CN103466607A - Graphene-metallic oxide nano-particle three-dimensional porous composite material - Google Patents
Graphene-metallic oxide nano-particle three-dimensional porous composite material Download PDFInfo
- Publication number
- CN103466607A CN103466607A CN201310406855XA CN201310406855A CN103466607A CN 103466607 A CN103466607 A CN 103466607A CN 201310406855X A CN201310406855X A CN 201310406855XA CN 201310406855 A CN201310406855 A CN 201310406855A CN 103466607 A CN103466607 A CN 103466607A
- Authority
- CN
- China
- Prior art keywords
- graphene
- dimensional porous
- matrix material
- metal oxide
- porous matrix
- 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.)
- Pending
Links
Images
Abstract
The invention discloses a method for preparing a graphene-metallic oxide nano-particle three-dimensional porous composite material. The method comprises the steps of (1) dissolving raw materials, namely graphene oxide and metal salt, into water, and mixing uniformly; (2) carrying out freeze drying treatment on a product; (3) carrying out heat treatment on the product obtained in the step (2) in a certain atmosphere or vacuum, thereby obtaining the graphene-metallic oxide nano-particle three-dimensional porous composite material, wherein the temperature of the heat treatment is 200-1,100 DEG C, and the time for the heat treatment is 10 seconds to 10 hours.
Description
Technical field
The present invention relates to nano material and manufacture field, particularly relate to the three-dimensional porous matrix material of a kind of Graphene-metal oxide nanoparticles.
Background technology
Metal oxide has vital role, and as four oxidation three aunts can be used for CO low-temperature catalytic oxidation, lithium ion battery electrode material etc., zinc oxide is a kind of important photoelectric material, and tindioxide is a kind of important gas sensitive etc.Metal oxide nano-material has high specific surface area, and its specific activity body material is stronger, thereby because of its people's broad research.Graphene is a kind of carbon material with bi-dimensional cellular shape structure formed by the monolayer carbon atomic arrangement, has good mechanical property, electric property.Simultaneously, Graphene has high specific surface area, can be used as the solid support material of nano material.Metal oxide nanoparticles and Graphene is compound, can suppress the reunion of nano particle, keep respective performances preferably simultaneously.
Preparation method about Graphene-metal oxide composite mainly concentrates on hydrothermal synthesis method at present, and this method energy consumption is higher, also higher to equipment requirements, is unfavorable for the heavy industrialization preparation.On the other hand, the Graphene-metal oxide composite obtained at present is mainly Powdered, is unfavorable for practical application.
Summary of the invention
In order to expand the range of application of Graphene-metal oxide composite, the invention provides the preparation method of the three-dimensional porous matrix material of a kind of Graphene-metal oxide nanoparticles, the matrix material that obtains is three-dimensional porous structure, is conducive to improve the over-all properties of matrix material.
The present invention is by the following technical solutions: the three-dimensional porous matrix material of a kind of Graphene-metal oxide nanoparticles, by the feed oxygen functionalized graphene with metal-salt is soluble in water mixes; The product obtained is carried out to lyophilize; Dried product exhibited thermal treatment under certain atmosphere or vacuum is obtained to the three-dimensional porous matrix material of a kind of Graphene-metal oxide nanoparticles.
Described metal-salt comprises any in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, iron nitrate, zinc nitrate, nitric acid tin, cupric nitrate, nickelous nitrate, cobaltous acetate, zinc acetate, venus crystals, nickelous acetate.
Described certain atmosphere be in air, hydrogen, nitrogen, argon gas any or appoint several mixed gass.
Thermal treatment temp is between 200-1100 degree centigrade, and heat treatment time is between 10 seconds-10 hours.
The mass ratio of described graphene oxide and metal nitrate is 1:10-100:1.
At first described freezing dry process comprises the mixing solutions of graphene oxide and metal-salt is become to solid-state by refrigeration compressor or liquid nitrogen freezing, under the low pressure condition, makes subsequently water sublimed obtain graphene oxide-metal-salt foam.
Beneficial effect of the present invention:
The present invention utilizes the high temperature pyrolysis of metal-salt to obtain metal oxide, does not need other chemical reagent, and method is simple, environmental protection.
Product of the present invention is three-dimensional porous structure, is conducive to improve the range of application of matrix material.
Metallic salt strength of solution soluble in water is even, also can keep being uniformly distributed after freezing, and when water sublimed, solute can evenly be separated out on graphene oxide, can guarantee that the later stage obtains uniform Graphene-metal oxide nanoparticles material.
The accompanying drawing explanation
Fig. 1 is the transmission electron microscope figure of the three-dimensional porous matrix material of Graphene-copper oxide nanometer particle that obtains of the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscope diagram of the three-dimensional porous matrix material of Graphene-copper oxide nanometer particle that obtains of the embodiment of the present invention 1.
Fig. 3 is the transmission electron microscope figure of the Graphene that obtains of the embodiment of the present invention 2-three-dimensional porous matrix material of cobaltosic oxide nano particle.
Embodiment:
Below in conjunction with embodiment and accompanying drawing, the present invention is done further and explains.According to following embodiment, can better understand the present invention.Yet the described concrete material proportion of embodiment, processing condition and result thereof be only for the present invention is described, and should can not limit the present invention described in detail in claims yet.
Embodiment 1
Get feed oxygen functionalized graphene 50mg and cupric nitrate 80mg and be dissolved in the 100ml deionized water, mix by ultrasonic;
The product obtained is carried out after the freezing acquisition solid of refrigeration compressor to drying and dehydrating under low-temperature negative-pressure to be processed;
The product obtained is heated to 200 ℃ of insulations in air and within 10 hours, obtains the three-dimensional porous matrix material of Graphene-copper oxide nanometer particle.
Product is carried out to the transmission electron microscope sign, and result as shown in Figure 1.Product is carried out to the scanning electron microscope sign, and as shown in Figure 2, visible matrix material is vesicular structure to result.
Get graphene oxide 20mg and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 50mg and be dissolved in the 20ml deionized water, by being uniformly mixed;
By the product obtained, immersing freezing in liquid nitrogen is solid, carries out subsequently the low-temperature negative-pressure processed in freeze drier;
The product obtained is heated to 800 ℃ of insulations in hydrogen and within 30 minutes, obtains Graphene-three-dimensional porous matrix material of cobaltosic oxide nano particle.
Product is carried out to the transmission electron microscope sign, and result as shown in Figure 3.
Embodiment 3
Get graphene oxide 10mg and zinc nitrate 100mg and be dissolved in the 50ml deionized water, after ultrasonic mixing;
The product obtained is carried out to the freezing and drying treatment of refrigeration compressor;
The product obtained is heated to 1100 ℃ of insulations in nitrogen and within 10 seconds, obtains the three-dimensional porous matrix material of Graphene-Zinc oxide nanoparticle.
Acquired results is similar to Example 1.
Claims (5)
1. the three-dimensional porous matrix material of Graphene-metal oxide nanoparticles, is characterized in that, by the feed oxygen functionalized graphene with metal-salt is soluble in water mixes; The product obtained is carried out to lyophilize; Dried product exhibited thermal treatment under certain atmosphere or vacuum is obtained to the three-dimensional porous matrix material of a kind of Graphene-metal oxide nanoparticles.
2. the three-dimensional porous matrix material of a kind of Graphene-metal oxide nanoparticles according to claim 1, it is characterized in that, described metal-salt comprises any in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, iron nitrate, zinc nitrate, nitric acid tin, cupric nitrate, nickelous nitrate, cobaltous acetate, zinc acetate, venus crystals, nickelous acetate.
3. the three-dimensional porous matrix material of a kind of Graphene-metal oxide nanoparticles according to claim 1, is characterized in that, described certain atmosphere be in air, hydrogen, nitrogen, argon gas any or appoint several mixed gass.
4. the three-dimensional porous matrix material of a kind of Graphene-metal oxide nanoparticles according to claim 1, is characterized in that, thermal treatment temp is between 200-1100 degree centigrade, and heat treatment time is between 10 seconds-10 hours.
5. the three-dimensional porous matrix material of a kind of Graphene-metal oxide nanoparticles according to claim 1, is characterized in that, the mass ratio of described graphene oxide and metal nitrate is 1:10-100:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310406855XA CN103466607A (en) | 2013-09-09 | 2013-09-09 | Graphene-metallic oxide nano-particle three-dimensional porous composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310406855XA CN103466607A (en) | 2013-09-09 | 2013-09-09 | Graphene-metallic oxide nano-particle three-dimensional porous composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103466607A true CN103466607A (en) | 2013-12-25 |
Family
ID=49791696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310406855XA Pending CN103466607A (en) | 2013-09-09 | 2013-09-09 | Graphene-metallic oxide nano-particle three-dimensional porous composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103466607A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104986755A (en) * | 2015-06-15 | 2015-10-21 | 江苏大学 | Preparing method and application of sulfur impurity graphene/zinc oxide nanocomposite |
| CN105070526A (en) * | 2015-09-08 | 2015-11-18 | 哈尔滨工业大学 | Preparation method of cobaltosic oxide/graphene three-dimensional mixed structure flexible electrode |
| CN105552338A (en) * | 2016-01-22 | 2016-05-04 | 浙江极力动力新能源有限公司 | Preparation method of zinc oxide modified graphene lithium ion battery anode material |
| CN105967286A (en) * | 2016-06-24 | 2016-09-28 | 华东师范大学 | Preparation method for capacitance desalination electrode of graphene hybrid sponge body |
| CN106140167A (en) * | 2015-05-15 | 2016-11-23 | 宝峰时尚国际控股有限公司 | A kind of nano composite photocatalytic material and preparation method thereof |
| CN106391015A (en) * | 2015-07-31 | 2017-02-15 | 南开大学 | Catalytic material, and preparation method and application thereof |
| CN106732514A (en) * | 2016-11-24 | 2017-05-31 | 河南师范大学 | Recoverable version zinc oxide/graphene aerogel photochemical catalyst and preparation method thereof |
| CN106970116A (en) * | 2017-03-20 | 2017-07-21 | 中国石油大学(华东) | A kind of polyhedral cobaltosic oxide three-dimensional porous Graphene gel composite material film sensitive to acetone |
| CN107324325A (en) * | 2017-07-20 | 2017-11-07 | 山西晋尤特环境科技有限公司 | A kind of preparation method of graphene composite material |
| CN108441282A (en) * | 2018-02-07 | 2018-08-24 | 河南大学 | A kind of dispersible graphene nano composite particles and its preparation method and application |
| CN108862248A (en) * | 2018-08-06 | 2018-11-23 | 南京工业大学 | A kind of quick macroblock quantization prepares graphene-metal oxide composite powder material method |
| CN111154461A (en) * | 2020-01-06 | 2020-05-15 | 宁波石墨烯创新中心有限公司 | Oriented assembly graphene, graphene-carbon nanotube composite heat-conducting film and preparation method thereof |
| CN112429722A (en) * | 2020-12-01 | 2021-03-02 | 武汉汉烯科技有限公司 | Nano metal particle doped graphene film and preparation method thereof |
| CN115215380A (en) * | 2022-07-13 | 2022-10-21 | 四川轻化工大学 | Cobaltosic oxide/nitrogen-doped graphene oxide material, preparation method thereof and application thereof in sodium-ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086371A (en) * | 2013-01-24 | 2013-05-08 | 东南大学 | Method for preparing hydrophobic graphene sponge |
| CN103112846A (en) * | 2013-02-06 | 2013-05-22 | 华中科技大学 | Preparation method of graphene-carbon nanotube-nano tin dioxide three-dimensional composite material and product thereof |
-
2013
- 2013-09-09 CN CN201310406855XA patent/CN103466607A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086371A (en) * | 2013-01-24 | 2013-05-08 | 东南大学 | Method for preparing hydrophobic graphene sponge |
| CN103112846A (en) * | 2013-02-06 | 2013-05-22 | 华中科技大学 | Preparation method of graphene-carbon nanotube-nano tin dioxide three-dimensional composite material and product thereof |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140167A (en) * | 2015-05-15 | 2016-11-23 | 宝峰时尚国际控股有限公司 | A kind of nano composite photocatalytic material and preparation method thereof |
| CN104986755A (en) * | 2015-06-15 | 2015-10-21 | 江苏大学 | Preparing method and application of sulfur impurity graphene/zinc oxide nanocomposite |
| CN106391015A (en) * | 2015-07-31 | 2017-02-15 | 南开大学 | Catalytic material, and preparation method and application thereof |
| CN105070526B (en) * | 2015-09-08 | 2017-08-25 | 哈尔滨工业大学 | A kind of preparation method of cobalt oxide/graphene three-dimensional hybrid structural flexibility electrode |
| CN105070526A (en) * | 2015-09-08 | 2015-11-18 | 哈尔滨工业大学 | Preparation method of cobaltosic oxide/graphene three-dimensional mixed structure flexible electrode |
| CN105552338A (en) * | 2016-01-22 | 2016-05-04 | 浙江极力动力新能源有限公司 | Preparation method of zinc oxide modified graphene lithium ion battery anode material |
| CN105967286A (en) * | 2016-06-24 | 2016-09-28 | 华东师范大学 | Preparation method for capacitance desalination electrode of graphene hybrid sponge body |
| CN105967286B (en) * | 2016-06-24 | 2019-04-30 | 华东师范大学 | A kind of preparation method of graphene hydridization cavernous body capacitive desalination electrode |
| CN106732514A (en) * | 2016-11-24 | 2017-05-31 | 河南师范大学 | Recoverable version zinc oxide/graphene aerogel photochemical catalyst and preparation method thereof |
| CN106732514B (en) * | 2016-11-24 | 2020-02-04 | 河南师范大学 | Recyclable zinc oxide/graphene aerogel photocatalyst and preparation method thereof |
| CN106970116A (en) * | 2017-03-20 | 2017-07-21 | 中国石油大学(华东) | A kind of polyhedral cobaltosic oxide three-dimensional porous Graphene gel composite material film sensitive to acetone |
| CN106970116B (en) * | 2017-03-20 | 2019-09-10 | 中国石油大学(华东) | The sensitive polyhedral cobaltosic oxide of a kind of pair of acetone-three-dimensional porous Graphene gel composite material film |
| CN107324325A (en) * | 2017-07-20 | 2017-11-07 | 山西晋尤特环境科技有限公司 | A kind of preparation method of graphene composite material |
| CN108441282A (en) * | 2018-02-07 | 2018-08-24 | 河南大学 | A kind of dispersible graphene nano composite particles and its preparation method and application |
| CN108441282B (en) * | 2018-02-07 | 2021-01-22 | 河南大学 | Dispersible graphene nano composite particles and preparation method and application thereof |
| CN108862248A (en) * | 2018-08-06 | 2018-11-23 | 南京工业大学 | A kind of quick macroblock quantization prepares graphene-metal oxide composite powder material method |
| CN111154461A (en) * | 2020-01-06 | 2020-05-15 | 宁波石墨烯创新中心有限公司 | Oriented assembly graphene, graphene-carbon nanotube composite heat-conducting film and preparation method thereof |
| CN111154461B (en) * | 2020-01-06 | 2021-10-08 | 宁波石墨烯创新中心有限公司 | Oriented assembly graphene, graphene-carbon nanotube composite heat-conducting film and preparation method thereof |
| CN112429722A (en) * | 2020-12-01 | 2021-03-02 | 武汉汉烯科技有限公司 | Nano metal particle doped graphene film and preparation method thereof |
| CN115215380A (en) * | 2022-07-13 | 2022-10-21 | 四川轻化工大学 | Cobaltosic oxide/nitrogen-doped graphene oxide material, preparation method thereof and application thereof in sodium-ion battery |
| CN115215380B (en) * | 2022-07-13 | 2023-12-08 | 四川轻化工大学 | Tricobalt tetraoxide/nitrogen-doped graphene oxide material, preparation method thereof and application thereof in sodium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103466607A (en) | Graphene-metallic oxide nano-particle three-dimensional porous composite material | |
| Uchaker et al. | Polyol-mediated solvothermal synthesis and electrochemical performance of nanostructured V2O5 hollow microspheres | |
| CN103145120B (en) | A kind of preparation method of porous graphene | |
| US20130230709A1 (en) | Porous graphene material and preparation method and uses as electrode material thereof | |
| CN103663438B (en) | A kind of preparation method of porous graphene | |
| CN103332681B (en) | Method for preparing porous carbon based nanomaterial through carbon dioxide conversion | |
| CN103449427B (en) | A kind of preparation method of porous graphene-ferric oxide composite material | |
| CN101698234B (en) | Chemical preparation method of metal cobalt nanowire | |
| CN105110315A (en) | Method for synthesis of double-casing layer carbon nanometer hollow polyhedron by metal-organic framework as template | |
| Gu et al. | Surfactant-free hydrothermal synthesis of sub-10 nm γ-Fe 2 O 3–polymer porous composites with high catalytic activity for reduction of nitroarenes | |
| CN103433037A (en) | Preparation method of graphene foam and precious metal nano-particle composite material | |
| CN108264037B (en) | Three-dimensional porous nitrogen-doped graphene answers the preparation method of material and nitrogen-doped graphene | |
| CN104004496B (en) | The preparation method of a kind of redox graphene/nickel oxide composite wave-suction material | |
| CN103956473A (en) | CuO-Cu2O/graphene nano compound material and preparation method thereof | |
| CN108654659B (en) | A kind of phosphating sludge/graphene composite nano material and preparation method thereof | |
| CN103450843A (en) | Preparation method of reduction-oxidation graphene/ferroferric oxide composite wave-absorbing hydrogel having three-dimensional structure | |
| CN103482615B (en) | A kind of preparation method of spumescence Graphene-ZnO matrix material | |
| CN105217622A (en) | A kind of preparation method of controlled three-dimensional grapheme microballoon | |
| CN105621406A (en) | Nitrogen-doped porous graphite and preparation method thereof | |
| CN102698666A (en) | Preparation method of graphene/nanometer particle composite materials based on infrared ray radiation | |
| CN103482619B (en) | A kind of Graphene-copper oxide three-dimensional foam composite material | |
| CN105834446A (en) | Synthetic method for ultrathin layered NiO-CoOx nanosheet loading NiCo nano particle composite | |
| CN105923625A (en) | Method for preparing single-oxide uniformly-loaded graphene quantum dots | |
| CN103432973B (en) | A kind of preparation method of graphene-ferric oxide nano-particle composite material | |
| CN108565131A (en) | A method of preparing N doping graphitized carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20131225 |