CN102226070B - Nano-quadrangular prism self-assembly hollow manganese dioxide absorbing agent and preparation method thereof - Google Patents
Nano-quadrangular prism self-assembly hollow manganese dioxide absorbing agent and preparation method thereof Download PDFInfo
- Publication number
- CN102226070B CN102226070B CN201110107946.4A CN201110107946A CN102226070B CN 102226070 B CN102226070 B CN 102226070B CN 201110107946 A CN201110107946 A CN 201110107946A CN 102226070 B CN102226070 B CN 102226070B
- Authority
- CN
- China
- Prior art keywords
- manganese dioxide
- assembly
- self
- quadrangular
- nanometer
- 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
Images
Abstract
The invention relates to a nano-quadrangular prism self-assembly hollow manganese dioxide absorbing agent and a preparation method thereof. The method is as follows: iron is chemically doped during the hydro-thermal synthesis reaction process for effectively preparing the particle appearance of manganese dioxide into a hollow structure formed by nano-quadrangular prism self-assembly, as the particle surface is radially formed by special nano-quadrangular prisms, the absorbing agent has great effects of absorbing and scattering electromagnetic waves and the magnetic loss performance of the manganese dioxide is further significantly improved; and manganese dioxide powder prepared by the method can be used as a dielectric loss type absorbing agent with excellent performances. Furthermore, the preparation method is simple, the cost is lower, the performances are stable and the application prospects are good.
Description
Technical field
The invention belongs to interleaving techniques field prepared by Materials science and chemosynthesis, relate to the technology of preparing of New Absorbent particle; Be particularly related to hollow manganese dioxide absorbent of a kind of nanometer quadrangular self-assembly and preparation method thereof.
Background technology
Electromagnetic wave absorbent material is extensive application aspect stealthy technique, heat preservation energy-saving and physical protection, along with to the going deep into of absorbing material research, broadband, minimal thickness, light weight, absorbs contour performance by force and has become current researchdevelopment direction.Wherein, wave absorbing agent plays key effect to the absorbing property of whole absorbing material, has caused various countries investigators' great attention.Tradition absorption agent is that to take graphite, ferrite, carbon black etc. be representative, and they all have the shortcomings such as the narrow and density of absorption band is large conventionally, and range of application is subject to certain limitation.Thereby research and development have light weight, wideband, pollution-free, environment resistant multifunctional efficient New Absorbent, will be focus and the difficult point of following absorbing material research.
Manganse Dioxide is a kind of oxide compound with essential industry purposes, its ion-exchange performance, molecular adsorption performance, chemical property and absorption of electromagnetic wave performance, make it in fields such as catalysis, electrode and absorbing materials, show superior practical value and commercial value.The microscopic appearance of Manganse Dioxide has great significance to its application, and recent result of study shows, some metal ion (Fe
3+, Cr
3+, Ag
+deng) intervention can significantly change the pattern of Manganse Dioxide, thereby its physical and chemical performance is impacted.Yet as a kind of dielectric loss absorbing material, the doping of Manganse Dioxide is very rare to the relevant report of its electromagnetic wave absorption performance impact.
Summary of the invention
For the existing above-mentioned deficiency of prior art, the present invention aims to provide manganese dioxide absorbent granules adopting the standby a kind of special appearance of chemical doping legal system and preparation method thereof, and it effectively improves the hertzian wave magnetic loss performance of Manganse Dioxide particle by chemical doping and control microscopic appearance.
Technical solution of the present invention is as follows:
A preparation method for the hollow manganese dioxide absorbent of nanometer quadrangular self-assembly, in hydrothermal synthesis reaction process, doping iron ion, comprises the steps:
The mixed in molar ratio that ferrous sulfate and manganous sulfate are pressed to 1-5:20, dilutes and stirs with distilled water, and add appropriate ammonium persulphate as oxygenant, and ammonium persulphate and manganous sulfate mol ratio are 0.8-3:1; After stirring and dissolving, proceed in the autoclave of inner liner polytetrafluoroethylene, be placed in the baking oven of 150-200 ℃, the control reaction times is 8-16 hour, and the chemical equation of generation is as follows:
Naturally cool to room temperature, filter, obtain black precipitate, with deionized water and alcohol, repeatedly rinse while being 6-8 to PH, be positioned over dry 18-48 hour in 60-100 ℃ of baking oven, obtain Manganse Dioxide black powder, described manganese dioxide powder is nanometer quadrangular self-assembly hollow structure.
Described Manganse Dioxide is the black powder of nanometer quadrangular self-assembly hollow structure, and Manganse Dioxide integral particle diameter is 1-3 micron, for by the length of side being the hollow structure that the quadrangular of 30-50 nanometer forms radially.
Described ferrous sulfate, manganous sulfate and ammonium persulphate are all analytical pure, do not do any purification test.
Adopt sem observation granule-morphology, as shown in Figure 1; The formation of manganese dioxide hollow sphere structure can be set forth by " Ewald slaking " mechanism, the Manganse Dioxide particles agglomerate that reaction generates becomes large solid sphere, surface particle crystallization is epitaxially grown to nanometer quadrangular, and makes inner particle dissolution, the final manganese dioxide hollow sphere generating.The energy that crystal growth needs is certain, iron ion add ionic forces and the partial potential that has strengthened reaction soln, thereby promoted the carrying out of maturing process.
And the magnetic loss characteristic of Adoption Network method test Manganse Dioxide particle.Under the condition of chemical doping iron, the contrast in the magnetic loss angle tangent of the prepared hollow manganese dioxide absorbent granules of nanometer quadrangular self-assembly and not doping situation, as shown in Figure 2; In figure, magnetic loss angle tangent is larger, illustrates that Manganse Dioxide particle is just higher to electromagnetic magnetic loss performance, and the correlation curve in figure can find out, mixes the magnetic loss performance of Manganse Dioxide particle after iron and effectively improves.This is because Fe
3+with Mn
4+ionic radius is suitable, likely replaces MnO
2in certain Mn
4+form a small amount of substitutional solid solution, the sosoloid of these iron content has relatively magnetic preferably, make Manganse Dioxide magnetic loss performance be improved significantly.
Technique effect emergence of the present invention is present: the present invention is by chemical doping iron, effectively the granule-morphology of Manganse Dioxide is prepared into the hollow structure being formed by the self-assembly of nanometer quadrangular, this particle surface is due to radial composition of nanometer quadrangular by special, hertzian wave is had to good absorption and scattering process, significantly improved thus the magnetic loss performance of Manganse Dioxide; The Manganse Dioxide powder of preparing with this method can be used as a kind of dielectric loss type absorption agent of excellent property.And described preparation method is simple, cost is lower, stable performance, and application prospect is good.
Accompanying drawing explanation
Fig. 1 is the hollow structure shape appearance figure that the prepared Manganse Dioxide particle of embodiment is formed by the self-assembly of a kind of nanometer quadrangular.
Fig. 2 be the prepared hollow manganese dioxide absorbent granules of nanometer quadrangular self-assembly of embodiment with chemical doping situation not under the magnetic loss angle tangent comparison diagram of the manganese dioxide absorbent granules prepared.
Embodiment
Specific solution is as follows: first 11.36g manganous sulfate and 4.67g ferrous sulfate are dissolved in the distilled water of 100ml, fully stir until solution becomes transparent.Then the ammonium persulphate of 19.17g is added to above-mentioned solution, under room temperature, stir 30 minutes until solution fully dissolves.Finally above-mentioned mixing solutions is moved in the autoclave of inner liner polytetrafluoroethylene, be placed in the baking oven of 180 ℃, controlling the reaction times is 12 hours, naturally cool to room temperature, filter, obtain black precipitate, with deionized water and alcohol, repeatedly rinse to PH and be about at 7 o'clock, be positioned in 80 ℃ of baking ovens and be dried 24 hours, obtain the hollow Manganse Dioxide black powder that the self-assembly of nanometer quadrangular forms, as shown in Figure 1; As can be seen from the figure, the about 1-3 micron of Manganse Dioxide integral particle diameter, and the quadrangular that is 30-50 nanometer by the length of side forms hollow structure radially.
Adopt HP8722ES grid method to measure the magnetic permeability parameter of magnetic loss performance characterization, fixture is coaxial reflection transmission system; Working sample within the scope of 2-18GHz magnetic parameter with the numerical value change of frequency.Concrete test is to be 0.87g/cm by the powder of gained and density
3solid paraffin press certain mass than mixing, in particular manufacturing craft, making thickness is 2mm, and interior warp is Ф 3mm, and external diameter is the coaxial sample of Ф 7mm, the filling ratio of filler is 30wt%, measures the complex permeability of Manganse Dioxide-solid paraffin matrix material and calculates magnetic loss performance; Measuring result as shown in Figure 2, under visible described chemical doping iron bar part, the magnetic loss angle tangent of the prepared hollow Manganse Dioxide particle of nanometer quadrangular self-assembly is apparently higher than the magnetic loss angle tangent of unadulterated Manganse Dioxide particle, and known Manganse Dioxide particle magnetic loss performance of mixing after iron obviously improves.
Claims (2)
1. a preparation method for the hollow manganese dioxide absorbent of nanometer quadrangular self-assembly, in hydrothermal synthesis reaction process, doping iron ion, the steps include:
First 11.36g manganous sulfate and 4.67g ferrous sulfate are dissolved in the distilled water of 100ml, fully stir until solution becomes transparent; Then the ammonium persulphate of 19.17g is added to above-mentioned solution, under room temperature, stir 30 minutes until solution fully dissolves; Finally above-mentioned mixing solutions is moved in the autoclave of inner liner polytetrafluoroethylene, be placed in the baking oven of 180 ℃, controlling the reaction times is 12 hours, naturally cool to room temperature, filter, obtain black precipitate, with deionized water and alcohol repeatedly rinse to PH be 7 o'clock, be positioned in 80 ℃ of baking ovens and be dried 24 hours, obtain the hollow Manganse Dioxide black powder that the self-assembly of nanometer quadrangular forms.
2. the hollow manganese dioxide absorbent of nanometer quadrangular self-assembly that as claimed in claim 1 prepared by method, is characterized in that:
Described Manganse Dioxide is the black powder of nanometer quadrangular self-assembly hollow structure, and Manganse Dioxide integral particle diameter is 1-3 micron, for by the length of side being the hollow structure that the quadrangular of 30-50 nanometer forms radially.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110107946.4A CN102226070B (en) | 2011-04-27 | 2011-04-27 | Nano-quadrangular prism self-assembly hollow manganese dioxide absorbing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110107946.4A CN102226070B (en) | 2011-04-27 | 2011-04-27 | Nano-quadrangular prism self-assembly hollow manganese dioxide absorbing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102226070A CN102226070A (en) | 2011-10-26 |
| CN102226070B true CN102226070B (en) | 2014-02-05 |
Family
ID=44807070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110107946.4A Expired - Fee Related CN102226070B (en) | 2011-04-27 | 2011-04-27 | Nano-quadrangular prism self-assembly hollow manganese dioxide absorbing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102226070B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915260B (en) * | 2017-11-30 | 2019-10-11 | 中国科学院大连化学物理研究所 | A kind of nanometer MnO of high entropy of transition2The preparation method of particle |
| CN110040782B (en) * | 2019-05-06 | 2021-07-27 | 东北大学秦皇岛分校 | Manganese dioxide, preparation method and application thereof |
| CN113800555B (en) * | 2021-09-02 | 2023-05-16 | 重庆大学 | Novel titanium sulfide nano material and preparation and wave-absorbing application of composite material thereof |
| CN114974910B (en) * | 2022-06-06 | 2024-03-22 | 安徽信息工程学院 | Electrode material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5277890A (en) * | 1992-09-28 | 1994-01-11 | Duracell Inc. | Process for producing manganese dioxide |
| CN1377832A (en) * | 2002-01-18 | 2002-11-06 | 清华大学 | Process for synthesizing different crystal form one-dimensional single crystal mangnesium dioxide nano wire |
| CN101327959A (en) * | 2008-08-01 | 2008-12-24 | 中国科学院电工研究所 | Preparation of epsilon-MnO2 laminate structure nanosphere |
| WO2009055090A1 (en) * | 2007-04-30 | 2009-04-30 | Inframat Corporation | Nanostructured compositions having reduced dissolution of manganese, method of making them and using them in water treatment |
| CN101624213A (en) * | 2009-08-13 | 2010-01-13 | 陕西师范大学 | Preparation method for manganese dioxide hollow sphere |
-
2011
- 2011-04-27 CN CN201110107946.4A patent/CN102226070B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5277890A (en) * | 1992-09-28 | 1994-01-11 | Duracell Inc. | Process for producing manganese dioxide |
| US5391365A (en) * | 1992-09-28 | 1995-02-21 | Duracell Inc. | Process for producing manganese dioxide |
| CN1377832A (en) * | 2002-01-18 | 2002-11-06 | 清华大学 | Process for synthesizing different crystal form one-dimensional single crystal mangnesium dioxide nano wire |
| WO2009055090A1 (en) * | 2007-04-30 | 2009-04-30 | Inframat Corporation | Nanostructured compositions having reduced dissolution of manganese, method of making them and using them in water treatment |
| CN101327959A (en) * | 2008-08-01 | 2008-12-24 | 中国科学院电工研究所 | Preparation of epsilon-MnO2 laminate structure nanosphere |
| CN101624213A (en) * | 2009-08-13 | 2010-01-13 | 陕西师范大学 | Preparation method for manganese dioxide hollow sphere |
Non-Patent Citations (2)
| Title |
|---|
| 水热合成法制备微纳米MnO2晶体不同形貌的电磁特性;马贺,等;《功能材料与器件学报》;20100228;第16卷(第1期);第35-40页 * |
| 马贺,等.水热合成法制备微纳米MnO2晶体不同形貌的电磁特性.《功能材料与器件学报》.2010,第16卷(第1期),第35-40页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102226070A (en) | 2011-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105255446B (en) | The compound microwave absorbing material of a kind of redox graphene and nano-cerium oxide and preparation method | |
| Ding et al. | Electromagnetic wave absorption in reduced graphene oxide functionalized with Fe 3 O 4/Fe nanorings | |
| CN102533216B (en) | Ferroferric oxide/reduced graphene oxide composite wave-absorbing material with hollow hemisphere structure and preparation method | |
| CN109762519B (en) | Preparation method of high-entropy alloy/oxide composite nano wave-absorbing material | |
| CN105923623A (en) | Preparation method of graphene powder with three-dimensional hierarchical porous structure | |
| CN110790316B (en) | Iron oxide-nitrogen doped carbon micron tube composite wave-absorbing material and preparation method thereof | |
| CN103571432A (en) | Ferrite hollow sphere-graphene composite wave-absorbing material and preparation method thereof | |
| CN105219345A (en) | A kind of preparation method of Z 250 iron nucleocapsid structure-Graphene composite wave-suction material | |
| CN102226070B (en) | Nano-quadrangular prism self-assembly hollow manganese dioxide absorbing agent and preparation method thereof | |
| CN104479626B (en) | A kind of greying multi-walled carbon nano-tubes/Nanocomposites wave absorbing agent and preparation method thereof | |
| CN100574598C (en) | W type ferrite electromagnetic-wave absorbent and preparation method thereof | |
| CN102992306A (en) | Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof | |
| CN103539193B (en) | Preparation method of cerium-praseodymium composite oxide nanoparticle and nanorod | |
| CN108878176A (en) | A kind of technology of preparing of supercapacitor N doping mesoporous carbon composite metal oxide electrode material | |
| He et al. | Bio-assisted synthesis of mesoporous Li3V2 (PO4) 3 for high performance lithium-ion batteries | |
| CN109896520A (en) | A kind of magnetizing reduction stannic oxide/graphene nano composite material and preparation method and application | |
| CN104673185A (en) | Method for preparing reduced graphene oxide/CoFe2O4/Ag composite wave-absorbing material | |
| CN107240508A (en) | A kind of preparation method of graphene/ferrite nano combination electrode material | |
| CN105895387A (en) | Spherical porous Fe3O4/MnO2 supercapacitor material and preparation method thereof | |
| CN102807840B (en) | Preparation method for nanometer Fe3O4-SrFe12O19 compound wave absorption material | |
| CN103922716B (en) | Zinc-doped W type barium ferrite composite wave-absorption material and preparation method thereof | |
| Hu et al. | Cobalt silicate: critical synthetic conditions affect its electrochemical properties for energy storage and conversion | |
| CN108557902B (en) | A kind of CoFe2O4The preparation method and applications of quantum dot | |
| CN109179381B (en) | Graphene/ferroferric oxide/copper silicate composite powder and preparation and application thereof | |
| CN105161716A (en) | Sodium-ion battery cathode 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140205 Termination date: 20170427 |