CN102344151B - Prussian blue nano-scale hollow olivary microballoons - Google Patents
Prussian blue nano-scale hollow olivary microballoons Download PDFInfo
- Publication number
- CN102344151B CN102344151B CN 201110171047 CN201110171047A CN102344151B CN 102344151 B CN102344151 B CN 102344151B CN 201110171047 CN201110171047 CN 201110171047 CN 201110171047 A CN201110171047 A CN 201110171047A CN 102344151 B CN102344151 B CN 102344151B
- Authority
- CN
- China
- Prior art keywords
- prussian blue
- microballoons
- olivary
- scale
- nano
- 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
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses prussian blue nano-scale hollow olivary microballoons, and belongs to the technical field of prussian blue materials. A preparation method of the prussian blue nano-scale hollow olivary microballoons comprises the following steps that 1, acrylamide as a monomer, N,N'-methylenebisacrylamide as a cross-linking agent, ammonium persulfate as an initiator and ethanol as a solvent are prepared into crosslinked polyacrylamide hydrogel microballoons by a dispersion polymerization technology; 2, hydrogel microballoon/ethanol suspending liquid is added with a Fe<3+> salt aqueous solution; 3 the mixed solution obtained by the step 2 is stirred violently for one night so that the crosslinked polyacrylamide hydrogel microballoons swelled by Fe<3+> deform; 4, a potassium ferrocyanide aqueous solution is added dropwisely into the mixed solution treated by the step 3 to form prussian blue shells; and 5, the solvent is removed so that the prussian blue nano-scale hollow olivary microballoons are obtained. The preparation method of the prussian blue nano-scale hollow olivary microballoons has the advantages of simple operation, low cost, good adaptability for large-scale production, and controllability of microballoon sizes. The prussian blue nano-scale hollow olivary microballoons have nano-scale short axis sizes and micron-scale long axis sizes, and can be utilized widely for drug slow release, sensors, electrode materials and the like.
Description
Technical field
The present invention relates to a kind of prussian blue nano particle, be specifically related to a kind of Prussian blue nano-scale hollow olivary microballoons that adopts the special methods preparation.
Background technology
Prussian blue have characteristics such as low toxicity, magnetic, reversible redox, can be widely used in biofuel cell, sensor field.The character of Prussian blue particle depends on its shape and size to a great extent, and the synthetic controlled Prussian blue structure (the particularly structure of asymmetric shape) of shape and size has great reality and scientific meaning.
Since adopting the inverted emulsion technology first in 2000, Stephen Mann prepared prussian blue nano isometric particle (Angew. Chem. Int. Ed. 2000,39:1793-1796), researcher successfully synthesizes the prussian blue nano particle of different shape, such as prussian blue nano cube, prussian blue nano rod, the Prussian blue lamella with two-dirnentional structure, prussian blue nano dish etc.The people such as Talham use the LB technology to prepare two-dimentional Prussian blue lamella (J.Am.Chem.Soc.2002,124:10083-10090) at the water-air interface.Stiegman etc. in the silica gel matrix, prepared prussian blue nano rod and nanometer plate (Angew. Chem., Int. Ed. 2007,46:8653-8655).Maclachlan etc. use alkyl chain to prepare (the Angew. Chem. Int. Ed. 2008 (47): 511-514) that has the Prussian blue particle of pipeline configuration as the ferrous cyanide ion of hydrophobic segment as the tensio-active agent of water-wet side.Use porous alumina formwork can prepare one dimension prussian blue nano structure (Nano Lett. 2005,5:1603-1606; Nano Lett. 2002,2:845-847).Liang Guodong, Wang Xiaosong etc. with poly-(ethylene oxide) of ferrous cyanide ion end-blocking-
b-poly-(propylene oxide alkene)-
b-poly-(ethylene oxide) is tensio-active agent, adopt miniemulsion shell polymerization technique to prepare Prussian blue hollow ball, Prussian blue is amorphous state, and the hollow ball size is (J. Am. Chem. Soc. 2009 between 65-198nm, 131,5378-5378).Wang Xiao pine is waited and has synthesized Prussian blue hollow cubic particle by reducing ferrous cyanide ion end-blocking rate subsequently, particle size be 200 nm (Chem. Commun. 2010,46,4574-4576).
Mainly containing about prussian blue nano material preparation method of patent documentation record: Nankai University's " pullulan complexe nano-crystal and preparation method and application " (patent No.: 200810053154.1) adopt hydrothermal method to synthesize prussian blue nano ball, nanometer blocks or nanometer sheet crystal.Zhejiang University's " a kind of method for preparing magnetic FeCo Prussian blue hollow nanometer diamond " (application number: 200910155629.2) adopt hydrothermal method to synthesize iron cobalt prussian blue nano square.(application number: the method that 200910199315.2) adopts mineral acid and hydrothermal treatment consists to combine has been synthesized the Prussian blue mesocrystals with hierarchy to East China Normal University's " a kind of Novel Prussian blue mesocrystals and preparation method thereof ", prepared mesomorphic particle integral body is shaggy octahedron, class octahedron, near-spherical and rocks shape, be made of countless small scale crystal, the small scale crystal is nanometer rod and the nanocubes of 150～250nm.
Prepare having of Prussian blue material take polymkeric substance as tensio-active agent: Zhejiang Normal University's " microemulsion method prepares polypyrrole parcel prussian blue nano particle and is used for electrochemical analysis " (application number: 200710111736.6), adopt microemulsion method to prepare the Prussian blue particle of polypyrrole parcel, particle diameter is less than 100 nm, and the electrode of prepared Prussian blue modification can be used for detecting H
2O
2, have good stability, the advantages such as sensitivity height.(application number: 200710059525.2) with after the PVP coating, Prussian blue size reduces with the increase of polymeric surface active agent content Nankai University's " magnetic nano-particle and preparation method and application that PVP coats ", nano particle magnetic generation considerable change.
Put down in writing respectively prussian blue nano ball, nanometer blocks, nanometer sheet, mesomorphic etc. in the above document, but the synthetic report that there is not yet of Prussian blue nano-scale hollow olivary microballoons up to now.
Summary of the invention
The object of the invention is to the above-mentioned deficiency according to prior art, a kind of Prussian blue nano-scale hollow olivary microballoons is provided.
The present invention is achieved through the following technical solutions above-mentioned purpose:
We adopt soft template method to prepare the controlled Prussian blue nano-scale hollow olivary microballoons of structure first, and method is as follows:
Adopt the dispersion polymerization technology to prepare the cross-linked polyacrylamide gel microballoon, then take the cross-linked polyacrylamide gel microballoon as template, synthetic Prussian blue nano-scale hollow olivary microballoons under the outside shearing force field effect.
Detailed process is:
A kind of Prussian blue nano-scale hollow olivary microballoons, its preparation method is:
(1) take acrylamide (AM) as monomer, N, N '-methylene-bisacrylamide (MBA) is linking agent, ammonium persulphate (APS) is initiator, ethanol is solvent, adopt the dispersion polymerization technology to prepare the cross-linked polyacrylamide gel microballoon, obtain cross-linked polyacrylamide gel microballoon/alcohol suspending liquid;
(2) in cross-linked polyacrylamide gel microballoon/alcohol suspending liquid, add Fe
3+Salt brine solution, this moment, solvent became aqueous ethanolic solution, and the vigorous stirring mixed solution spends the night, and makes Fe
3+The cross-linked polyacrylamide microballoon distortion of swelling dropwise adds and Fe at last
3+Equimolar ferrocyanide aqueous solutions of potassium (is yellow prussiate of potash and Fe
3+Mol ratio is 1:1), form Prussian blue shell after the reaction, remove aqueous ethanolic solution, obtain Prussian blue nano-scale hollow olivary microballoons.
Prussian blue nano-scale hollow olivary microballoons particle properties of the present invention depends primarily on its shape and size, and acrylamide monomer concentration, acrylamide monomer and N in the preparation process, the amount ratio of N '-methylene-bisacrylamide linking agent etc. all can affect net shape and the size of this particle.Through large quantity research, draw following preferred technical scheme:
Acrylamide monomer concentration is 0.17 mol/L ~ 0.53 mol/L in the step (1), the size of prepared Prussian blue rugby in the step (2) can be limited in the nano level scope in this concentration range.
Acrylamide monomer and N in the step (1), the usage ratio of N '-methylene-bisacrylamide linking agent is between 1 ~ 10:1.Can regulate well the degree of crosslinking of polyacrylamide microsphere in this proportional range, make it existing suitable swelling ratio, reasonable mechanical properties is arranged again.
The stirring velocity of vigorous stirring is 800 ~ 1000 rpm described in the step (2).
Described in the step (2) in the aqueous ethanolic solution ethanol and water volume ratio exist: between 1:2 ~ 7.
The application of Prussian blue nano-scale hollow olivary microballoons of the present invention in preparation Thermosensitive Material Used for Controlled Releasing of Medicine, sensor material or electrode materials.
Compared with prior art, the present invention has following beneficial effect:
Adopt the Prussian blue nano-scale hollow olivary microballoons minor axis dimension of synthetic method preparation of the present invention at nanometer scale (ca. 320 nm), major axis dimension can be widely used in the fields such as medicament slow release, sensor, electrode materials at micron number magnitude (ca. 1.1 μ m).And have the preparation method easy and simple to handle, with low cost, can be mass-produced, the advantage such as the particle size controllability is good.
Compare with the nanometer ball of mentioning in the background technology, hollow rugby of the present invention is asymmetric geometry, and performance shows as anisotropy, can be used for the fields such as directional selectivity medicament slow release, nano-electric machine.
Description of drawings
Fig. 1. FTIR detects the spectrogram of cross-linked polyacrylamide microballoon;
Fig. 2. the optical microscope photograph of cross-linked polyacrylamide, scale are 20 μ m;
Fig. 3. different Fe
2+/ Fe
3+The time mixed solution the UV-vis spectrogram;
Fig. 4. the FE-SEM picture of Prussian blue nano-scale hollow olivary microballoons particle.
Embodiment
The preparation of embodiment 1 Prussian blue nano-scale hollow olivary microballoons
(1) preparation of cross-linked polyacrylamide microballoon
Take acrylamide (AM) as monomer, N, N '-methylene-bisacrylamide (MBA) is linking agent, and ammonium persulphate (APS) is initiator, and ethanol is solvent, adopts the dispersion polymerization technology to prepare polyacrylamide microsphere.Typical building-up process is as follows: add 0.375 g acrylamide (AM), 0.125 g linking agent MBA and 9.5 mL dehydrated alcohols in the round-bottomed flask of 50 mL, the concussion dissolving, drum nitrogen 20 min remove the oxygen that is dissolved in the solution under the magnetic agitation, then add 1.91 mg APS, continue drum nitrogen 10 min, in solution, add 0.1 mL TMEDA(Tetramethyl Ethylene Diamine again).Place 40 ° of C oil baths to stir and spend the night, stirring velocity is 600 rpm.Acrylamide monomer concentration is 0.53 mol/L, acrylamide monomer and N, and the usage ratio of N '-methylene-bisacrylamide linking agent is 3:1.Change the size of polyacrylamide microsphere by changing monomer concentration, change the degree of crosslinking that linking agent/monomer stoicheiometry is regulated polyacrylamide microsphere.
With the composition (Fig. 1) of FTIR sign cross-linked polyacrylamide microballoon, wave number 3300 cm
-1Absorption band is attributed to the N-H antisymmetric stretching vibration, wave number 3063 cm
-1Absorption band is the N-H symmetrical stretching vibration, 1659 cm
-1The place is absorbed as C=O stretching vibration, 1627 cm
-1Be NH
2Scissoring vibration absorbs, 1548 cm
-1For the C-H formation vibration absorbs, 1125cm
-1Absorption band is attributed to the C-N stretching vibration, at 1000～650 cm
-1Between do not observe the carbon-to-carbon double bond absorption band, show the formation cross-linked polyacrylamide.
With observation by light microscope cross-linked polyacrylamide granule-morphology (see figure 2), show that the cross-linked polyacrylamide particle is spherical, diameter is 2 μ m, cross-linked polyacrylamide particle Uniform Dispersion in the visual field is not observed obvious reunion.Usually dispersion polymerization need to add a certain amount of dispersion agent, and acrylamide can form stable dispersion system in the alcohol-water mixing solutions, do not need to add dispersion agent, this is because ammonium persulphate is ionic initiator, it is polymerizing acrylamide triggered to form radical anion in the alcohol-water mixed system, the cross-linked polyacrylamide particle that generates is with ionic end groups, and the ion of like charges repels mutually makes polymer microballoon be suspended in the stable dispersion system of formation in the solvent.
(2) Prussian blue hollow rugby is synthetic
The cross-linked polyacrylamide microballoon is three-dimensional net structure, and specific surface area is large, and the ion in can adsorbent solution adds Dissolvable Fe in cross-linked polyacrylamide microballoon aqueous ethanolic solution
3+During salts solution, Fe
3+Diffuse into polymer microballoon inside, this moment, the vigorous stirring mixed solution made Fe
3+The distortion of the cross-linked polyacrylamide microballoon of swelling adds yellow prussiate of potash at last, makes it and diffuses into cross-linked polyacrylamide microballoon Fe
3+Reaction forms Prussian blue shell, obtains Prussian blue hollow rugby after the desolventizing.Typical building-up process is: add respectively magnetic stir bar, 1 mL polyacrylamide/ethanolic soln (concentration of polyacrylamide is 50 g/mL) and 1 mL deionized water in the vial of 10 mL, dropwise add the Fe (NO that 1 mL concentration is 50 mg/mL under magnetic agitation
3)
39H
2The O aqueous solution, vigorous stirring under the room temperature (1000 rpm) is spent the night.Dropwise add again the ferrocyanide aqueous solutions of potassium that 1 mL concentration is 64 mg/mL, continue under the room temperature to stir and spend the night, get product.
The FTIR spectrogram (Fig. 1) of Prussian blue particle shows 2084 cm
-1There is a sharp-pointed absorption band at the place, is attributed to Prussian blue Fe(II)-CN-Fe(III) characteristic absorbance of CN in the chain structure, can infer form Prussian blue.We have further followed the tracks of Prussian blue particle building-up process with UV-vis, see Fig. 3, and Fig. 3 shows and do not add Fe
2+The time mixed solution do not absorb at 712 nm places, and add Fe
2+Rear mixed solution has obvious absorption peak at 712 nm places, be Prussian blue charateristic avsorption band, and absorption peak strength is along with Fe
2+/ Fe
3+The increase of ratio and increasing, show generated Prussian blue.Work as Fe
2+: Fe
3+1 o'clock, no longer increase in 712 nm absorption peak strength.
With the synthetic Prussian blue granule-morphology (see figure 4) of FE-SEM observation post, show that Prussian blue particle presents the rugby pattern, diameter is 320 nm, length is 1.1 μ m.Except complete rugby, also observe damaged particle, the cavity structure in these damaged particles shows that Prussian blue rugby is hollow structure.
More than the Prussian blue nano-scale hollow olivary microballoons of preparation can be applied to prepare sensor, medicament slow release etc. by this area ordinary method.
The preparation of embodiment 2 Prussian blue nano-scale hollow olivary microballoons
(1) preparation of cross-linked polyacrylamide microballoon
In the round-bottomed flask of 50 mL, add 0.12 g acrylamide (AM), 0.04 g linking agent MBA and 9.5 mL dehydrated alcohols, the concussion dissolving, drum nitrogen 20 min remove the oxygen that is dissolved in the solution under the magnetic agitation, then add 1.91 mg APS, continue drum nitrogen 10 min, in solution, add 0.1 mL TMEDA(Tetramethyl Ethylene Diamine again).Place 40 ° of C oil baths to stir and spend the night, stirring velocity is 600 rpm.Acrylamide monomer concentration is 0.17 mol/L, acrylamide monomer and N, and the usage ratio of N '-methylene-bisacrylamide linking agent is 3:1.
(2) Prussian blue hollow rugby is synthetic
In the vial of 10 mL, add respectively magnetic stir bar, 1 mL polyacrylamide/ethanolic soln (concentration of polyacrylamide is 50 g/mL) and 4 mL deionized waters, under magnetic agitation, dropwise add the Fe (NO that 1 mL concentration is 50 mg/mL
3)
39H
2The O aqueous solution, vigorous stirring under the room temperature (1000 rpm) is spent the night.Dropwise add again the ferrocyanide aqueous solutions of potassium that 1 mL concentration is 64 mg/mL, continue under the room temperature to stir and spend the night, get product.
The preparation of embodiment 3 Prussian blue nano-scale hollow olivary microballoons
(1) preparation of cross-linked polyacrylamide microballoon
In the round-bottomed flask of 50 mL, add 0.375 g acrylamide (AM), 0.375 g linking agent MBA and 9.5 mL dehydrated alcohols, the concussion dissolving, drum nitrogen 20 min remove the oxygen that is dissolved in the solution under the magnetic agitation, then add 1.91 mg APS, continue drum nitrogen 10 min, in solution, add 0.1 mL TMEDA(Tetramethyl Ethylene Diamine again).Place 40 ℃ of oil baths to stir and spend the night, stirring velocity is 600 rpm.Acrylamide monomer concentration is 0.53 mol/L, acrylamide monomer and N, and the usage ratio of N '-methylene-bisacrylamide linking agent is 1:1.
(2) Prussian blue hollow rugby is synthetic
In the vial of 10 mL, add respectively magnetic stir bar, 1 mL polyacrylamide/ethanolic soln (concentration of polyacrylamide is 50 g/mL) and 5 mL deionized waters, under magnetic agitation, dropwise add the Fe (NO that 1 mL concentration is 50 mg/mL
3)
39H
2The O aqueous solution, vigorous stirring under the room temperature (900 rpm) is spent the night.Dropwise add again the ferrocyanide aqueous solutions of potassium that 1 mL concentration is 64 mg/mL, continue under the room temperature to stir and spend the night, get product.
The preparation of embodiment 4 Prussian blue nano-scale hollow olivary microballoons
(1) preparation of cross-linked polyacrylamide microballoon
In the round-bottomed flask of 50 mL, add 0.375 g acrylamide (AM), 0.0375 g linking agent MBA and 9.5 mL dehydrated alcohols, the concussion dissolving, drum nitrogen 20 min remove the oxygen that is dissolved in the solution under the magnetic agitation, then add 1.91 mg APS, continue drum nitrogen 10 min, in solution, add 0.1 mL TMEDA(Tetramethyl Ethylene Diamine again).Place 40 ℃ of oil baths to stir and spend the night, stirring velocity is 600 rpm.Acrylamide monomer concentration is 0.53 mol/L, acrylamide monomer and N, and the usage ratio of N '-methylene-bisacrylamide linking agent is 10:1.
(2) Prussian blue hollow rugby is synthetic
In the vial of 10 mL, add respectively magnetic stir bar, 1 mL polyacrylamide/ethanolic soln (concentration of polyacrylamide is 50 g/mL) and 6 mL deionized waters, under magnetic agitation, dropwise add the Fe (NO that 1 mL concentration is 50 mg/mL
3)
39H
2The O aqueous solution, vigorous stirring under the room temperature (1000 rpm) is spent the night.Dropwise add again the ferrocyanide aqueous solutions of potassium that 1 mL concentration is 64 mg/mL, continue under the room temperature to stir and spend the night.
Claims (4)
1. Prussian blue nano-scale hollow olivary microballoons is characterized in that the preparation method is:
(1) take acrylamide as monomer, N, N '-methylene-bisacrylamide are linking agent, ammonium persulphate is initiator, ethanol is solvent, adopts the dispersion polymerization technology to prepare the cross-linked polyacrylamide gel microballoon, obtains cross-linked polyacrylamide gel microballoon/alcohol suspending liquid;
(2) in cross-linked polyacrylamide gel microballoon/alcohol suspending liquid, add Fe
3+Salt brine solution, this moment, solvent became aqueous ethanolic solution, and the vigorous stirring mixed solution spends the night, and makes Fe
3+The cross-linked polyacrylamide microballoon distortion of swelling dropwise adds and Fe at last
3+Equimolar ferrocyanide aqueous solutions of potassium forms Prussian blue shell after the reaction, remove aqueous ethanolic solution, obtains Prussian blue nano-scale hollow olivary microballoons.
Wherein, acrylamide monomer concentration is 0.17 mol/L ~ 0.53 mol/L in the step (1), acrylamide monomer and N, and the mass ratio of N '-methylene-bisacrylamide linking agent is 1 ~ 10:1.
2. Prussian blue nano-scale hollow olivary microballoons according to claim 1, the stirring velocity that it is characterized in that vigorous stirring described in the step (2) is 800 ~ 1000 rpm.
3. Prussian blue nano-scale hollow olivary microballoons according to claim 1 is characterized in that described in the step (2) that ethanol and water volume ratio are between 1:2 ~ 7 in the aqueous ethanolic solution.
