CN101704536A - Novel Prussian blue mesocrystals and preparation method thereof - Google Patents
Novel Prussian blue mesocrystals and preparation method thereof Download PDFInfo
- Publication number
- CN101704536A CN101704536A CN200910199315A CN200910199315A CN101704536A CN 101704536 A CN101704536 A CN 101704536A CN 200910199315 A CN200910199315 A CN 200910199315A CN 200910199315 A CN200910199315 A CN 200910199315A CN 101704536 A CN101704536 A CN 101704536A
- Authority
- CN
- China
- Prior art keywords
- mesocrystals
- prussian blue
- blue
- preparation
- novel
- 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
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses novel Prussian blue mesocrystals and a preparation method thereof, and belongs to the technical field of the preparation of inorganic materials. The Prussian blue mesocrystals with novel hierarchical self-assembly structures are prepared by mixing ferrocyanide salt serving as a raw material with inorganic acid at a specific concentration through hydro-thermal treatment. The prepared integral mesomorphous particles are in shapes of scobinate octahedrons, similar octahedrons, similar spheroids and great lake rocks and consist of numerous small-scale crystals, and all the small-scale crystals are nanorods and nanocubes of between 150 and 250 nm. The Prussian blue mesocrystals can be applied in the field of catalysis due to larger specific surface areas and a mass of pore spaces; and the invention has the advantages of novel morphology of product particles, low cost, simple equipment, easy operation and the like.
Description
Technical field
The present invention relates to the preparing technical field of inorganic materials, specifically a kind of Novel Prussian blue mesocrystals and preparation method thereof.
Background technology
Mesomorphic (mesocrystal) is the similar polycrystal of complex contour, but a class complex crystals of diffraction behavior single crystal-like body.With respect to common monocrystalline and polycrystalline structure, mesomorphic character with uniqueness, it has the long-range symmetry and the complicated and diversified pattern of polycrystalline of monocrystalline concurrently, becomes the novel crystal material with potential using value.Mesomorphicly can find at occurring in nature usually, multiple biological mineral matter is mesomorphic structure.The mesomorphic material of synthetic is inspired by natural mesomorphic mineral, obtains by bionical approach is synthetic usually, and its method is confined to organic template, needs gentle temperature and pH value.The mesomorphic synthetic method of developing under the specified conditions becomes focus just gradually.On the other hand, limit by existing synthesis condition, the known mesomorphic carbonate that concentrates on, simple salt such as vitriol is not extensively promoted.Seek new mesomorphic system and help promoting mesomorphic synthetic technology, expand mesomorphic application.
Prussian blue owing to its special physics, chemical property, in the application in fields such as molecular magnet, electrochemistry, catalyzer, magneto-optic memory technique, biosensor, pigment, hydrogen storage, show the performance of many excellences.For example, the prussian blue nano array is made transmitter, can improve the ability that detects glucose greatly; The hydrogen storage material hydrogen storage ability that with Prussian blue is skeleton is up to 1.8wt.%.Because the factors such as composition structure, size and shape characteristic of material have conclusive effect to its character, realize that the application of material not only needs to give full play to its intrinsic properties, can also regulate and control its character by size and morphology control.Thereby preparing have specific dimensions and a pattern Prussian blue by different preparation methods and technology has become one of focus that the Materials science worker payes attention to.
So far, the Prussian blue micro-/ nano particle of having reported with diverse microcosmic appearance is colourful, comprising bar-shaped, and tubulose, sphere, multiple microtexture such as cubic.These reports have confirmed that the variation of material microscopic appearance can bring significant variation to material property.For example: [Litong Jin et al., Biosensors and Bioelectronics, 22 (2007) 2827-2833] such as Litong Jin are template with the anodised aluminium, prepared prussian blue nano pipe array, and it is applied as biosensor.Because its special nanostructure, this transmitter is very sensitive in the application that detects glucose, is better than traditional Prussian blue biosensor greatly.Chen Jianrong etc. [Chinese invention patent, application number: 200710147356.8] utilize reverse micelle method to prepare the prussian blue nano particle, by it is modified on the electrode, are successfully applied to the detection of H2O2, have highly sensitive and advantages of excellent stability.In mesomorphic synthetic field, what obtain at present widely applying is gaseous diffusion process under the bionical environment.As Helmut
Deng [Helmut
Et al., Advanced Functional Materials, 16 (2006) 903-908] be template with parents' polymkeric substance, utilize under the room temperature condition, the slow diffusion process of the carbon dioxide in the neutral environment, it is mesomorphic to have prepared hexagonal sheet calcium carbonate.
Summary of the invention
The purpose of this invention is to provide a kind of novel Prussian blue mesocrystals, this is mesomorphic because of its bigger specific surface area, and a large amount of holes will obtain important use at catalytic field.
Prussian blue mesocrystals of the present invention, be to be raw material with ferrocyanide salt, be equipped with the mineral acid of specific concentrations, by hydrothermal treatment consists prepared have novel rank groups assembling structure Prussian blue crystal. prepared mesomorphic particle is whole to be 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.
Advantages such as another object of the present invention provides the method for the above-mentioned Prussian blue mesocrystals of preparation, and this method has with low cost, and equipment is simple, and is easy and simple to handle.
The preparation of described Prussian blue mesocrystals comprises following concrete steps:
1) raw material is prepared
Raw materials usedly be: K
4[Fe (CN)
6] 3H
2O; Hydrochloric acid;
2) preparation of reaction solution
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution; K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.016～0.1mol/L, the HCl volumetric molar concentration is 1～3mol/L;
3) hydrothermal treatment consists
With the 2nd) reaction solution of step gained changes over to and has in the teflon-lined stainless steel autoclave, again autoclave put into drying baker; Set drying baker and be warming up to 100～160 ℃ and be incubated 4～48 hours; Close the heating unit of drying baker then, treat to take out autoclave after the temperature inside the box naturally cools to room temperature;
4) washing separates desciccate
Open autoclave, solution becomes achromaticity and clarification in the polytetrafluoroethyllining lining, and the blue solid precipitation is arranged at the bottom; This blue meal is products therefrom; Use deionized water and absolute ethanol washing product several times respectively, centrifugation goes out pressed powder, places 40～60 ℃ of vacuum drying ovens dry 6～10 hours, obtains described Prussian blue mesocrystals.
Adopt K among the present invention
4[Fe (CN)
6] be raw material, HCl is a mineral acid, is mixed with certain density yellow prussiate of potash acidic solution, mixed solution is moved into have in the teflon-lined stainless steel autoclave, puts into baking oven hydrothermal treatment consists for some time.After treating that autoclave naturally cools to room temperature, by centrifugal, washing, drying process obtains product; And can be by the concentration of hydrochloric acid of control solution and the pattern that the ferrocyanide potassium concn is controlled products therefrom.
Beneficial effect of the present invention:
(1), the present invention prepares Prussian blue mesomorphic structure by yellow prussiate of potash.The microscopic appearance novelty of particle is special.Compare with tradition is Prussian blue, this particle has application promise in clinical practice in catalysis and sensor field.
(2), characteristics such as the method among the present invention compares with traditional biological mineralising method, and it is cheap to have a raw material, and speed is quick, and equipment is simple, and technological process is convenient easy to operate, and condition is not harsh, therefore can significantly reduce the cost of preparation.
(3), method of the present invention is easy to the mesomorphic pattern of product.
Description of drawings
Fig. 1 is scanning electron microscope (SEM) photo with the prepared typical octahedra shape Prussian blue mesocrystals sample of the inventive method
Embodiment
All embodiment all operate by the operation steps of technique scheme.
Embodiment 1
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic mixed solution. K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.032mol/L, the HCl volumetric molar concentration is 2mol/L.Mixing solutions is changed in the teflon-lined autoclave, be warming up to 120 ℃ and be incubated 24 hours.Naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom.With deionized water and dehydrated alcohol washed product repeatedly, centrifugation, place vacuum drying oven in 50 ℃ dry 10 hours down, obtain blue powdered product.Product is octahedra Prussian blue mesocrystals.
Embodiment 2
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
20 is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic mixed solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.016mol/L, the HCl volumetric molar concentration is 2mol/L.Mixing solutions is changed in the teflon-lined autoclave, be warming up to 120 ℃ and be incubated 24 hours.Naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom.With deionized water and dehydrated alcohol washed product repeatedly, centrifugation, place vacuum drying oven in 50 ℃ dry 10 hours down, obtain blue powdered product.Product is octahedra Prussian blue monocrystalline.
Embodiment 3
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic mixed solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.1mol/L, the HCl volumetric molar concentration is 2mol/L.Mixing solutions is changed in the teflon-lined autoclave, be warming up to 120 ℃ and be incubated 24 hours.Naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom.With deionized water and dehydrated alcohol washed product repeatedly, centrifugation, place vacuum drying oven in 50 ℃ dry 10 hours down, obtain blue powdered product.Product is octahedra Prussian blue mesocrystals.
Embodiment 4
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.032mol/L, the HCl volumetric molar concentration is 3mol/L.Mixing solutions is changed in the teflon-lined autoclave, be warming up to 120 ℃ and be incubated 24 hours.Naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom.With deionized water and dehydrated alcohol washed product repeatedly, centrifugation, place vacuum drying oven in 50 ℃ dry 10 hours down, obtain blue powdered product.Product is the octahedra Prussian blue mesocrystals of class.
Embodiment 5
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.032mol/L, the HCl volumetric molar concentration is 3mol/L.Mixing solutions is changed in the teflon-lined autoclave, be warming up to 120 and ℃ the insulation 4 hours.Naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom.With deionized water and dehydrated alcohol washed product repeatedly, centrifugation, place vacuum drying oven in 50 ℃ dry 10 hours down, obtain blue powdered product.Product is the near-spherical Prussian blue mesocrystals.
Embodiment 6
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.032mol/L, the HCl volumetric molar concentration is that 2mol/L. changes mixing solutions in the teflon-lined autoclave over to, be warming up to 100 ℃ and be incubated 24 hours. naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom. use repeatedly washed product of deionized water and dehydrated alcohol, centrifugation, placing vacuum drying oven in 50 ℃ times dry 10 hours, obtain blue powdered product. product is octahedra Prussian blue mesocrystals.
Embodiment 7
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.032mol/L, the HCl volumetric molar concentration is 2mol/L.Mixing solutions is changed in the teflon-lined autoclave, be warming up to 160 and also protected ℃ temperature 24 hours.Naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom.With deionized water and dehydrated alcohol washed product repeatedly, centrifugation, place vacuum drying oven in 50 ℃ dry 10 hours down, obtain blue powdered product.Product is a rocks shape Prussian blue mesocrystals.
Embodiment 8
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.032mol/L, the HCl volumetric molar concentration is 3mol/L.Mixing solutions is changed in the teflon-lined autoclave, be warming up to 120 ℃ and be incubated 4 hours.Naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom.With deionized water and dehydrated alcohol washed product repeatedly, centrifugation, place vacuum drying oven in 50 ℃ dry 10 hours down, obtain blue powdered product.Product is the near-spherical Prussian blue mesocrystals.
Embodiment 9
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.032mol/L, the HCl volumetric molar concentration is 2mol/L.Mixing solutions is changed in the teflon-lined autoclave, be warming up to 120 ℃ and be incubated 48 hours.Naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom.With deionized water and dehydrated alcohol washed product repeatedly, centrifugation, place vacuum drying oven in 50 ℃ dry 10 hours down, obtain blue powdered product.Product is octahedra shape Prussian blue mesocrystals.
Embodiment 10
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.032mol/L, the HCl volumetric molar concentration is 2mol/L.Mixing solutions is changed in the teflon-lined autoclave, be warming up to 120 ℃ and be incubated 24 hours.Naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom.With deionized water and dehydrated alcohol washed product repeatedly, centrifugation, place vacuum drying oven in 40 times ℃ of dryings 10 hours, obtain blue powdered product.Product is octahedra shape Prussian blue mesocrystals.
Embodiment 11
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.032mol/L, the HCl volumetric molar concentration is 2mol/L.Mixing solutions is changed in the teflon-lined autoclave, be warming up to 120 ℃ and be incubated 24 hours.Naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom.With deionized water and dehydrated alcohol washed product repeatedly, centrifugation, place vacuum drying oven in 60 ℃ dry 10 hours down, obtain blue powdered product.Product is octahedra shape Prussian blue mesocrystals.
Embodiment 12
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.032mol/L, the HCl volumetric molar concentration is that 2mol/L. changes mixing solutions in the teflon-lined autoclave over to, be warming up to 120 ℃ and be incubated 24 hours. naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom. use repeatedly washed product of deionized water and dehydrated alcohol, centrifugation, placing vacuum drying oven in 40 ℃ times dry 6 hours, obtain blue powdered product. product is octahedra shape Prussian blue mesocrystals.
Embodiment 13
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution.K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.032mol/L, the HCl volumetric molar concentration is 2mol/L.Mixing solutions is changed in the teflon-lined autoclave, be warming up to 120 ℃ and be incubated 24 hours.Naturally cool to room temperature, this moment, blue particle was deposited on the teflon-lined bottom.With deionized water and dehydrated alcohol washed product repeatedly, centrifugation, place vacuum drying oven in 60 ℃ dry 6 hours down, obtain blue powdered product.Product is octahedra shape Prussian blue mesocrystals.
Claims (3)
1. novel Prussian blue mesocrystals, it is characterized in that: with ferrocyanide salt is raw material, is equipped with mineral acid, must have the Prussian blue mesocrystals of novel rank groups assembling structure through the hydrothermal treatment consists preparation; Prepared mesomorphic particle integral body is shaggy octahedron, class octahedron, near-spherical and rocks shape, is made of countless small scale crystal, and the small scale crystal is nanometer rod and the nanocubes of 150～250nm.
2. method for preparing the described Prussian blue mesocrystals of claim 1, it is characterized in that: preparation process is as follows:
1) raw material is prepared
Raw materials usedly be: K
4[Fe (CN)
6] 3H
2O; Hydrochloric acid;
2) preparation of reaction solution
Take by weighing the solid K of certain mass
4[Fe (CN)
6] 3H
2O is dissolved in deionized water, adds a certain amount of hydrochloric acid and is mixed with and has certain density yellow prussiate of potash acidic solution; K wherein
4[Fe (CN)
6] volumetric molar concentration be 0.016～0.1mol/L, the HCl volumetric molar concentration is 1～3mol/L;
3) hydrothermal treatment consists
With the 2nd) reaction solution of step gained changes over to and has in the teflon-lined stainless steel autoclave, again autoclave put into drying baker; Set drying baker and be warming up to 100～160 ℃ and be incubated 4～48 hours; Close the heating unit of drying baker then, treat to take out autoclave after the temperature inside the box naturally cools to room temperature;
4) washing separates desciccate
Open autoclave, solution becomes achromaticity and clarification in the polytetrafluoroethyllining lining, and the blue solid precipitation is arranged at the bottom; This blue meal is products therefrom; Use deionized water and absolute ethanol washing product several times respectively, centrifugation goes out pressed powder, places 40～60 ℃ of vacuum drying ovens dry 6～10 hours, obtains described Prussian blue mesocrystals.
3. method according to claim 2 is characterized in that: by the concentration of hydrochloric acid of control reaction solution and the pattern that the ferrocyanide potassium concn is controlled products therefrom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910199315A CN101704536A (en) | 2009-11-25 | 2009-11-25 | Novel Prussian blue mesocrystals and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910199315A CN101704536A (en) | 2009-11-25 | 2009-11-25 | Novel Prussian blue mesocrystals and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101704536A true CN101704536A (en) | 2010-05-12 |
Family
ID=42374807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910199315A Pending CN101704536A (en) | 2009-11-25 | 2009-11-25 | Novel Prussian blue mesocrystals and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101704536A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556151A (en) * | 2013-10-12 | 2015-04-29 | 西北大学 | Preparation method for prussian blue |
| CN105098157A (en) * | 2015-07-24 | 2015-11-25 | 北京理工大学 | Preparation method of Fe4[Fe(CN)6]3@Co3[Co(CN)6]2 composite material and application of Fe4[Fe(CN)6]3@Co3[Co(CN)6]2 composite material |
| CN105271307A (en) * | 2015-10-12 | 2016-01-27 | 上海第二工业大学 | Prussian-blue derivative Cd2[Fe(CN)6] nanorod and preparation method thereof |
| CN106242310A (en) * | 2016-08-08 | 2016-12-21 | 上海第二工业大学 | A kind of method directly growing Prussian blue thin film on FTO electro-conductive glass |
| CN107342418A (en) * | 2017-06-21 | 2017-11-10 | 浙江大学 | A kind of ferrocyanogen positive electrode and its preparation method and application |
| CN108217691A (en) * | 2016-12-10 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of simple synthesis for adjusting spinelle or prussian blue nano material morphology |
| CN109382128A (en) * | 2018-10-29 | 2019-02-26 | 兰州大学 | The method and catalyst of catalytically synthesizing cyclic carbonate ester |
| CN109715558A (en) * | 2016-09-22 | 2019-05-03 | 阿尔特里斯股份制有限公司 | Produce the method that six cyanogen close iron (II) sour iron (II) sodium material |
| CN109824060A (en) * | 2019-04-01 | 2019-05-31 | 西北工业大学 | A kind of Prussian blue material in richness ammonia concave surface and preparation method |
| CN112194178A (en) * | 2020-10-20 | 2021-01-08 | 福州大学 | Titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material and preparation method thereof |
| CN112707413A (en) * | 2020-12-29 | 2021-04-27 | 佛山仙湖实验室 | Preparation method and application of high-crystallinity Prussian blue micro-flower electrode material |
| CN113514413A (en) * | 2021-04-22 | 2021-10-19 | 华东师范大学 | Continuous flow synthesis method for controllable particle size of metal-organic framework material |
| CN113860330A (en) * | 2021-08-19 | 2021-12-31 | 北京理工大学 | Preparation method of Prussian blue secondary battery cathode material with low-defect crystal structure |
-
2009
- 2009-11-25 CN CN200910199315A patent/CN101704536A/en active Pending
Cited By (20)
| 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 |
| CN104556151A (en) * | 2013-10-12 | 2015-04-29 | 西北大学 | Preparation method for prussian blue |
| CN105098157A (en) * | 2015-07-24 | 2015-11-25 | 北京理工大学 | Preparation method of Fe4[Fe(CN)6]3@Co3[Co(CN)6]2 composite material and application of Fe4[Fe(CN)6]3@Co3[Co(CN)6]2 composite material |
| CN105271307A (en) * | 2015-10-12 | 2016-01-27 | 上海第二工业大学 | Prussian-blue derivative Cd2[Fe(CN)6] nanorod and preparation method thereof |
| CN106242310A (en) * | 2016-08-08 | 2016-12-21 | 上海第二工业大学 | A kind of method directly growing Prussian blue thin film on FTO electro-conductive glass |
| CN106242310B (en) * | 2016-08-08 | 2019-03-01 | 上海第二工业大学 | A method of directly growing Prussian blue film on FTO electro-conductive glass |
| CN109715558A (en) * | 2016-09-22 | 2019-05-03 | 阿尔特里斯股份制有限公司 | Produce the method that six cyanogen close iron (II) sour iron (II) sodium material |
| CN109715558B (en) * | 2016-09-22 | 2022-05-27 | 阿尔特里斯股份制有限公司 | Method for producing iron (II) sodium hexacyanoferrate (II) material |
| CN108217691A (en) * | 2016-12-10 | 2018-06-29 | 中国科学院大连化学物理研究所 | A kind of simple synthesis for adjusting spinelle or prussian blue nano material morphology |
| CN107342418A (en) * | 2017-06-21 | 2017-11-10 | 浙江大学 | A kind of ferrocyanogen positive electrode and its preparation method and application |
| CN109382128B (en) * | 2018-10-29 | 2022-04-01 | 兰州大学 | Method and catalyst for catalytic synthesis of cyclic carbonate |
| CN109382128A (en) * | 2018-10-29 | 2019-02-26 | 兰州大学 | The method and catalyst of catalytically synthesizing cyclic carbonate ester |
| CN109824060A (en) * | 2019-04-01 | 2019-05-31 | 西北工业大学 | A kind of Prussian blue material in richness ammonia concave surface and preparation method |
| CN109824060B (en) * | 2019-04-01 | 2022-07-05 | 西北工业大学 | Ammonia-rich concave Prussian blue material and preparation method thereof |
| CN112194178B (en) * | 2020-10-20 | 2021-06-01 | 福州大学 | Titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material and preparation method thereof |
| CN112194178A (en) * | 2020-10-20 | 2021-01-08 | 福州大学 | Titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material and preparation method thereof |
| CN112707413A (en) * | 2020-12-29 | 2021-04-27 | 佛山仙湖实验室 | Preparation method and application of high-crystallinity Prussian blue micro-flower electrode material |
| CN112707413B (en) * | 2020-12-29 | 2022-11-04 | 佛山仙湖实验室 | Preparation method and application of high-crystallinity Prussian blue micro-flower electrode material |
| CN113514413A (en) * | 2021-04-22 | 2021-10-19 | 华东师范大学 | Continuous flow synthesis method for controllable particle size of metal-organic framework material |
| CN113860330A (en) * | 2021-08-19 | 2021-12-31 | 北京理工大学 | Preparation method of Prussian blue secondary battery cathode material with low-defect crystal structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101704536A (en) | Novel Prussian blue mesocrystals and preparation method thereof | |
| CN107983300B (en) | The charcoal composite material and preparation method and application of manganese dioxide modification | |
| Zhang et al. | Polyacrylamide gel synthesis and photocatalytic performance of Bi2Fe4O9 nanoparticles | |
| CN103785859B (en) | Method for manufacturing nanometer mesoporous material | |
| CN104148047B (en) | Macro preparation method for carbon doped zinc oxide-based visible-light catalyst | |
| CN102060330B (en) | Method for synthetizing bismuth molybdate octahedral nanoparticle by microwave radiation heating | |
| Zhang et al. | Synthesis of BiOBr–graphene and BiOBr–graphene oxide nanocomposites with enhanced visible light photocatalytic performance | |
| CN105060351B (en) | Flower-like cobaltosic oxide material composed of nanoparticles and preparation method thereof | |
| He et al. | Microwave-assisted synthesis of BiOCl and its adsorption and photocatalytic activity | |
| CN108636395A (en) | A kind of composite photo-catalyst of weakly visible photoresponse and its preparation and application | |
| CN108217691A (en) | A kind of simple synthesis for adjusting spinelle or prussian blue nano material morphology | |
| CN105833887B (en) | A kind of BiOCl/ β FeOOH composite nano materials and preparation method thereof | |
| CN107185547A (en) | A kind of C/Fe FeVO4Composite photo-catalyst and its preparation method and application | |
| CN109734056A (en) | Metal oxide/preparation method of fold rGO composite nano materials and the preparation method of fold nano-metal-oxide | |
| He et al. | Biologically formed hollow cuprous oxide microspheres | |
| CN112516997A (en) | CeO2/MnO2Method for preparing nano-rod | |
| CN108313993B (en) | Synthesis method of nitric acid | |
| CN102070178A (en) | Method for preparing yttrium oxide micro-nano-materials based on hydrothermal technology regulation and control | |
| CN106082298B (en) | Preparation method of cerium-bismuth composite oxide nanorod material | |
| CN108927138A (en) | A kind of Bi2O3/ diatomite composite photocatalytic material and preparation method thereof | |
| CN114570402A (en) | Preparation method of carbon-defect-containing and oxygen-doped carbon nitride photocatalytic material and application of carbon-defect-containing and oxygen-doped carbon nitride photocatalytic material in removal of tetracycline in water body | |
| Lian et al. | Surfactant-assisted solvothermal preparation of submicrometer-sized hollow hematite particles and their photocatalytic activity | |
| CN103833080A (en) | Preparation method for cadmium molybdate porous spheres | |
| CN107416899B (en) | A kind of nano wire α-Bi2O3The preparation method of dusty material | |
| CN109133144A (en) | A kind of preparation method of monodisperse ultra-small grain size ceria nano-crystalline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100512 |