CN105967167A - Method for preparing one-dimensional carbon nano material - Google Patents
Method for preparing one-dimensional carbon nano material Download PDFInfo
- Publication number
- CN105967167A CN105967167A CN201610325417.4A CN201610325417A CN105967167A CN 105967167 A CN105967167 A CN 105967167A CN 201610325417 A CN201610325417 A CN 201610325417A CN 105967167 A CN105967167 A CN 105967167A
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- halloysite nanotubes
- preparation
- method described
- water solution
- 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.)
- Granted
Links
Classifications
-
- 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
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The invention relates to a method for preparing a one-dimensional carbon nano material, belonging to the technical field of preparation of nano carbon materials. The method comprises the following steps: by using natural halloysite nanotubes as a template and polyvinyl alcohol as a carbon source, attaching the carbon source onto the halloysite nanotube surface by combining the carbon source with hydroxy groups on the template surface, and carrying out high-temperature carbonization, acid washing and template removal to obtain the carbon nanotube material; or fully filling and accumulating the carbon source in the template tubes, and carrying out high-temperature carbonization, acid washing and template removal to obtain the carbon nanorod material. Therefore, the product prepared by the technique is nanotubes, or nanorods or a nanotube-nanorod mixed material.
Description
Technical field
The invention belongs to the preparing technical field of nano-carbon material.
Background technology
CNT has typical stratiform hollow structure feature, and carbon nano rod is then solid club shaped structure feature.The good physical and chemical performance given owing to they have special structure so that it is can be used for the aspects such as battery, semi-conducting material, catalyst carrier, and it is described as environmental friendliness and for the wonder-working new material of the mankind.
The template of development in recent years is prepared carbon nanomaterial and is caused and pay attention to widely.Template has that synthesis technique is simple, the homogeneous plurality of advantages such as controlled of Stability Analysis of Structures and the pattern of synthetic material, size, dimension, at present, a lot of document report has been had to use hard template method to prepare one-dimensional carbon nano material, Hou etc. utilize anodic alumina films for template, prepare CNT [Hou P X. Templatesynthesis of ultra-thin and by chemical vapour deposition technique
short carbon nanotubes with two open ends[J].J.Mater.chem,2012,
22(30):15221-15226.].Liu et al. grows from titania nanotube and is evenly distributed, standing upright carbon nano rod [Liu S, Yang L, Xu S, Luo S, and Cai Q. on substrate
Photocatalytic activities of C-N-doped TiO2nanotube array/carbon
nanorod composite[J].Electrochem. Commun., 2009, 11(9):1748-1751.]。
The template used at present prepares 1-dimention nano pipe or carbon nano rod all exists template used and carbon source expensive, and preparation process is loaded down with trivial details, and condition is harsher, and environment is unfriendly, and safety coefficient is low, and the shortcoming such as consume energy higher.
Summary of the invention
The present invention seeks to propose a kind of to reduce production cost, improve the method preparing one-dimensional carbon nano material of safety coefficient.
The present invention comprises the following steps:
1) natural halloysite nanotubes is processed during roasting 6～8h is placed on 100～200 DEG C of baking ovens under 500～700 DEG C of temperature conditionss 12～24h, obtains halloysite nanotubes；Polyvinyl alcohol is dissolved in deionized water, forms the polyvinyl alcohol water solution that concentration is 15～30wt%；
2) halloysite nanotubes is mixed with polyvinyl alcohol water solution, drying, obtain polyvinyl alcohol/halloysite nanotubes complex；
3) polyvinyl alcohol/halloysite nanotubes complex is placed in tube furnace; in the lower calcining of nitrogen protection; then the halloysite nanotubes in polyvinyl alcohol/halloysite nanotubes complex is removed with the hydrofluoric acid aqueous solution that concentration is 20～40wt%; again through filtering, washing and be dried, obtain one-dimensional carbon nano material.
Above step 1) in natural halloysite nanotubes is carried out roasting after the specific surface area of halloysite nanotubes be increased to 30～60m2/ g, then be placed in baking oven process remove halloysite nanotubes be placed in air, the water that its surface is adsorbed.
The present invention is with natural halloysite nanotubes as template, with polyvinyl alcohol as carbon source, if carbon source is by the hydroxy combining with template surface, is attached to halloysite nanotubes surface, removes template procedure through high temperature cabonization pickling, then obtains carbon nano-tube material.As carbon source is filled in template caliber, and pile up in caliber, caliber is filled up, remove template procedure through high temperature cabonization pickling, then obtain carbon nano rod material.Therefore, present invention process is made product or for nanotube or for nanometer rods or for nanotube and the mixing material of nanometer rods.
Advantages of the present invention is as follows:
1, selected template is halloysite nanotubes, for natural clay, it is not necessary to preparation, and wide material sources,
Nontoxic, cheap.
2, simple to operate, it is not necessary to complex device, and carbon source/template composite under low temperature, can be prepared, fall
Low energy consumption, experimentation green safety.
3, by changing the addition of carbon source, controlled carbon nano-tube material or carbon nano rod material are prepared,
The aperture of gained CNT reaches 381.5m in about 20nm, specific surface area2/ g, the diameter of carbon nano rod reaches 400～420m at about 15nm and specific surface2/g。
Further, the aperture of described natural halloysite nanotubes is about 20～30nm, and specific surface is about 30～50m2/g.The halloysite nanotubes of this parameter is more beneficial for preparing product.
In step 1), the molecular weight of described polyvinyl alcohol is 11～130,000, and when being dissolved in deionized water by polyvinyl alcohol, solution temperature condition is 70～90 DEG C.The polyvinyl alcohol of this parameter is more beneficial for preparing product.
Step 2) in, halloysite nanotubes is 1: 0.5～3 with the mixing quality ratio of polyvinyl alcohol.Select this materials ratio that polyvinyl alcohol can be made sufficiently to be carried on halloysite nanotubes surface, or make polyvinyl alcohol be packed into more fully inside halloysite nanotubes.
Step 2) in, the temperature conditions carrying out halloysite nanotubes with polyvinyl alcohol water solution mixing is 40～60 DEG C；Described drying temperature is 40～60 DEG C.Select this temperature conditions can make reaction more fully so as to get polyvinyl alcohol/halloysite nanotubes complex evenly.
The method that halloysite nanotubes carries out mixing with polyvinyl alcohol water solution there are two kinds:
One, under condition of heating and stirring, is slowly added to halloysite nanotubes in polyvinyl alcohol water solution, then, is transferred to the halloysite nanotubes having adsorbed polyvinyl alcohol in baking oven dry, obtains polyvinyl alcohol/halloysite nanotubes complex.
Another kind of, polyvinyl alcohol water solution is dripped on halloysite nanotubes, until halloysite nanotubes all moistens, then the halloysite nanotubes having adsorbed polyvinyl alcohol is put in baking oven and dry, the process of dropping and drying that repeats, until polyvinyl alcohol water solution is all added dropwise to complete, obtains polyvinyl alcohol/halloysite nanotubes complex.
First method, simple to operate, polyvinyl alcohol, by the hydroxy combining with halloysite nanotubes surface, is attached to halloysite nanotubes surface, obtains polyvinyl alcohol/halloysite nanotubes complex, and this method can prepare carbon nano-tube material.
Second method, simple to operate, polyvinyl alcohol is populated in the caliber of halloysite nanotubes, and piles up in caliber, is filled up by caliber, obtains polyvinyl alcohol/halloysite nanotubes complex, and this method can prepare carbon nano rod material.
In step 3), described calcining heat is 500～800 DEG C, and heating rate is 5～10 DEG C/min, and calcination time is 2h～4h.Selecting this temperature, time conditions that reaction can be made more abundant, products therefrom effect is best.
In step 3), first use 5～10wt % aqueous hydrochloric acid solutions to wash during washing 4～5 times, clean 4～5 times with distilled water the most again.HF washing can be removed clean, make the pH of product present neutrality.
Accompanying drawing explanation
Fig. 1 is the TEM figure of embodiment 1 gained carbon nano-tube material.
Fig. 2 is the SEM figure of embodiment 3 gained carbon nano rod material.
Fig. 3 is the TEM figure of embodiment 3 gained carbon nano rod material.
Detailed description of the invention
The invention will be further described below in conjunction with the accompanying drawings.
Example 1:
Halloysite nanotubes is placed in 550 DEG C of roasting 6h in Muffle furnace, and cooling is placed in 100 DEG C of baking ovens and is dried 24h.
2g polyvinyl alcohol is added in deionized water, stirring and dissolving at 80 DEG C, be configured to the polyvinyl alcohol water solution of 15wt %.
Halloysite nanotubes after 3g roasting, drying and processing is slowly added in above polyvinyl alcohol water solution, at 50 DEG C, stirring makes the water in mixed system be dried as far as possible, then the halloysite nanotubes having adsorbed polyvinyl alcohol is put in 50 DEG C of baking ovens and dry, obtain polyvinyl alcohol/halloysite nanotubes complex.
This complex is placed in tube furnace; nitrogen (purity is 99.99%) protects lower 700 DEG C of calcining 3 h; heating rate is 5 DEG C/min; finally remove removing template halloysite nanotubes with Fluohydric acid. (30 wt%) stirring 48h washing; after filtration; use 5% dilute hydrochloric acid to wash 5 times, clean 5 times with distilled water the most again, be dried to obtain product carbon nano-tube material.
Scheme from the TEM of the embodiment 1 gained carbon nano-tube material of Fig. 1: the carbon nano-tube material aperture prepared reaches 381.5m in about 20nm, specific surface area2/g。
Example 2:
Halloysite nanotubes is placed in 550 DEG C of roasting 6h in Muffle furnace, and cooling is placed in 120 DEG C of baking ovens and is dried 24h.
4g polyvinyl alcohol is added in deionized water, stirring and dissolving at 80 DEG C, be configured to the polyvinyl alcohol water solution of 15 wt %.
Polyvinyl alcohol water solution is dropwise dripped in the 3g galapectite that just will take out from baking oven, make it fully absorb, until halloysite nanotubes the most all moistens, put in 50 DEG C of baking ovens and dry, repeat dropping and the process being dried, until polyvinyl alcohol water solution is all added dropwise to complete, obtain polyvinyl alcohol/halloysite nanotubes complex.
Being placed in tube furnace by this complex, nitrogen (purity is 99.999%) protects lower 700 DEG C of calcining 3h, and heating rate is 5 DEG C/min, finally uses HF(40
Wt%) the template halloysite nanotubes in product is removed in stirring 48h washing, after filtration, uses 5% dilute hydrochloric acid to wash 5 times, cleans 5 times with distilled water, be dried, obtain product carbon nano rod material, and diameter reaches 402.7m in about 15nm, specific surface area2/g。
Example 3:
Halloysite nanotubes is placed in 550 DEG C of roasting 6h in Muffle furnace, and cooling is placed in 120 DEG C of baking ovens and is dried 24h.
2g polyvinyl alcohol is added in deionized water, stirring and dissolving at 70 DEG C, be configured to the polyvinyl alcohol water solution of 15 wt %.
Polyvinyl alcohol water solution is dropwise dripped in the 1g galapectite that just will take out from baking oven, make it fully absorb, until halloysite nanotubes the most all moistens, put in 40 DEG C of baking ovens and dry, repeat dropping and the process being dried, until polyvinyl alcohol water solution is all added dropwise to complete, obtain polyvinyl alcohol/halloysite nanotubes complex.
Being placed in tube furnace by this complex, nitrogen (purity is 99.999%) protects lower 800 DEG C of calcining 2h, and heating rate is 10 DEG C/min, finally uses HF(40
Wt%) the template halloysite nanotubes in product is removed in stirring 48h washing, after filtration, uses 5% dilute hydrochloric acid to wash 5 times, cleans 5 times with distilled water, be dried, obtain product carbon nano rod material.
Scheme from the SEM of the embodiment 3 gained carbon nano rod material of Fig. 2: be that polyvinyl alcohol is filled in the aperture of halloysite nanotubes by reaction, synthesized carbon nanomaterial.Gained carbon nanomaterial presents bar-shaped, and diameter is at about 15nm.
Scheme from the TEM of the embodiment 3 gained carbon nano rod material of Fig. 3: product presents solid club shaped structure, and diameter is at about 15nm.
The carbon nano rod material diameter that this example is made reaches 408.5m in about 15nm, specific surface area2/g。
Example 4:
Halloysite nanotubes is placed in 550 DEG C of roasting 6h in Muffle furnace, and cooling is placed in 120 DEG C of baking ovens and is dried 24h.
8g polyvinyl alcohol is added in deionized water, stirring and dissolving at 90 DEG C, be configured to the polyvinyl alcohol water solution of 30 wt %.
Polyvinyl alcohol water solution is dropwise dripped in the 3g galapectite that just will take out from baking oven, make it fully absorb, until halloysite nanotubes the most all moistens, put in 60 DEG C of baking ovens and dry, repeat dropping and the process being dried, until polyvinyl alcohol water solution is all added dropwise to complete, obtain polyvinyl alcohol/halloysite nanotubes complex.
Being placed in tube furnace by this complex, nitrogen (purity is 99.999%) protects lower 500 DEG C of calcining 4h, and heating rate is 8 DEG C/min, finally uses HF(20
Wt%) the template halloysite nanotubes in product is removed in stirring 48h washing, after filtration, uses 10% dilute hydrochloric acid to wash 4 times, cleans 4 times with distilled water, be dried, obtain product carbon nano rod material, and diameter reaches 418.7m in about 15nm, specific surface area2/g。
Claims (9)
1. the preparation method preparing one-dimensional carbon nano material, it is characterised in that comprise the following steps:
1) natural halloysite nanotubes is processed during roasting 6～8h is placed on 100～200 DEG C of baking ovens under 500～700 DEG C of temperature conditionss 12～24h, obtains halloysite nanotubes；Polyvinyl alcohol is dissolved in deionized water, forms the polyvinyl alcohol water solution that concentration is 15～30wt%；
2) halloysite nanotubes is mixed with polyvinyl alcohol water solution, drying, obtain polyvinyl alcohol/halloysite nanotubes complex；
3) polyvinyl alcohol/halloysite nanotubes complex is placed in tube furnace; in the lower calcining of nitrogen protection; then the halloysite nanotubes in polyvinyl alcohol/halloysite nanotubes complex is removed with the hydrofluoric acid aqueous solution that concentration is 20～40wt%; again through filtering, washing and be dried, obtain one-dimensional carbon nano material.
2. according to preparation method described in claim 1, it is characterised in that the aperture of described natural halloysite nanotubes is about 20～30nm, and specific surface is about 20～40m2/g。
3. according to preparation method described in claim 1, it is characterised in that in step 1), the molecular weight of described polyvinyl alcohol is 11～130,000, and when being dissolved in deionized water by polyvinyl alcohol, solution temperature condition is 70～90 DEG C.
4. according to preparation method described in claim 1, it is characterised in that step 2) in, halloysite nanotubes is 1: 0.5～3 with the mixing quality ratio of polyvinyl alcohol.
5. according to preparation method described in claim 1, it is characterised in that step 2) in, the temperature conditions carrying out halloysite nanotubes with polyvinyl alcohol water solution mixing is 40～60 DEG C；Described drying temperature is 40～60 DEG C.
6. according to preparation method described in claim 1, it is characterized in that step 2) in, under condition of heating and stirring, halloysite nanotubes is slowly added in polyvinyl alcohol water solution, then, it is transferred to the halloysite nanotubes having adsorbed polyvinyl alcohol in baking oven dry, obtains polyvinyl alcohol/halloysite nanotubes complex.
7. according to preparation method described in claim 1, it is characterized in that step 2) in, polyvinyl alcohol water solution is dripped on halloysite nanotubes, until halloysite nanotubes all moistens, then the halloysite nanotubes having adsorbed polyvinyl alcohol is put in baking oven and dry, the process of dropping and drying that repeats, until polyvinyl alcohol water solution is all added dropwise to complete, obtains polyvinyl alcohol/halloysite nanotubes complex.
8. according to preparation method described in claim 1, it is characterised in that in step 3), described calcining heat is 500～800 DEG C, and heating rate is 5～10 DEG C/min, and calcination time is 2h～4h.
9., according to preparation method described in claim 1, it is characterised in that in step 3), first use 5～10wt % aqueous hydrochloric acid solutions to wash during washing 4～5 times, clean 4～5 times with distilled water the most again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610325417.4A CN105967167B (en) | 2016-05-17 | 2016-05-17 | A kind of method for preparing one-dimensional carbon nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610325417.4A CN105967167B (en) | 2016-05-17 | 2016-05-17 | A kind of method for preparing one-dimensional carbon nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105967167A true CN105967167A (en) | 2016-09-28 |
| CN105967167B CN105967167B (en) | 2018-01-09 |
Family
ID=56956551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610325417.4A Active CN105967167B (en) | 2016-05-17 | 2016-05-17 | A kind of method for preparing one-dimensional carbon nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105967167B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107128903A (en) * | 2017-06-02 | 2017-09-05 | 扬州大学 | To crimp the method that the halloysite nanotubes of layer structure prepare graphene |
| CN107413365A (en) * | 2017-05-17 | 2017-12-01 | 大连理工大学 | A kind of preparation method of N doping super large tube chamber carbon nano tube compound material |
