as claimed in claim 1, wherein the pure-phase manganese carbonate obtained in S4 is MnCO with shuttle-shaped morphology assembled by nanorods3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811417697.7A CN109437309B (en) | 2018-11-26 | 2018-11-26 | Synthetic method of shuttle-shaped structure manganese carbonate nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811417697.7A CN109437309B (en) | 2018-11-26 | 2018-11-26 | Synthetic method of shuttle-shaped structure manganese carbonate nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109437309A CN109437309A (en) | 2019-03-08 |
| CN109437309B true CN109437309B (en) | 2021-04-30 |
Family
ID=65555160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811417697.7A Active CN109437309B (en) | 2018-11-26 | 2018-11-26 | Synthetic method of shuttle-shaped structure manganese carbonate nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109437309B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116550320B (en) * | 2023-05-12 | 2024-02-02 | 河北地质大学 | Synthesis method of manganese dioxide nano material with neuron-like cell structure |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318706A (en) * | 2008-07-17 | 2008-12-10 | 湖北开元化工科技股份有限公司 | Method for preparing high-purity manganese carbonate with pyrolusite |
| WO2009157620A1 (en) * | 2008-06-25 | 2009-12-30 | Dongbu Fine Chemicals Co., Ltd. | Method of recovering a compound comprising manganese from dust of electronic furnace |
| CN101805024A (en) * | 2010-04-27 | 2010-08-18 | 江苏大学 | Preparation method of manganese carbonate nanorod |
| CN102531065A (en) * | 2010-12-30 | 2012-07-04 | 河南科隆集团有限公司 | Spherical manganese carbonate synthetic method |
| CN106865618A (en) * | 2017-02-23 | 2017-06-20 | 广西大学 | One kind " peanut shape " Mn2O3The preparation method of/C particles |
| CN106887606A (en) * | 2017-02-23 | 2017-06-23 | 广西大学 | One kind " peach-shaped " Mn2 O3The preparation method of/C particles |
| CN106914234A (en) * | 2017-02-23 | 2017-07-04 | 广西大学 | One kind " almond-shaped " Mn2O3The preparation method of/C particles |
-
2018
- 2018-11-26 CN CN201811417697.7A patent/CN109437309B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009157620A1 (en) * | 2008-06-25 | 2009-12-30 | Dongbu Fine Chemicals Co., Ltd. | Method of recovering a compound comprising manganese from dust of electronic furnace |
| CN101318706A (en) * | 2008-07-17 | 2008-12-10 | 湖北开元化工科技股份有限公司 | Method for preparing high-purity manganese carbonate with pyrolusite |
| CN101805024A (en) * | 2010-04-27 | 2010-08-18 | 江苏大学 | Preparation method of manganese carbonate nanorod |
| CN102531065A (en) * | 2010-12-30 | 2012-07-04 | 河南科隆集团有限公司 | Spherical manganese carbonate synthetic method |
| CN106865618A (en) * | 2017-02-23 | 2017-06-20 | 广西大学 | One kind " peanut shape " Mn2O3The preparation method of/C particles |
| CN106887606A (en) * | 2017-02-23 | 2017-06-23 | 广西大学 | One kind " peach-shaped " Mn2 O3The preparation method of/C particles |
| CN106914234A (en) * | 2017-02-23 | 2017-07-04 | 广西大学 | One kind " almond-shaped " Mn2O3The preparation method of/C particles |
Non-Patent Citations (1)
| Title |
|---|
| Controlled Synthesis of Mesoporous MnO2 Nanospindles;HAN Ling et al.;《Acta Physico⁃Chimica Sinica》;20111231;第27卷(第3期);摘要及第2部分实验 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109437309A (en) | 2019-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103949253B (en) | Cuprous oxide-titanium dioxide composite structure and preparation method thereof | |
| CN101372363B (en) | Synthetic alpha-MnO 2 Method for micron hollow sphere and nanocluster | |
| CN101514029B (en) | Method for preparing zinc oxide (ZnO) nanorods | |
| CN102942206A (en) | Method for preparing cerium dioxide nanometer hollow spheres | |
| CN106373785A (en) | Nickel cobalt oxide<@>manganese dioxide nuclear shell heterostructure nanowire array grown on carbon cloth and preparation method and application thereof | |
| CN105129857A (en) | Flower-shaped tungsten oxide nanometer material and preparing method thereof | |
| CN111099650A (en) | CeO2Molten salt method for synthesizing nano spherical particles | |
| CN102951669B (en) | Method for preparing CeO2 nano solid spheres by microwave-assisted urea hydrolysis | |
| CN109437309B (en) | Synthetic method of shuttle-shaped structure manganese carbonate nano material | |
| CN107039649A (en) | A kind of multistage hollow microsphere of copper based composite metal oxidate, preparation method and the usage | |
| CN105110384B (en) | Porous cobaltosic oxide and preparation method thereof | |
| CN105869907A (en) | Preparation method of carbon-nitrogen-codoped NiFe2O4-Ni nanocomposite material with cubic structure | |
| CN103979597A (en) | Preparation method of rod-like copper-cerium composite oxide | |
| CN113428890B (en) | CuS hollow sphere with secondary structure, preparation method and application thereof | |
| CN103130266A (en) | Preparation method of titanium dioxide hollow ball constructed by nano slices | |
| CN108046340B (en) | Method for preparing cobaltosic oxide multi-layer hollow nanospheres without template | |
| CN104609456B (en) | A kind of preparation method of the C/N codope cuprous nanosphere of porous oxidation based on sericin | |
| CN104336069B (en) | Fe3+Bacteria mildew-proof agent of doping multi-needle nano-ZnO and preparation method thereof | |
| CN113351216A (en) | Low-dimensional self-assembled flower-shaped Cu2Preparation method and application of O-ZnO catalyst | |
| CN101891246B (en) | Method for preparing composite-grain diameter nano titanium dioxide powder | |
| CN104445340A (en) | Method for preparing octahedral cerium oxide self-assembled by nano blocks | |
| CN102942204A (en) | Method for preparing cerium dioxide nanometer powder | |
| Habibi-Yangjeh et al. | Fabrication of magnetically recoverable nanocomposites by combination of Fe3O4/ZnO with AgI and Ag2CO3: Substantially enhanced photocatalytic activity under visible light | |
| CN103588244B (en) | Without the method for the sandwich hollow titanium dioxide nano material of template synthesis | |
| CN105776327B (en) | A kind of brockite and anatase mixed phase TiO of nanometer rods assembling2Micrometre hollow sphere and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210402 Address after: 050000 No.136 Huaian East Road, Shijiazhuang City, Hebei Province Applicant after: HEBEI GEO University Address before: 050000 NO.67 Yuhua West Road, Qiaoxi District, Shijiazhuang City, Hebei Province Applicant before: Hao Xinli |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |