CN109437338A - The preparation method of one type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material - Google Patents
The preparation method of one type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Abstract
The present invention provides the preparation methods of a type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material, belong in field of material technology.The present invention is with the nano nickel ferro-cobalt Prussian blue analogue presoma of Nickelous nitrate hexahydrate, three citric acid monohydrate trisodiums, the potassium ferricyanide and potassium cobalticyanide synthesis of cubic structure, then it is centrifugated after being corroded with ammonia spirit, wash sample, class sawtooth pattern nickel cobalt iron Prussian blue analogue nano material is obtained after drying, it is sintered, " Z "-O is obtainedxNano material."Z"-OxNano material can effectively be catalyzed permonosulphuric acid salt and generate hydroxyl radical free radical and potentiometric titrations, and then bisphenol-A of degrading.The present invention is unevenly distributed the position to determine corrosion with metal coordinate bond in presoma, form anisotropic etch, new approach is opened up for the fine tuning of the structure and property of MOF material, and this method has the characteristics that easy to operate, short preparation period, high financial profit, is suitble to large-scale production.
Description
Technical field
The invention belongs to field of material technology, and in particular to a type sawtooth pattern Prussian blue analogue sintered oxide nanometer material
The preparation method of material.
Background technique
Strategy based on chemical etching is that there is the metal organic frame (MOF) of neomorph to have warded off new approach for preparation.Energy
The presence for enough destroying metal/organic linker etchant (such as H+ or OH-) of MOF, which can be such that MOF presoma becomes, to be had
The crystal of adjustable spherical shape, cube or tetrahedral configuration.Due to being had differences between the inside and facet of MOF presoma crystal
Property reaction, sometimes, nanometer MOF(such as zeolite imidazole ester frame structure material (ZIF), Prussian blue analogue (PBA)) can obtain
Hollow structure, the structure for further modulating pre-synthesis MOF can create the MOF of higher complexity.
It is still challenging to the MOF for preparing higher complexity although achieving these progress.By taking PBA as an example, erosion
Preferentially occur on the center surface of PBA cube when being carved with, sometimes on their angle, leads to the PBA of different shape.This can
It can be the uneven reactivity due to surface and angle.The etching degree and location of etch of MOF crystal may be related with defect, or
It is related with metal-ligand key.Unfortunately, the example about the research of this respect is seldom, and especially many researchs are still concentrated
In the synthesis and characterization of material, and the understanding of MOF etching behavior is lacked and limits the comprehensive spy of the MOF with labyrinth
Rope.Therefore, the structure of existing nanometer synthesis MOF still is limited to mesoporous or hollow structure.
As far as we know, this be first part about by corrode Prussian blue analogue presoma obtain that there is unprecedented class
The report of sawtooth pattern Prussian blue analogue in this respect.It enriches the complicated appearance structure design about nanometer MOF, to realize
The multifunctionality of MOF brings more research aircraft meetings.It also provides for the anisotropic etching mechanism of MOF ideal flat
Platform.By the heat treatment of " Z "-PBA, it is successfully prepared for nickel cobalt Iron mixed oxide nano material (" Z "-Ox), to catalysis
Permonosulphuric acid salt (PMS) shows excellent catalytic performance with bisphenol-A of degrading.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a type sawtooth pattern Prussian blue analogue nano material
Preparation method.The present invention corrodes to obtain class by ammonium hydroxide using nickel cobalt iron Prussian blue analogue (NiCoFe-PBA) as template
Sawtooth pattern Prussian blue analogue (" Z "-PBA) enriches the appearance structure design about nanometer MOFs complexity；Using being heat-treated
To mixed oxide nanoparticle material can keep the structure of " Z "-PBA after corrosion well, and can effectively catalytic degradation it is double
Thus phenol A solves the pollution problem as caused by bisphenol-A.
For achieving the above object, the present invention adopts the following technical scheme:
The preparation method of one type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material, comprising the following steps:
(1) preparation of nano nickel ferro-cobalt Prussian blue analogue (NiCoFe-PBA) presoma of cubic structure: with the potassium ferricyanide, cobalt cyanogen
Changing potassium, three citric acid monohydrate trisodiums and Nickelous nitrate hexahydrate is raw material, and the nanometer of cubic structure is prepared through hydrothermal synthesis method
Nickel cobalt iron Prussian blue analogue (NiCoFe-PBA)；
(2) preparation of class sawtooth pattern nickel cobalt iron Prussian blue analogue (" Z "-PBA) nano material: will be obtained vertical in step (1)
Nano nickel ferro-cobalt Prussian blue analogue (NiCoFe-PBA) presoma of square structure is evenly dispersed into 10 ml ethyl alcohol, stirs to complete
Full dispersion, obtains mixed solution；Then ammonia spirit is slowly poured into mixed solution, stirs 1 h；Then reaction solution is carried out
Centrifuge separation, washing；Sample after washing is put into baking oven and keeps the temperature 12 h at 70 DEG C and is dried, obtains class sawtooth pattern nickel
Ferro-cobalt Prussian blue analogue (" Z "-PBA) nano material；
(3) class sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide (" Z "-Ox) nano material preparation: will be obtained by step (2)
Class sawtooth pattern nickel cobalt iron Prussian blue analogue (" Z "-PBA) nano material be put into Muffle furnace, 1.5 h are kept the temperature at 350 DEG C, rise
Warm rate is 2 DEG C/min, finally obtains class sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide (" Z "-Ox) nano material.
In above-mentioned preparation method, in the ammonia spirit of step (2), the volume ratio of deionized water and ammonium hydroxide is 1:2.
In above-mentioned preparation method, nano nickel ferro-cobalt Prussian blue analogue (NiCoFe-PBA) forerunner of step (1) cubic structure
The preparation of body, comprising the following specific steps
1) a certain amount of three citric acid monohydrates trisodium and Nickelous nitrate hexahydrate are put into beaker, deionized water is then added, obtained
To mixed system, mixed system is stirred to raw material and is completely dissolved, obtains mixed solution A；
2) a certain amount of potassium cobalticyanide is put into beaker, deionized water, wiring solution-forming is added；
3) potassium cobalticyanide solution is added in mixed solution 1,1 h of magnetic agitation obtains mixed solution B；
4) a certain amount of potassium ferricyanide is put into beaker, deionized water, wiring solution-forming is added；
5) potassium ferricyanide solution is added in mixed solution 2,1 h of magnetic agitation obtains mixed solution C；
6) mixed solution C is poured into reaction kettle, 80 DEG C of 20 h of reaction；Reaction product is through centrifuge washing, 70 DEG C of 12 h of drying,
Obtain the nano nickel ferro-cobalt Prussian blue analogue (NiCoFe-PBA) of cubic structure.
Further, the dosage of three citric acid monohydrate trisodiums is 0.264 g in step 1), and the dosage of Nickelous nitrate hexahydrate is
0.174 g, the dosage of deionized water are 20 mL；
Further, the dosage of potassium cobalticyanide is 0.026 g in step 2, and the dosage of deionized water is 10 mL；Further,
The dosage of the potassium ferricyanide is 0.105 g in step 4), and the dosage of deionized water is 10 mL；
One type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide Application of micron is in the degradation of catalysis bisphenol-A.
The beneficial effects of the present invention are:
1) present invention using NiCoFe-PBA as presoma, then ammonium hydroxide corroded, obtain class sawtooth pattern nickel cobalt iron class
Prussian blue (" Z "-PBA).The complicated appearance structure design about nanometer MOF is enriched, for the multi-functional band for realizing MOF
More development opportunities are carried out.It provides new thinking also for the anisotropic etching of MOF.
2) the class sawtooth pattern nickel cobalt iron Prussian blue analogue that the present invention obtains after heat treatment obtains class sawtooth pattern nickel cobalt iron class
Prussian blue sintered oxide (" Z "-Ox), due to increasing surface area at sawtooth pattern, provide more catalytic active sites
Point improves degradation bis-phenol so that it, which is catalyzed permonosulphuric acid salt (PMS), generates more potentiometric titrations and hydroxyl radical free radical
The efficiency of A.
3) equipment and material required for preparation method of the invention are easily obtained, and technological operation is simple, process conditions letter
It is clean, there is at low cost, safety, high-efficient advantage, application easy to spread.
Detailed description of the invention
Fig. 1 is the microscopic appearance for implementing NiCoFe-PBA in 1.
Fig. 2 is the microscopic appearance of " Z "-PBA in embodiment 1.
Fig. 3 is the X-ray diffraction (XRD) figure of NiCoFe-PBA and " Z "-PBA in example 1.
Fig. 4 is X-ray photoelectron spectroscopic analysis (XPS) figure of NiCoFe-PBA and " Z "-PBA in embodiment 1.
Fig. 5 is that " Z "-PBA through being sintered at 350 DEG C obtains " Z "-O in embodiment 1xScanning microgram.
Fig. 6 is NiCoFe-O of the NiCoFe-PBA through being sintered at 350 DEG C in comparative example 1xScanning microgram.
Fig. 7 is to obtain " Z "-O through sintering in Application Example 1 and Comparison study example 1xNano material and NiCoFe-OxIt receives
Scattergram of the rice material as catalyst PMS degradation bisphenol-A.
Fig. 8 is to obtain " Z "-O through sintering in Application Example 1 and Comparison study example 1xNano material and NiCoFe-OxIt receives
Schematic diagram of the rice material as the efficiency value K of catalyst PMS degradation bisphenol-A.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, right below in conjunction with attached drawing, that is, embodiment
The present invention is further elaborated.It should be appreciated that described herein, the specific embodiments are only for explaining the present invention, not
For limiting the present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below that
Not constituting conflict between this can combine.
Embodiment 1
The preparation method of one type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material, comprising the following steps:
(1) preparation of NiCoFe-PBA presoma:
Using the potassium ferricyanide, potassium cobalticyanide, three citric acid monohydrate trisodiums and Nickelous nitrate hexahydrate as raw material, prepared through hydrothermal synthesis method
Obtain NiCoFe-PBA；
(2) preparation of " Z "-PBA nano material:
NiCoFe-PBA obtained in (1) is evenly dispersed into 10 ml ethyl alcohol, it stirs to being completely dispersed, obtains mixed solution；So
Ammonia spirit is slowly poured into mixed solution afterwards, stirs 1 h；Then reaction solution is centrifuged, is washed；Washing
Sample afterwards, which is put into baking oven, to be kept the temperature 12 h at 70 DEG C and is dried, and " Z "-PBA nano material is obtained.
(3) preparation of " Z "-Ox nano material:
" Z "-PBA nano material sample obtained in step (2) is put into Muffle furnace, 1.5 h are kept the temperature at 350 DEG C, is heated up
Rate is 2 DEG C/min, finally obtains " Z "-Ox nano material.
In above-mentioned preparation method, in the ammonia spirit of step (2), the volume ratio of deionized water and ammonium hydroxide is 1:2.
In above-mentioned preparation method, the preparation of step (1) NiCoFe-PBA presoma, comprising the following specific steps
1) the three citric acid monohydrate trisodiums of 0.264 g and 0.174 g Nickelous nitrate hexahydrate are put into beaker, are then added 20
ML deionized water, obtains mixed system, and mixed system is stirred to raw material and is completely dissolved, and obtains mixed solution A；
2) a certain amount of 0.026 g potassium cobalticyanide is put into beaker, 10 mL deionized waters, wiring solution-forming is added；
3) potassium cobalticyanide solution is added in mixed solution 1,1 h of magnetic agitation obtains mixed solution B；
4) potassium ferricyanide of 0.105 g is put into beaker, 10 mL deionized waters, wiring solution-forming is added；
5) potassium ferricyanide solution is added in mixed solution 2,1 h of magnetic agitation obtains mixed solution C；
6) mixed solution C is poured into reaction kettle, 80 DEG C of 20 h of reaction；Reaction product is through centrifuge washing, 70 DEG C of 12 h of drying,
Up to NiCoFe-PBA.
Comparative example 1
(1) preparation of NiCoFe-PBA presoma:
Using the potassium ferricyanide, potassium cobalticyanide, three citric acid monohydrate trisodiums and Nickelous nitrate hexahydrate as raw material, prepared through hydrothermal synthesis method
Obtain NiCoFe-PBA；
(2) synthesis of nickel cobalt iron Prussian blue analogue sintered oxide (NiCoFe- Ox) nano material
NiCoFe-PBA sample obtained in (1) is installed with small crucible and is covered, and is put it into Muffle furnace, is protected at 350 DEG C
1.5 h of temperature, heating rate are 2 DEG C/min, finally obtain NiCoFe- OxNano material.
Gained NiCoFe-OxScanning microgram such as Fig. 6 of nano material.
Bisphenol-A degradation experiment
Application Example 1
By " Z "-O obtained in embodiment 1xNano material is used for the catalytic degradation of bisphenol-A, the specific steps are as follows:
(1) the bisphenol-A solution of 30 ppm is configured；
(2) the configured bisphenol-A solution of 50 mL (30 ppm) is measured, weighs " Z "-O of 5 mgxNano material is put into double
In phenol solution A, ultrasound 10 min, 30 min of magnetic agitation obtain mixed solution, establish desorption-adsorption equilibrium；
(3) it weighs 10 mg permonosulphuric acid salt (PMS) to put into mixed solution obtained by step (2), magnetic agitation；Exist respectively
Degradation experiment start after 0 min, 10 min, 20 min, 30 min, 40 min, 50 min be sampled, take 1 mL every time
Solution, quenched with the methanol of 0.5 mL；Bisphenol-A is measured by liquid chromatograph.
Comparison study example 1
By NiCoFe- O obtained in comparative example 1xNano material is used for the catalytic degradation of bisphenol-A, the specific steps are as follows:
(1) the bisphenol-A solution of 30 ppm is configured；
(2) the configured bisphenol-A solution of 50 mL (30 ppm) is measured, weighs the NiCoFe- O of 5mgxNano material is put into
In bisphenol-A solution, ultrasound 10 min, 30 min of magnetic agitation obtain mixed solution, establish desorption-adsorption equilibrium；
(3) it weighs 10 mg permonosulphuric acid salt (PMS) to put into mixed solution obtained by step (2), magnetic agitation；Exist respectively
Degradation experiment start after 0 min, 10 min, 20 min, 30 min, 40 min, 50 min be sampled, take 1 mL every time
Solution, quenched with the methanol of 0.5 mL；Bisphenol-A is measured by liquid chromatograph.
Interpretation of result
The microscopic appearance of 1 gained NiCoFe-PBA of embodiment is as shown in Figure 1.The microscopic appearance of gained " Z "-PBA is as shown in Figure 2.
X-ray diffraction (XRD) result such as Fig. 3 of NiCoFe-PBA and " Z "-PBA.The X-ray photoelectricity of NiCoFe-PBA and " Z "-PBA
Sub- energy spectrum analysis (XPS) result such as Fig. 4.Analysis finds during synthesizing NiCoFe-PBA, cobalt, nickel element valence state do not have
Redox reaction occurs for the ferric iron of variation, addition, and partial reduction is at ferrous iron.When being corroded to obtain to it with ammonium hydroxide
When " Z "-PBA, combination corresponding to ferric iron can peak disappear, illustrate that ferric iron reacts with ammonia water, and ferrous iron not with ammonia
Water reaction, so that anisotropic etch occur, obtains class sawtooth pattern Prussian blue analogue.
" Z "-PBA is through being sintered obtained " Z "-O in embodiment 1 at 350 DEG CxScanning microgram such as Fig. 5；In comparative example 1
Scanning microgram such as Fig. 6 of NiCoFe-Ox of the NiCoFe-PBA through being sintered at 350 DEG C；
From Fig. 5 and Fig. 6 can be seen that " Z "-Ox that " Z "-PBA and NiCoFe-PBA are respectively obtained after Overheating Treatment and
NiCoFe-Ox is still able to maintain original appearance structure.
Through being sintered obtained " Z "-O in Application Example 1 and Comparison study example 1xNano material and NiCoFe-OxNanometer material
Expect the scattergram as catalyst PMS degradation bisphenol-A, as shown in Figure 7.Through burning in Application Example 1 and Comparison study example 1
Tie obtained " Z "-OxNano material and NiCoFe-OxEfficiency value K of the nano material as catalyst PMS degradation bisphenol-A
Schematic diagram, as shown in Figure 8.Compare the catalytic degradation efficiency of Application Example 1 and Comparison study example 1, it is found that pass through etching
" Z "-PBA that NiCoFe-PBA is obtained is sintered obtained " Z "-OxNano material in 50 minutes can catalytic degradation it is complete
The bisphenol-A of 30 ppm, efficiency reach 99.9 %, and catalytic performance is higher than NiCoFe- OxNano material, apparent reaction rates
Constant k improves 1.22 times.This is because " Z "-OxThe sawtooth pattern pattern of nano material, provides more catalytic active sites
Point, to be catalyzed, PMS generates more potentiometric titrations and hydroxyl radical free radical, catalytic performance greatly improve.
As it will be easily appreciated by one skilled in the art that the foregoing is merely preferred embodiments of the invention, not to limit
The system present invention, any modifications, equivalent replacements, and improvements done within the spirit and principles of the present invention should be included in this
Within the protection scope of invention.
Claims (9)
1. a Prussia type sawtooth pattern nickel cobalt Tie Lei receives the preparation method of sintered oxide indigo plant rice material, which is characterized in that packet
Include following steps:
(1) preparation of the nano nickel ferro-cobalt Prussian blue analogue presoma of cubic structure: with the potassium ferricyanide, potassium cobalticyanide, three hydrations
Trisodium citrate and Nickelous nitrate hexahydrate are raw material, and the general Shandong of nano nickel ferro-cobalt class of cubic structure is prepared through hydrothermal synthesis method
Scholar is blue；
(2) preparation of class sawtooth pattern nickel cobalt iron Prussian blue analogue nano material: obtained cubic structure in step (1) is received
Rice nickel cobalt iron Prussian blue analogue presoma is evenly dispersed into 10 ml ethyl alcohol, stirs to being completely dispersed, obtains mixed solution；Then
Ammonia spirit is slowly poured into mixed solution, 1 h is stirred；Then reaction solution is centrifuged, is washed；After washing
Sample be put into baking oven and keep the temperature 12 h at 70 DEG C and dried, obtain class sawtooth pattern nickel cobalt iron Prussian blue analogue nano material；
(3) preparation of class sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material: by the resulting class sawtooth of step (2)
Type nickel cobalt iron Prussian blue analogue nano material is put into Muffle furnace, and 1.5 h are kept the temperature at 350 DEG C, and heating rate is 2 DEG C/min,
Finally obtain class sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material.
2. the preparation of type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material according to claim 1
Method, it is characterised in that: the preparation of the nano nickel ferro-cobalt Prussian blue analogue presoma of step (1) cubic structure, including following tool
Body step:
1) a certain amount of three citric acid monohydrates trisodium and Nickelous nitrate hexahydrate are put into beaker, deionized water is then added, obtained
To mixed system, mixed system is stirred to raw material and is completely dissolved, obtains mixed solution A；
2) a certain amount of potassium cobalticyanide is put into beaker, deionized water, wiring solution-forming is added；
3) potassium cobalticyanide solution is added in mixed solution 1,1 h of magnetic agitation obtains mixed solution B；
4) a certain amount of potassium ferricyanide is put into beaker, deionized water, wiring solution-forming is added；
5) potassium ferricyanide solution is added in mixed solution 2,1 h of magnetic agitation obtains mixed solution C；
6) mixed solution C is poured into reaction kettle, 80 DEG C of 20 h of reaction；Reaction product is through centrifuge washing, 70 DEG C of 12 h of drying,
Obtain the nano nickel ferro-cobalt Prussian blue analogue of cubic structure.
3. the preparation of type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material according to claim 1
Method, it is characterised in that: in ammonia spirit described in step (2), the volume ratio of deionized water and ammonium hydroxide is 1:2.
4. the preparation of type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material according to claim 2
Method, it is characterised in that: the dosage of three citric acid monohydrate trisodiums is 0.264 g in step 1), and the dosage of Nickelous nitrate hexahydrate is
0.174 g, the dosage of deionized water are 20 mL.
5. the preparation of type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material according to claim 2
Method, it is characterised in that: the dosage of potassium cobalticyanide is 0.026 g in step 2, and the dosage of deionized water is 10 mL.
6. the preparation of type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material according to claim 2
Method, it is characterised in that: the dosage of the potassium ferricyanide is 0.105 g in step 4), and the dosage of deionized water is 10 Ml.
7. a kind of the method as described in claim 1 prepares class sawtooth pattern nickel cobalt iron Prussian blue analogue nano material.
8. a kind of method as claimed in any one of claims 1 to 6 prepares class sawtooth pattern nickel cobalt iron Prussian blue analogue sintering oxygen
Compound nano material.
9. class sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide Application of micron as claimed in claim 8 is double in catalysis
The degradation of phenol A.
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| CN111235575A (en) * | 2020-02-20 | 2020-06-05 | 肇庆市华师大光电产业研究院 | Selective etching method for preparing material with controllable morphology |
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| CN113121836A (en) * | 2021-03-04 | 2021-07-16 | 华南师范大学 | Nano-framework-shaped super-structure Fe-Co-Ni metal organic framework and preparation method and application thereof |
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| CN114790014A (en) * | 2022-03-25 | 2022-07-26 | 中山大学 | Hollow mesh nano cage structure metal oxide and preparation method and application thereof |
| CN115090287A (en) * | 2022-06-02 | 2022-09-23 | 中国科学技术大学 | Fe-Co doped ozone activation catalyst Fe-CoO x And preparation method |
| CN115090287B (en) * | 2022-06-02 | 2024-02-27 | 中国科学技术大学 | Fe-CoO (Fe-CoO) ozone activation catalyst doped with iron and cobalt x Method for preparing the same |
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