CN105967167B - A kind of method for preparing one-dimensional carbon nano material - Google Patents
A kind of method for preparing one-dimensional carbon nano material Download PDFInfo
- Publication number
- CN105967167B CN105967167B CN201610325417.4A CN201610325417A CN105967167B CN 105967167 B CN105967167 B CN 105967167B CN 201610325417 A CN201610325417 A CN 201610325417A CN 105967167 B CN105967167 B CN 105967167B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- halloysite nanotubes
- preparation
- carbon nano
- template
- 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
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
A kind of method for preparing one-dimensional carbon nano material, belong to the preparing technical field of nano-carbon material.The present invention is using natural halloysite nanotubes as template, using 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 obtain carbon nano-tube material.As carbon source is filled into template caliber, and accumulated in caliber, caliber is filled up, removed template procedure through high temperature cabonization pickling, then obtain carbon nano rod material.Therefore, product made of present invention process or it is nanotube or is nanometer rods or is the mixing material of nanotube and nanometer rods.
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.
By the good physical and chemical performance that they have special structure and assign, it is set to be used for battery, semiconductor
Material, catalyst carrier etc., and be described as environment-friendly and be the wonder-working new material of the mankind.
The template developed in recent years prepares carbon nanomaterial and causes extensive attention.Template has synthesis technique simple
Many advantages, such as pattern, size, the dimension of single, Stability Analysis of Structures and synthetic material are homogeneous controllable, at present, has there is many document reports
It is template that road prepares one-dimensional carbon nano material, Hou etc. using anodic alumina films using hard template method, passes through chemical vapor deposition
CNT [Hou P X. Templatesynthesis of ultra-thin and short carbon are prepared in method
nanotubes with two open ends[J].J.Mater.chem,2012, 22(30):15221-15226.].Liu etc.
People grows from titania nanotube and is evenly distributed, standing upright on substrate carbon nano rod [Liu S, Yang L,
Xu S, Luo S, and Cai Q. 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 and template used and carbon source costliness, system all be present
The shortcomings of standby process is cumbersome, and condition is harsher, and environment is unfriendly, and safety coefficient is low, and power consumption is higher.
The content of the invention
The present invention seeks to propose a kind of one-dimensional carbon nano material of preparing for reducing production cost, improving safety coefficient
Method.
The present invention comprises the following steps:
1)Natural halloysite nanotubes are calcined after 6~8h under 500~700 DEG C of temperature conditionss and are placed in 100~200 DEG C of bakings
12~24h is handled in case, obtains halloysite nanotubes;Polyvinyl alcohol is dissolved in deionized water, formed concentration for 15~
30wt% polyvinyl alcohol water solution;
2)Halloysite nanotubes are mixed with polyvinyl alcohol water solution, drying, obtain polyvinyl alcohol/halloysite nanotubes
Compound;
3)Polyvinyl alcohol/halloysite nanotubes compound is placed in tube furnace, lower calcining is protected in nitrogen, then with dense
The hydrofluoric acid aqueous solution spent for 20~40wt% removes the halloysite nanotubes in polyvinyl alcohol/halloysite nanotubes compound, then
Filtered, washing and drying, obtain one-dimensional carbon nano material.
Above step 1)It is middle natural halloysite nanotubes are calcined after halloysite nanotubes specific surface area increase
For 30~60m2/ g, then be placed in processing removal halloysite nanotubes in baking oven and be placed in air, the water that its surface is adsorbed.
The present invention using natural halloysite nanotubes as template, using polyvinyl alcohol as carbon source, as carbon source by with template surface
Hydroxy combining, be attached to halloysite nanotubes surface, through high temperature cabonization pickling remove template procedure, then obtain CNT material
Material.As carbon source is filled into template caliber, and accumulated in caliber, caliber is filled up, removing template is removed through high temperature cabonization pickling
Process, then obtain carbon nano rod material.Therefore, product made of present invention process or it is nanotube or is nanometer rods or is nanometer
The mixing material of pipe and nanometer rods.
Advantages of the present invention is as follows:
1st, selected template is halloysite nanotubes, is natural clay, without preparing, and wide material sources,
It is nontoxic, it is cheap.
2nd, it is simple to operate, without complex device, and carbon source/template composite can be prepared under low temperature, drop
Low energy consumption, experimentation are green safe.
3rd, by changing the addition of carbon source, controllable preparation obtains carbon nano-tube material or carbon nano rod material,
The aperture of gained CNT reaches 381.5m in 20nm or so, specific surface area2/ g, the diameter of carbon nano rod exist
15nm or so and reach 400~420m than surface2/g。
Further, the aperture of the natural halloysite nanotubes is about 20~30nm, is about 30~50m than surface2/g。
The halloysite nanotubes of the parameter are more beneficial for that product is prepared.
Step 1)In, the molecular weight of the polyvinyl alcohol is 11~130,000, when polyvinyl alcohol is dissolved in deionized water
Solution temperature condition is 70~90 DEG C.The polyvinyl alcohol of the parameter is more beneficial for that product is prepared.
Step 2)In, the mixing quality ratio of halloysite nanotubes and polyvinyl alcohol is 1: 0.5~3.Can from the materials ratio
Polyvinyl alcohol is sufficiently carried on halloysite nanotubes surface, or polyvinyl alcohol is more fully packed into halloysite nanotubes
It is internal.
Step 2)In, the temperature conditionss that halloysite nanotubes are mixed with polyvinyl alcohol water solution are 40~60 DEG C;
The drying temperature is 40~60 DEG C.From the temperature conditionss reaction can be made more abundant, so as to get polyvinyl alcohol/galapectite receive
Mitron compound is evenly.
The method that halloysite nanotubes are mixed with polyvinyl alcohol water solution there are two kinds:
One kind, under condition of heating and stirring, halloysite nanotubes are slowly added in polyvinyl alcohol water solution, then, will be inhaled
The halloysite nanotubes of attached polyvinyl alcohol, which are transferred in baking oven, dries, and obtains polyvinyl alcohol/halloysite nanotubes compound.
Another kind, polyvinyl alcohol water solution is added dropwise on halloysite nanotubes, moistened until halloysite nanotubes are whole,
Then the halloysite nanotubes for having adsorbed polyvinyl alcohol are put into baking oven and dried, repeated to be added dropwise and the process of drying is until poly- second
The enol aqueous solution is all added dropwise to complete, and obtains polyvinyl alcohol/halloysite nanotubes compound.
First method, simple to operate, polyvinyl alcohol is attached to angstrom by the hydroxy combining with halloysite nanotubes surface
Lip river stone nanotube surface, obtains polyvinyl alcohol/halloysite nanotubes compound, and CNT material can be prepared in this method
Material.
Second method, simple to operate, polyvinyl alcohol is populated into the caliber of halloysite nanotubes, and in caliber
Accumulation, caliber is filled up, obtains polyvinyl alcohol/halloysite nanotubes compound, carbon nano rod material can be prepared in this method
Material.
In step 3)In, the calcining heat is 500~800 DEG C, and heating rate is 5~10 DEG C/min, and calcination time is
2h~4h.From the temperature, time conditions reaction can be made more abundant, products therefrom effect is best.
Step 3)In, first washed 4~5 times using 5~10wt % aqueous hydrochloric acid solutions during washing, then cleaned again with distilled water
4~5 times.HF can be washed to remove totally, makes the pH presentations of product neutral.
Brief description of the drawings
Fig. 1 is that the TEM of the gained carbon nano-tube material of embodiment 1 schemes.
Fig. 2 is that the SEM of the gained carbon nano rod material of embodiment 3 schemes.
Fig. 3 is that the TEM of the gained carbon nano rod material of embodiment 3 schemes.
Embodiment
The invention will be further described below in conjunction with the accompanying drawings.
Example 1:
Halloysite nanotubes are placed in 550 DEG C of roasting 6h in Muffle furnace, is placed in after cooling in 100 DEG C of baking ovens and dries 24h.
2g polyvinyl alcohol is added in deionized water, the stirring and dissolving at 80 DEG C, be configured to 15wt % polyvinyl alcohol water
Solution.
3g is calcined, the halloysite nanotubes after drying and processing are slowly added in above polyvinyl alcohol water solution, in 50 DEG C
Lower stirring makes the water in mixed system try one's best drying, and the halloysite nanotubes for having adsorbed polyvinyl alcohol then are put into 50 DEG C of baking ovens
Middle drying, obtain polyvinyl alcohol/halloysite nanotubes compound.
The compound is placed in tube furnace, nitrogen(Purity is 99.99%)Protect 3 h of lower 700 DEG C of calcinings, heating rate
For 5 DEG C/min, hydrofluoric acid is finally used(30 wt%)Removing template halloysite nanotubes are removed in stirring 48h washings, dilute using 5% after filtering
Salt acid elution 5 times, then cleaned 5 times with distilled water again, be dried to obtain product carbon nano-tube material.
From the TEM figures of Fig. 1 gained carbon nano-tube material of embodiment 1:Obtained carbon nano-tube material aperture exists
20nm or so, specific surface area reach 381.5m2/g。
Example 2:
Halloysite nanotubes are placed in 550 DEG C of roasting 6h in Muffle furnace, is placed in after cooling in 120 DEG C of baking ovens and dries 24h.
4g polyvinyl alcohol is added in deionized water, the stirring and dissolving at 80 DEG C, be configured to 15 wt % polyvinyl alcohol
The aqueous solution.
Polyvinyl alcohol water solution is added dropwise dropwise, by the 3g galapectites taken out from baking oven, fully absorbs it in just,
Until halloysite nanotubes just all moisten, it is put into 50 DEG C of baking ovens and dries, the process for being added dropwise and drying is repeated, until poly- second
The enol aqueous solution is all added dropwise to complete, and obtains polyvinyl alcohol/halloysite nanotubes compound.
The compound is placed in tube furnace, nitrogen(Purity is 99.999%)Protect lower 700 DEG C of calcinings 3h, heating rate
For 5 DEG C/min, HF is finally used(40 wt%)The template halloysite nanotubes in 48h washing removal products are stirred, after filtering, are used
5% watery hydrochloric acid washs 5 times, is then cleaned 5 times with distilled water again, dries, and obtains product carbon nano rod material, and diameter is left in 15nm
The right side, specific surface area reach 402.7m2/g。
Example 3:
Halloysite nanotubes are placed in 550 DEG C of roasting 6h in Muffle furnace, is placed in after cooling in 120 DEG C of baking ovens and dries 24h.
2g polyvinyl alcohol is added in deionized water, the stirring and dissolving at 70 DEG C, be configured to 15 wt % polyvinyl alcohol
The aqueous solution.
Polyvinyl alcohol water solution is added dropwise dropwise, by the 1g galapectites taken out from baking oven, fully absorbs it in just,
Until halloysite nanotubes just all moisten, it is put into 40 DEG C of baking ovens and dries, the process for being added dropwise and drying is repeated, until poly- second
The enol aqueous solution is all added dropwise to complete, and obtains polyvinyl alcohol/halloysite nanotubes compound.
The compound is placed in tube furnace, nitrogen(Purity is 99.999%)Protect lower 800 DEG C of calcinings 2h, heating rate
For 10 DEG C/min, HF is finally used(40 wt%)The template halloysite nanotubes in 48h washing removal products are stirred, after filtering, are adopted
Washed 5 times with 5% watery hydrochloric acid, then cleaned 5 times with distilled water again, dried, obtain product carbon nano rod material.
From the SEM figures of Fig. 2 gained carbon nano rod material of embodiment 3:It is that polyvinyl alcohol is filled into by reaction
In the aperture of halloysite nanotubes, carbon nanomaterial is synthesized.The presentation of gained carbon nanomaterial is bar-shaped, and diameter is left in 15nm
It is right.
From the TEM figures of Fig. 3 gained carbon nano rod material of embodiment 3:Solid club shaped structure is presented in product, and diameter exists
15nm or so.
Carbon nano rod material diameter reaches 408.5m in 15nm or so, specific surface area made of this example2/g。
Example 4:
Halloysite nanotubes are placed in 550 DEG C of roasting 6h in Muffle furnace, is placed in after cooling in 120 DEG C of baking ovens and dries 24h.
8g polyvinyl alcohol is added in deionized water, the stirring and dissolving at 90 DEG C, be configured to 30 wt % polyvinyl alcohol
The aqueous solution.
Polyvinyl alcohol water solution is added dropwise dropwise, by the 3g galapectites taken out from baking oven, fully absorbs it in just,
Until halloysite nanotubes just all moisten, it is put into 60 DEG C of baking ovens and dries, the process for being added dropwise and drying is repeated, until poly- second
The enol aqueous solution is all added dropwise to complete, and obtains polyvinyl alcohol/halloysite nanotubes compound.
The compound is placed in tube furnace, nitrogen(Purity is 99.999%)Protect lower 500 DEG C of calcinings 4h, heating rate
For 8 DEG C/min, HF is finally used(20 wt%)The template halloysite nanotubes in 48h washing removal products are stirred, after filtering, are used
10% watery hydrochloric acid washs 4 times, is then cleaned 4 times with distilled water again, dries, and obtains product carbon nano rod material, and diameter is left in 15nm
The right side, specific surface area reach 418.7m2/g。
Claims (7)
1. a kind of preparation method for preparing one-dimensional carbon nano material, it is characterised in that comprise the following steps:
1)Be 20~30nm by aperture, specific surface area be 20~40m2/ g natural halloysite nanotubes are in 500~700 DEG C of temperature
Under the conditions of be calcined 6~8h after be placed in 100~200 DEG C of baking ovens 12~24h of processing, obtain halloysite nanotubes;By polyvinyl alcohol
It is dissolved in deionized water, forms the polyvinyl alcohol water solution that concentration is 15~30wt%;
2)Halloysite nanotubes are mixed with polyvinyl alcohol water solution, drying, it is compound to obtain polyvinyl alcohol/halloysite nanotubes
Thing;
3)Polyvinyl alcohol/halloysite nanotubes compound is placed in tube furnace, lower calcining, the calcining heat are protected in nitrogen
For 500~800 DEG C, heating rate is 5~10 DEG C/min, and calcination time is 2h~4h;Then it is 20~40wt%'s with concentration
Hydrofluoric acid aqueous solution removes the halloysite nanotubes in polyvinyl alcohol/halloysite nanotubes compound, then filtered, washing and dry
It is dry, obtain one-dimensional carbon nano material;Wherein, first washed 4~5 times using 5~10wt % aqueous hydrochloric acid solutions during washing, then used again
Distilled water cleans 4~5 times.
2. the preparation method according to claim 1, it is characterised in that step 1)In, the molecular weight of the polyvinyl alcohol is 11
~13 ten thousand, solution temperature condition is 70~90 DEG C when polyvinyl alcohol is dissolved in deionized water.
3. the preparation method according to claim 1, it is characterised in that step 2)In, halloysite nanotubes and polyvinyl alcohol
Mixing quality ratio is 1: 0.5~3.
4. the preparation method according to claim 1, it is characterised in that step 2)In, by halloysite nanotubes and polyvinyl alcohol
The temperature conditionss that the aqueous solution is mixed are 40~60 DEG C;The drying temperature is 40~60 DEG C.
5. the preparation method according to claim 1, it is characterised in that step 2)In, under condition of heating and stirring, galapectite is received
Mitron is slowly added in polyvinyl alcohol water solution, and then, the halloysite nanotubes for having adsorbed polyvinyl alcohol are transferred in baking oven
Drying, obtain polyvinyl alcohol/halloysite nanotubes compound.
6. the preparation method according to claim 1, it is characterised in that step 2)In, by polyvinyl alcohol water solution be added dropwise in angstrom
On the stone nanotube of Lip river, until halloysite nanotubes all moisten, then the halloysite nanotubes for having adsorbed polyvinyl alcohol are put into
Dried in baking oven, repeat be added dropwise and drying process until polyvinyl alcohol water solution be all added dropwise to complete, obtain polyvinyl alcohol/angstrom
Lip river stone nanotube complex.
7. the preparation method according to claim 1, it is characterised in that in step 3)In, the calcining heat is 500~800
DEG C, heating rate is 5~10 DEG C/min, and calcination time is 2h~4h.
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 CN105967167A (en) | 2016-09-28 |
CN105967167B true 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) |
Families Citing this family (3)
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 |
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 |
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 |
Also Published As
Publication number | Publication date |
---|---|
CN105967167A (en) | 2016-09-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103816905B (en) | A kind of preparation method of carbon nanotube loaded nanometer cobalt catalyst | |
CN104591301B (en) | A kind of porous nano CoFe 2o 4preparation method | |
US20190127225A1 (en) | Carbon nitride modified with perylenetetracarboxylic dianhydride / graphene oxide aerogel composite material, preparation method and application thereof | |
CN103599769A (en) | ZnSn (OH)6 nanometer cubic particle/graphene sandwich structure compound light catalyst | |
CN105967167B (en) | A kind of method for preparing one-dimensional carbon nano material | |
CN105521789B (en) | A kind of porous nano BiFeO3Preparation method | |
CN105600828B (en) | A kind of porous nano CuFe2O4Preparation method | |
CN105129805B (en) | Preparation method of silicon oxide/tin antimony oxide/zinc oxide ternary composite material | |
CN104492409A (en) | Preparation method for TiO2 crystal/graphene nanocomposite | |
CN107029777B (en) | Composite visible light catalyst and its preparation method and application | |
CN103537237A (en) | Preparation method of Fe3O4@C@PAM core-shell magnetic nano material | |
CN104439276B (en) | A kind of quick method and product preparing hollow porous silica/argentum nano composite material | |
CN102701163B (en) | Titanium nitride nanometer material having three-dimensional connected pore channel structure and preparation method of titanium nitride nanometer material | |
CN108948368B (en) | Method for rapidly preparing nickel-based metal organic framework material | |
CN103361065B (en) | CdSe quantum dot load Graphene with different-shape feature and uses thereof and preparation method | |
CN108212089B (en) | Functional hemp biomass carbon aerogel and preparation method and application thereof | |
CN110227515B (en) | Bi2MoO6/BiPO4P-n heterojunction photocatalyst, preparation method and application thereof | |
CN106215968B (en) | A kind of carbon coating CuO composite material and preparation methods of doping nitrogen | |
CN107096537B (en) | Fe2O3Doped TiO 22Floating type environment repairing material loaded with expanded perlite and preparation method thereof | |
CN104445340B (en) | By the preparation method of the octahedra cerium oxide of nanometer blocks self-assembly | |
CN109126814B (en) | Method for in-situ growth of copper molybdate with micro-nano structure | |
CN108452802A (en) | A kind of Nb-Rh codoping titanium dioxide nanos rod photo-catalyst and its preparation method and application | |
CN103894157A (en) | Preparation method and application of paper pulp/nano-carbon composite material | |
CN105198006B (en) | The application of porous cobaltosic oxide | |
CN104888708B (en) | Corn scytoblastema three-dimensional multistage pore structure carbon material and preparation method thereof |
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 |