| CN107936292A (en) * | 2017-11-29 | 2018-04-20 | 扬州大学 | Carbon nanotubes carbon nano rod PTFE micro-nano composite materials and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102303861A (en) * | 2011-07-21 | 2012-01-04 | 中国地质大学（武汉） | Method for preparing mesoporous carbon material based on natural halloysite as template |
| CN102398902A (en) * | 2011-07-21 | 2012-04-04 | 中国地质大学（武汉） | Method for preparing carbon nano material by using natural endellite as formwork |
| CN103224704A (en) * | 2013-04-22 | 2013-07-31 | 常州纳欧新材料科技有限公司 | Preparation method for polyaniline/polypyrrole binary composite nanotube |
| CN104401965A (en) * | 2014-11-19 | 2015-03-11 | 中国科学院长春应用化学研究所 | Method for preparing carbon material |
-
2016
- 2016-05-17 CN CN201610325417.4A patent/CN105967167B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102303861A (en) * | 2011-07-21 | 2012-01-04 | 中国地质大学（武汉） | Method for preparing mesoporous carbon material based on natural halloysite as template |
| CN102398902A (en) * | 2011-07-21 | 2012-04-04 | 中国地质大学（武汉） | Method for preparing carbon nano material by using natural endellite as formwork |
| CN103224704A (en) * | 2013-04-22 | 2013-07-31 | 常州纳欧新材料科技有限公司 | Preparation method for polyaniline/polypyrrole binary composite nanotube |
| CN104401965A (en) * | 2014-11-19 | 2015-03-11 | 中国科学院长春应用化学研究所 | Method for preparing carbon material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107413365A (en) * | 2017-05-17 | 2017-12-01 | 大连理工大学 | A kind of preparation method of N doping super large tube chamber carbon nano tube compound material |
| CN107128903A (en) * | 2017-06-02 | 2017-09-05 | 扬州大学 | To crimp the method that the halloysite nanotubes of layer structure prepare graphene |
| CN107936292A (en) * | 2017-11-29 | 2018-04-20 | 扬州大学 | Carbon nanotubes carbon nano rod PTFE micro-nano composite materials and preparation method thereof |
| CN107936292B (en) * | 2017-11-29 | 2019-08-13 | 扬州大学 | Carbon nanotube-carbon nano rod-PTFE micro-nano composite material and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105967167B (en) | 2018-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104118908B (en) | A kind of regulation and control preparation method of orderly titanium dioxide nano material | |
| CN103537237B (en) | A kind of Fe 3o 4the preparation method of CPAM core-shell magnetic nano material | |
| CN104591301B (en) | A kind of porous nano CoFe 2o 4preparation method | |
| CN105502286B (en) | A kind of porous nano NiFe2O4Preparation method | |
| CN105521789B (en) | A kind of porous nano BiFeO3Preparation method | |
| CN102701163B (en) | Titanium nitride nanometer material having three-dimensional connected pore channel structure and preparation method of titanium nitride nanometer material | |
| CN105967167B (en) | A kind of method for preparing one-dimensional carbon nano material | |
| CN105664950A (en) | Preparation method of nano porous ZnFe2O4 | |
| CN108948368B (en) | Method for rapidly preparing nickel-based metal organic framework material | |
| CN108793228A (en) | A kind of synthetic method of carbon-coated indium oxide hollow bar | |
| CN101538034A (en) | Preparation method of one-step synthesis carbon ball | |
| CN108452767A (en) | A kind of preparation method of nano zine oxide-sisal fiber Carbon composites | |
| CN103361065B (en) | CdSe quantum dot load Graphene with different-shape feature and uses thereof and preparation method | |
| CN107572509A (en) | A kind of hollow carbon graphite ball nano material of N doping and preparation method thereof | |
| CN107096537B (en) | Fe2O3Doped TiO 22Floating type environment repairing material loaded with expanded perlite and preparation method thereof | |
| CN109046421B (en) | It is a kind of to prepare C, N co-doped nano pipe/stick catalysis material method using quaternary ammonium base | |
| CN109126814B (en) | Method for in-situ growth of copper molybdate with micro-nano structure | |
| CN108457000B (en) | CuO/ZnO heterostructure loaded on nanofiber membrane and preparation method thereof | |
| CN103074661B (en) | Method for controlling hydrophily and hydrophobicity of array surface of titanium dioxide nanotube | |
| CN105060272B (en) | A kind of using artemia chorion as carbon source low temperature under prepare the method for CNT | |
| CN104888708B (en) | Corn scytoblastema three-dimensional multistage pore structure carbon material and preparation method thereof | |
| CN102671687B (en) | Composite metal nitrogen-doped carbon nanotube catalyst, preparation method thereof and method for catalyzing biodiesel by utilizing catalyst | |
| CN105198006B (en) | The application of porous cobaltosic oxide | |
| CN101343043A (en) | Amphoteric metal compound nano-material and method of preparing the same | |
| CN103833080A (en) | Preparation method for cadmium molybdate porous spheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |