CN103922425B - A kind of preparation method of porous cobaltosic oxide nano band - Google Patents
A kind of preparation method of porous cobaltosic oxide nano band Download PDFInfo
- Publication number
- CN103922425B CN103922425B CN201410133891.8A CN201410133891A CN103922425B CN 103922425 B CN103922425 B CN 103922425B CN 201410133891 A CN201410133891 A CN 201410133891A CN 103922425 B CN103922425 B CN 103922425B
- Authority
- CN
- China
- Prior art keywords
- preparation
- oxide nano
- cobaltosic oxide
- nano band
- cobalt salt
- 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.)
- Expired - Fee Related
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to inorganic nano material synthesis technical field, the invention discloses a kind of preparation method of porous cobaltosic oxide nano band, the concrete steps of described method are as follows: (1) first by cobalt salt and precipitation agent soluble in water, formed mixing solutions; (2) then put in water heating kettle by mixing solutions, at 100 ~ 250 DEG C, carry out hydro-thermal reaction, the reaction times is 5 ~ 24h; (3), after hydro-thermal reaction terminates, reaction product is carried out be separated, wash, then reaction product roasting at 350 ~ 800 DEG C is obtained porous cobaltosic oxide nano band.Present invention achieves surfactant-free in building-up process, organic solvent-free, providing a new synthetic method for having multilevel hierarchy copper oxide material.Preparation technology of the present invention is succinct, and whole technological process is carried out in a kettle., without the need to any complex apparatus, is a kind of simple and effective, cheap, environmental friendliness, is easy to the preparation method preparing cobaltosic oxide nano band of mass-producing synthesis.
Description
Technical field
The present invention relates to inorganic nano material synthesis technical field, particularly relate to a kind of preparation method of porous cobaltosic oxide nano band.
Background technology
As a class p-type transition metal oxide, tricobalt tetroxide shows peculiar process based prediction model in fields such as electricity, magnetic, air-sensitive, catalysis, is widely used in the key areas such as lithium ion battery electrode material, magneticsubstance, heterogeneous catalyst.The process based prediction model of tricobalt tetroxide is by pattern, size and structure influence.In recent years, the tricobalt tetroxide material with different-shape structure causes the great interest of people, has synthesized cobaltosic oxide nano line, nanometer rod, nanometer sheet, nanotube, nano belt, nano flower, nanometer ball etc.Wherein, nano belt, with the constitutional features of its uniqueness and high surface-area and volume ratio, causes it to have higher active sites, is conducive to improving gas-solid phase reaction speed.Therefore, cobaltosic oxide nano band has higher application prospect in gas sensitive element device material and heterogeneous catalyst field, becomes the study hotspot of tricobalt tetroxide material.At present, tricobalt tetroxide strip material mainly adopts organic solvent and water to carry out solvent thermal reaction as mixed solvent to carry out synthetic ribbon cobalt precursor, then carry out roasting and finally obtain cobaltosic oxide nano band.Neutralized verdigris is dissolved in the mixed solvent of propylene glycol and water (volume ratio 1:1) and carries out solvent thermal reaction by the people such as Tian, then carries out roasting and obtain cobaltosic oxide nano band (Tian, H.Zou after reaction terminates, J.Fu, X.Yang, Y.Wang, H.Guo, X.Fu, C.Liang, M.Wu, P.K.ShenandQ.Gao, Adv.Funct.Mater., 2010,20,617.).Cobalt chloride is dissolved in N by the people such as Sasaki, in the mixed solvent of dinethylformamide and water (volume ratio 1:1), solvent thermal reaction is carried out using palmityl trimethyl ammonium chloride as tensio-active agent, then carry out roasting and obtain cobaltosic oxide nano band (J.Yang, H.Hyodo, K.Kimura andT.Sasaki, Nanotechnology, 2010,21,045605).As can be seen from above-mentioned document, the solvent adopted in cobaltosic oxide nano band building-up process all contains a large amount of organic solvents, employs tensio-active agent in addition, and its disadvantage is that synthesis cost is high, is not easy to large-scale production.Therefore, carry out low cost, be easy to the research of mass-producing synthesis cobaltosic oxide nano band its preparation method there is important scientific meaning and using value.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide organic solvent-free and tensio-active agent in a kind of building-up reactions and be easy to the preparation method of mass-producing synthesis four oxidation three nano belt.