4. the application of Prussian blue nano-scale hollow olivary microballoons claimed in claim 1 in preparation Thermosensitive Material Used for Controlled Releasing of Medicine, sensor material or electrode materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110171047 CN102344151B (en) | 2011-06-23 | 2011-06-23 | Prussian blue nano-scale hollow olivary microballoons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110171047 CN102344151B (en) | 2011-06-23 | 2011-06-23 | Prussian blue nano-scale hollow olivary microballoons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102344151A CN102344151A (en) | 2012-02-08 |
| CN102344151B true CN102344151B (en) | 2013-03-20 |
Family
ID=45543279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110171047 Expired - Fee Related CN102344151B (en) | 2011-06-23 | 2011-06-23 | Prussian blue nano-scale hollow olivary microballoons |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102344151B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556151B (en) * | 2013-10-12 | 2018-01-23 | 西北大学 | A kind of Prussian blue preparation method |
| CN105836762A (en) * | 2016-03-16 | 2016-08-10 | 西北大学 | Preparation method and application of hollow Prussian-blue nanometer cube |
| CN106525931B (en) * | 2016-09-28 | 2018-10-26 | 中国科学院长春应用化学研究所 | The detection method of copper ion concentration in a kind of solution |
| CN106876706A (en) * | 2017-03-25 | 2017-06-20 | 宁波吉电鑫新材料科技有限公司 | A kind of monolithic conductive original position C/Bi/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method thereof |
| CN106848263A (en) * | 2017-03-25 | 2017-06-13 | 宁波吉电鑫新材料科技有限公司 | A kind of continuous conduction liquid phase synthesis C/Ag, Bi/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method thereof |
| CN106972159A (en) * | 2017-03-25 | 2017-07-21 | 宁波吉电鑫新材料科技有限公司 | A kind of continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2Positive pole and preparation method |
| CN106953080A (en) * | 2017-03-25 | 2017-07-14 | 宁波吉电鑫新材料科技有限公司 | A kind of continuous conduction liquid phase synthesis C/Cu, Zn/CuF2Anode material of lithium battery and preparation method |
| CN106953085A (en) * | 2017-03-25 | 2017-07-14 | 宁波吉电鑫新材料科技有限公司 | A kind of continuous conduction original position C/Ag, metal solid solution/Mg2+Adulterate BiF3Positive pole and preparation method |
| CN106972158A (en) * | 2017-03-25 | 2017-07-21 | 宁波吉电鑫新材料科技有限公司 | A kind of continuous conduction original position C/Cu/CuF2Compound electric positive electrode of copper fluoride lithium and preparation method thereof |
| CN106848259A (en) * | 2017-03-25 | 2017-06-13 | 宁波吉电鑫新材料科技有限公司 | A kind of continuous conduction original position C/Ag, Zr/ZrF4Compound zirconium fluoride anode material for lithium-ion batteries and preparation method thereof |
| CN106876680A (en) * | 2017-03-25 | 2017-06-20 | 宁波吉电鑫新材料科技有限公司 | A kind of continuous conduction original position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof |
| CN106953083A (en) * | 2017-03-25 | 2017-07-14 | 宁波吉电鑫新材料科技有限公司 | A kind of continuous conduction original position C/ metal solid solutions/Ni2+,Ca2+Adulterate BiF3Positive pole and preparation method |
| CN106876681A (en) * | 2017-03-25 | 2017-06-20 | 宁波吉电鑫新材料科技有限公司 | A kind of continuous conduction liquid phase synthesis C/Bi/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method thereof |
| CN106848265A (en) * | 2017-03-25 | 2017-06-13 | 宁波吉电鑫新材料科技有限公司 | A kind of monolithic conductive original position C/Bi, Ag/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method |
| CN106953086A (en) * | 2017-03-25 | 2017-07-14 | 宁波吉电鑫新材料科技有限公司 | A kind of continuous conduction original position C/ metal solid solutions/Ce4+Adulterate CuF2Positive pole and preparation method |
| CN108461765B (en) * | 2018-05-29 | 2021-04-16 | 武汉大学 | N-Fe/FeC3Air cathode electro-catalytic material of @ AC microbial fuel cell and preparation method thereof |
| CN109065883B (en) * | 2018-07-27 | 2021-02-09 | 张五星 | Prussian blue and modification method of Prussian blue analogue and sodium ion battery |
| CN115072740B (en) * | 2022-06-23 | 2023-10-10 | 齐齐哈尔大学 | Preparation method of Prussian blue nanospheres with core-shell structure |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368928A (en) * | 2007-09-05 | 2009-02-18 | 浙江师范大学 | Prussian blue nanometer particle produced by reverse micelle method for electrochemical analysis |
-
2011
- 2011-06-23 CN CN 201110171047 patent/CN102344151B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368928A (en) * | 2007-09-05 | 2009-02-18 | 浙江师范大学 | Prussian blue nanometer particle produced by reverse micelle method for electrochemical analysis |
Non-Patent Citations (4)
| Title |
|---|
| Erik Dujardin et al..Morphosynthesis of Molecular Magnetic Materials.《Advanced Materials》.2004,第16卷(第13期),第1125-1129页. |
| Guodong Liang et al..Synthesis and Characterization of Organometallic Coordination Polymer Nanoshells of Prussian Blue Using Miniemulsion Periphery Polymerization (MEPP)..《Journal of American Chemistry Society》.2009,第131卷第5378-5379页. |
| Morphosynthesis of Molecular Magnetic Materials;Erik Dujardin et al.;《Advanced Materials》;20040705;第16卷(第13期);第1125-1129页 * |
| Synthesis and Characterization of Organometallic Coordination Polymer Nanoshells of Prussian Blue Using Miniemulsion Periphery Polymerization (MEPP).;Guodong Liang et al.;《Journal of American Chemistry Society》;20090330;第131卷;第5378-5379页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102344151A (en) | 2012-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102344151B (en) | Prussian blue nano-scale hollow olivary microballoons | |
| Fu et al. | Control of molecular transport through stimuli‐responsive ordered mesoporous materials | |
| CN102226029B (en) | Preparation method of temperature responsive nanohydrogel carrying silver nanoparticles | |
| CN1186377C (en) | Multifunctional organic-inorganic composite polymeric microball and preparing method thereof | |
| CN101792514B (en) | Preparation method of magnetic fluorescent dual-function nano particle with nuclear shell structure | |
| CN104710584A (en) | Polymer hydrogel and preparation method thereof | |
| Zheng et al. | Synthesis and characterization of dopamine-modified Ca-alginate/poly (N-isopropylacrylamide) microspheres for water retention and multi-responsive controlled release of agrochemicals | |
| CN103601847A (en) | Core-shell type magnetic surface imprinting nanometer composite material preparation method | |
| CN104479072A (en) | Method for preparing magnetic molecularly-imprinted adsorbent | |
| CN102321255A (en) | Ion type nano-composite hydrogel and preparation method thereof | |
| Ji et al. | Preparation of hollow magnetic molecularly imprinted polymer and its application in silybin recognition and controlled release | |
| CN104436199A (en) | Preparation method of porous ferroferric oxide composite nanometre microspheres efficiently loaded with pharmorubicin | |
| CN102492250A (en) | Temperature-sensitive polymer/gold nanoparticle hybrid microspheres and preparation method thereof | |
| CN106478904A (en) | A kind of preparation method of the segmented copolymer material with temperature and pH-sensitivity | |
| CN104262812A (en) | Magnetic fluorescent polymer microsphere with high load stability and preparation method of magnetic fluorescent polymer microsphere | |
| Tyliszczak et al. | Novel hydrogels containing nanosilver for biomedical applications-synthesis and characterization | |
| CN102489273B (en) | Preparation method of magnetic beads of dendritic molecular imprinting polymer on surface of estrogenic nano silica gel | |
| CN107880877A (en) | A kind of preparation method and applications of monodisperse polymer fluorescent microsphere | |
| CN104403041A (en) | PH-responsive type magnetic composite microsphere with Janus structure, and preparation method thereof | |
| CN104387712A (en) | Nano composite carrier with superparamagnetism and preparation method thereof | |
| CN107828032B (en) | Hyperbranched starlike poly ion liquid of one kind and its preparation method and application | |
| CN104177628A (en) | Composite nano sliver polymer antibacterial micelle and preparation method thereof | |
| CN104342431A (en) | Preparation method of magnetic nanometer carrier for immobilized enzyme | |
| CN103497292A (en) | Preparation method for thermo-responsive mesoporous silicon nanoparticles | |
| CN103386135B (en) | Preparation method of multifunctional medicine carrier integrating magnetism, fluorescence and thermosensitivity |
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: 20130320 Termination date: 20140623 |
|
| EXPY | Termination of patent right or utility model |