The present invention adopts following technical scheme:
The concrete steps of the preparation method of porous cobaltosic oxide nano band of the present invention are as follows:
(1) first by cobalt salt and precipitation agent soluble in water, formed mixing solutions, the mol ratio of cobalt salt and precipitation agent is 1:1 ~ 1:10;
(2) then put in water heating kettle by mixing solutions, at 100 ~ 250 DEG C, carry out hydro-thermal reaction, the reaction times is 5 ~ 24h;
(3), after hydro-thermal reaction terminates, reaction product is carried out be separated, wash, then reaction product roasting 1 ~ 10h at 350 ~ 800 DEG C is obtained porous cobaltosic oxide nano band.
In step (1), described cobalt salt is Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, and precipitation agent is Dyhard RU 100, and the concentration of described cobalt salt is 5 ~ 200mmol/l; The concentration of preferred described cobalt salt is 10 ~ 150mmol/l; More preferably the concentration of described cobalt salt is 30 ~ 100mmol/l.
In step (1), the mol ratio of described cobalt salt and precipitation agent is preferably 1:1 ~ 1:7, is more preferably 1:3 ~ 1:5.
In step (2), preferably at 130 ~ 200 DEG C, carry out hydro-thermal reaction, the reaction times is 8 ~ 20h; More preferably at 160 ~ 190 DEG C, carry out hydro-thermal reaction, the reaction times is 10 ~ 15h.
In step (3), maturing temperature is preferably 400 ~ 700 DEG C; Be more preferably 450 ~ 600 DEG C.
In step (3), roasting time is 1 ~ 10h
Positively effect of the present invention is as follows:
1) present invention achieves surfactant-free in building-up process, organic solvent-free, providing a new synthetic method for having multilevel hierarchy copper oxide material.
2) pattern of the present invention by regulating the mol ratio of cobalt salt concentration, cobalt salt and precipitation agent, hydrothermal temperature and time to regulate and control tricobalt tetroxide, control condition and means easy to implement.
3) preparation technology of the present invention is succinct, and whole technological process is carried out in a kettle., without the need to any complex apparatus, is a kind of simple and effective, cheap, environmental friendliness, is easy to the preparation method preparing cobaltosic oxide nano band of mass-producing synthesis.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the cobaltosic oxide nano band that embodiment 1 obtains;
Fig. 2 is the SEM figure of the cobaltosic oxide nano band that embodiment 1 obtains;
Fig. 3 is the TEM figure of the cobaltosic oxide nano band that embodiment 1 obtains;
Fig. 4 is the nitrogen adsorption/desorption isotherm figure of the cobaltosic oxide nano band that embodiment 1 obtains;
Fig. 5 is the graph of pore diameter distribution of the cobaltosic oxide nano band that embodiment 1 obtains.
Embodiment
The following examples describe in further detail of the present invention.
Embodiment 1
(1) first by Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and Dyhard RU 100 soluble in water, formed mixing solutions, the concentration of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is 50mmol/l, and the mol ratio of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and Dyhard RU 100 is 1:4;
(2) then put in water heating kettle by mixing solutions, at 180 DEG C, carry out hydro-thermal reaction, the reaction times is 12h;
(3), after hydro-thermal reaction terminates, reaction product is carried out be separated, wash, then reaction product roasting 2h at 500 DEG C is obtained porous cobaltosic oxide nano band.
X ' PertPROMPD type the Multi-functional X ray diffractometer produced Dutch Panalytical company (PANalytical) by the black powder product of above-mentioned preparation carries out XRD test.Fig. 1 is the XRD spectra of the black powder product that embodiment 1 obtains, and the diffraction peak in spectrogram is typical spinel structure tricobalt tetroxide characteristic diffraction peak, and according to standard powdery diffractometry card (JCPDSNo.42-1467), its crystalline structure is isometric system.XRD spectra confirms that gained black product is tricobalt tetroxide.
By the JSM-7001F model field emission scanning electron microscope observation surface topography that the black tricobalt tetroxide of above-mentioned preparation is produced in NEC company.Fig. 2 is the SEM figure of the black tricobalt tetroxide that embodiment 1 obtains, and tricobalt tetroxide pattern is in banded as seen from the figure, and its width is at 100nm ~ 300nm, and nano belt has vesicular structure on the surface.
By the JEM-2100 lanthanum hexaborane transmission electron microscopy observation particle information that the black tricobalt tetroxide of above-mentioned preparation is produced in NEC company.Fig. 3 is the TEM figure of the black tricobalt tetroxide that embodiment 1 obtains, and black cobaltosic oxide nano band size is about 200nm as seen from the figure, is assembled and is formed, and define the vesicular structure that aperture is about 30nm by the nanoparticle being of a size of 50nm ~ 100nm.
The specific surface of the NOVA3200e model that the black tricobalt tetroxide of above-mentioned preparation is produced in Kang Ta company of the U.S. and lacunarity analysis instrument test specific surface and pore size distribution.Figure 4 and 5 are respectively nitrogen adsorption/desorption isotherm figure and the graph of pore diameter distribution of the black tricobalt tetroxide that embodiment 1 obtains.At the IV type thermoisopleth at relative partial pressure about 0.8 ~ 1.0 place, hysteresis loop shows that cobaltosic oxide nano band has the secondary meso-hole structure of particle packing, BET specific surface is 31.6m
2/ g, can and aperture be 28.6nm.
Embodiment 2
(1) first by Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and Dyhard RU 100 soluble in water, formed mixing solutions, the concentration of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is 10mmol/l, and the mol ratio of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and Dyhard RU 100 is 1:1;
(2) then put in water heating kettle by mixing solutions, at 130 DEG C, carry out hydro-thermal reaction, the reaction times is 20h;
(3), after hydro-thermal reaction terminates, reaction product is carried out be separated, wash, then reaction product roasting 10h at 400 DEG C is obtained porous cobaltosic oxide nano band.
XRD spectra assay products is isometric system tricobalt tetroxide.SEM photo display tricobalt tetroxide pattern presents porous zonal structure, its width 150nm ~ 200nm.TEM photo display cobaltosic oxide nano band size is about 200nm, and assembled by the nanoparticle being of a size of 30nm ~ 50nm and formed, aperture is about 25nm.It is 37.9m that nitrogen adsorption instrument measures specific surface
2/ g, can and aperture be about 24.3nm.
Embodiment 3
(1) first by Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and Dyhard RU 100 soluble in water, formed mixing solutions, the concentration of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is 150mmol/l, and the mol ratio of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and Dyhard RU 100 is 1:7;
(2) then put in water heating kettle by mixing solutions, at 200 DEG C, carry out hydro-thermal reaction, the reaction times is 8h;
(3), after hydro-thermal reaction terminates, reaction product is carried out be separated, wash, then reaction product roasting 1h at 700 DEG C is obtained porous cobaltosic oxide nano band.
XRD spectra assay products is isometric system tricobalt tetroxide.SEM photo display tricobalt tetroxide pattern presents porous zonal structure, its width 100nm ~ 500nm.TEM photo display cobaltosic oxide nano band size is about 250nm, and assembled by the nanoparticle being of a size of 40nm ~ 60nm and formed, aperture is about 25nm.It is 33.1m that nitrogen adsorption instrument measures specific surface
2/ g, can and aperture be about 25.7nm.
Embodiment 4
(1) first by Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and Dyhard RU 100 soluble in water, formed mixing solutions, the concentration of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is 100mmol/l, and the mol ratio of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and Dyhard RU 100 is 1:3;
(2) then put in water heating kettle by mixing solutions, at 190 DEG C, carry out hydro-thermal reaction, the reaction times is 10h;
(3), after hydro-thermal reaction terminates, reaction product is carried out be separated, wash, then reaction product roasting 3h at 600 DEG C is obtained porous cobaltosic oxide nano band.
XRD spectra assay products is isometric system tricobalt tetroxide.SEM photo display tricobalt tetroxide pattern presents porous zonal structure, its width 100nm ~ 500nm.TEM photo display cobaltosic oxide nano band size is about 310nm, and assembled by the nanoparticle being of a size of 50nm ~ 60nm and formed, aperture is about 28nm.It is 30.2m that nitrogen adsorption instrument measures specific surface
2/ g, can and aperture be about 27.5nm.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (9)
1. a preparation method for porous cobaltosic oxide nano band, is characterized in that: the concrete steps of described method are as follows:
(1) first by cobalt salt and precipitation agent soluble in water, formed mixing solutions, described cobalt salt is Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, and precipitation agent is Dyhard RU 100, and the concentration of described cobalt salt is 5 ~ 200mmol/l, and the mol ratio of cobalt salt and precipitation agent is 1:1 ~ 1:10;
(2) then put in water heating kettle by mixing solutions, at 100 ~ 250 DEG C, carry out hydro-thermal reaction, the reaction times is 5 ~ 24h;
(3), after hydro-thermal reaction terminates, reaction product is carried out be separated, wash, then reaction product roasting 1 ~ 10h at 350 ~ 800 DEG C is obtained porous cobaltosic oxide nano band.
2. preparation method as claimed in claim 1, it is characterized in that: in step (1), the concentration of described cobalt salt is 10 ~ 150mmol/l.
3. preparation method as claimed in claim 1, it is characterized in that: in step (1), the concentration of described cobalt salt is 30 ~ 100mmol/l.
4. preparation method as claimed in claim 1, it is characterized in that: in step (1), the mol ratio of described cobalt salt and precipitation agent is 1:1 ~ 1:7.
5. preparation method as claimed in claim 1, it is characterized in that: in step (1), the mol ratio of described cobalt salt and precipitation agent is 1:3 ~ 1:5.
6. preparation method as claimed in claim 1, is characterized in that: in step (2), at 130 ~ 200 DEG C, carry out hydro-thermal reaction, the reaction times is 8 ~ 20h.
7. preparation method as claimed in claim 1, is characterized in that: in step (2), at 160 ~ 190 DEG C, carry out hydro-thermal reaction, the reaction times is 10 ~ 15h.
8. preparation method as claimed in claim 1, it is characterized in that: in step (3), maturing temperature is 400 ~ 700 DEG C.
9. preparation method as claimed in claim 1, it is characterized in that: in step (3), maturing temperature is 450 ~ 600 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410133891.8A CN103922425B (en) | 2014-04-04 | 2014-04-04 | A kind of preparation method of porous cobaltosic oxide nano band |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410133891.8A CN103922425B (en) | 2014-04-04 | 2014-04-04 | A kind of preparation method of porous cobaltosic oxide nano band |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103922425A CN103922425A (en) | 2014-07-16 |
| CN103922425B true CN103922425B (en) | 2015-10-28 |
Family
ID=51140860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410133891.8A Expired - Fee Related CN103922425B (en) | 2014-04-04 | 2014-04-04 | A kind of preparation method of porous cobaltosic oxide nano band |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103922425B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478007A (en) * | 2014-12-17 | 2015-04-01 | 江苏合志锂硫电池技术有限公司 | Preparation method of cobaltosic oxide |
| CN104478006B (en) * | 2015-01-06 | 2017-01-25 | 南京工业大学 | Preparation method of cobaltosic oxide mesoporous nanosheet |
| CN104609479A (en) * | 2015-02-11 | 2015-05-13 | 天津理工大学 | Method for preparing Co3O4 nanoribbon |
| CN105870439B (en) * | 2016-04-22 | 2018-03-16 | 济南大学 | A kind of preparation method and applications of porous cobaltosic oxide |
| CN108046341B (en) * | 2018-01-11 | 2019-09-10 | 燕山大学 | A kind of preparation method of hollow coralliform cobaltosic oxide nanoparticles |
| CN108611659B (en) * | 2018-05-03 | 2019-12-17 | 山东大学 | High-efficiency stable Co3O4Nanoribbon array chlorine evolution electrode |
| CN108918603B (en) * | 2018-07-11 | 2023-03-28 | 山东大学 | Porous zinc oxide nanosheet load transition metal doped g-C 3 N 4 Synthesis method of composite gas-sensitive material |
| CN110479274B (en) * | 2018-11-05 | 2021-06-22 | 吉林大学 | Co taking aluminum powder as sacrificial agent3O4-CuCoO2Preparation method of nano net material |
| CN110357171B (en) * | 2019-05-07 | 2021-11-02 | 淮阴师范学院 | Preparation method of strip-shaped porous cobaltosic oxide |
| CN113600194B (en) * | 2021-07-21 | 2023-10-20 | 西安近代化学研究所 | Nanometer photocatalyst containing cobalt with different valence states, preparation method and application thereof |
| CN114887579A (en) * | 2022-05-28 | 2022-08-12 | 昆明理工大学 | Preparation and application of vanadium-based material for adsorbing and recovering organic cationic dye in wastewater |
-
2014
- 2014-04-04 CN CN201410133891.8A patent/CN103922425B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| "Nanocrystal-Constructed Mesoporous Single-Crystalline Co3O4 Nanobelts with Superior Rate Capability for Advanced Lithium-Ion Batteries";Hui Huang, et al.;《Applied materials and interfaces》;20121010;第5947 - 5980页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103922425A (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103922425B (en) | A kind of preparation method of porous cobaltosic oxide nano band | |
| Sun et al. | Synthesis and photocatalytic activity of nano-cobalt ferrite catalyst for the photo-degradation various dyes under simulated sunlight irradiation | |
| Liu et al. | Facile synthesis of ultrafine cobalt oxide nanoparticles for high-performance supercapacitors | |
| Farhadi et al. | Simple and low-temperature synthesis of NiO nanoparticles through solid-state thermal decomposition of the hexa (ammine) Ni (II) nitrate,[Ni (NH3) 6](NO3) 2, complex | |
| Zhu et al. | Microwave-assisted hydrothermal synthesis of Ni (OH) 2 architectures and their in situ thermal convention to NiO | |
| Wu et al. | Morphology-controllable Bi2O3 crystals through an aqueous precipitation method and their photocatalytic performance | |
| Xian et al. | Preparation of high-quality BiFeO3 nanopowders via a polyacrylamide gel route | |
| Luo et al. | Wet chemical synthesis of Bi2S3 nanorods for efficient photocatalysis | |
| CN102502783B (en) | Method for preparing alkali zinc chloride nano-powder in hexagonal flake structures | |
| Yang et al. | One-step aqueous solvothermal synthesis of In2O3 nanocrystals | |
| Farhadi et al. | Simple and low-temperature preparation of Co3O4 sphere-like nanoparticles via solid-state thermolysis of the [Co (NH3) 6](NO3) 3 complex | |
| Farhadi et al. | Solid-state thermal decomposition of the [Co (NH3) 5CO3] NO3· 0.5 H2O complex: A simple, rapid and low-temperature synthetic route to Co3O4 nanoparticles | |
| CN101985367B (en) | Method for preparing multilayer alpha-Ni(OH)2 or NiO nanocrystal by microwave solvothermal method | |
| Wang et al. | Synthesis of Co3O4 nanoparticles via the CTAB-assisted method | |
| Su et al. | Preparation and characterization of Y3Al5O12 (YAG) nano-powder by co-precipitation method | |
| Du et al. | Preparation and characterization of flower-like microspheres of nano-NiO as electrode material for supercapacitor | |
| Motlagh et al. | Structural properties of nickel hydroxide/oxyhydroxide and oxide nanoparticles obtained by microwave-assisted oxidation technique | |
| Ruiz-Gómez et al. | Innovative solvo-combustion route for the rapid synthesis of MoO3 and Sm2O3 materials | |
| Zhong et al. | Synthesis of nanocrystalline Ni–Zn ferrite powders by refluxing method | |
| Che et al. | Synthesis of one-dimensional porous Co3O4 nanobelts and their ethanol gas sensing properties | |
| Sivakumar et al. | Conserved crystal phase and morphology: electrochemical supremacy of copper (Cu) and iron (Fe) dual-doped nickel oxide and its supercapacitor applications | |
| Liu et al. | Solvothermal synthesis of monodisperse self-assembly CeO2 nanospheres and their enhanced blue-shifting in ultraviolet absorption | |
| Zhang et al. | Electrocatalytic performance of Sb-modified Bi25FeO40 for nitrogen fixation | |
| CN104402065B (en) | The preparation method of the spherical cobalt disulfide nano-powder of one kind | |
| Vivek et al. | Facile synthesis of 2D Ni (OH) 2 anchored g-C3N4 as electrode material for high-performance supercapacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151028 Termination date: 20170404 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |