CN106732232B - A kind of preparation method of the yolk type Fenton microreactor of inner surface supported precious metal nano-particle - Google Patents
A kind of preparation method of the yolk type Fenton microreactor of inner surface supported precious metal nano-particle Download PDFInfo
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Abstract
A kind of preparation method of the yolk type Fenton microreactor of inner surface supported precious metal nano-particle, is related to a kind of preparation method of Fenton microreactor.It is to solve existing out-phase Fenton reagent H2O2The problem of utilization ratio is low, Fenton's reaction rate is slow and Fenton reagent is easily reunited.Method：One, magnetic nano-particle is distributed in water, ethyl orthosilicate and ammonium hydroxide is then added, product A is obtained by the reaction；Two, product A is added in precious metal salt solution, stirring is added reducing agent, product B is obtained by the reaction；Three, product B is scattered in conductive high polymer monomer, initiator is added and causes polymerization, product C is obtained by the reaction；Four, product C is put into etching agent, etches, obtains final product.Microreactor prepared by this method can improve out-phase Fenton's reaction rate, to H2O2Utilization ratio higher, it is cost-effective.Magnetic nano-particle has higher stability, is not susceptible to assemble.The present invention is used to prepare Fenton microreactor.
Description
Technical field
The present invention relates to a kind of preparation methods of Fenton microreactor.
Background technology
In recent years, global water pollution form is increasingly severe.By being found to a large amount of water pollution case works, wherein quite big
A part is caused by organic matter.The pollutant is widely present in pesticide, chemical fertilizer and industrial wastewater, has toxicity
The features such as high, characteristic of concentration is by force and flowing is big, the safety in production of healthy living and industrial or agricultural to the people, which causes, to be seriously threatened.Such as
The pollutant is effectively treated in what, becomes the important topic for being related to China's strategy of sustainable development.
Due to generally very low, the traditional sewage water treatment method of concentration of the pollutant in water source：Such as the precipitation method, filtering
Method and biological degradation method etc. are difficult to be effectively treated to it.Developing a kind of new method of economical and efficient just becomes urgently to be resolved hurrily
The problem of.In recent years, the method for handling light concentration organic pollutant using Fenton's reaction obtains the very big pass of researcher
Note.However, in actual application, it has been found that although out-phase Fenton reagent high-efficiency environment friendly, the presence of following defect, sternly
The extensive use of out-phase Fenton reagent is limited again：(1) when being reacted, it is necessary to H be excessively used2O2, not only reduce H2O2's
Utilization ratio, and increase cost；(2) reaction can only carry out on the surface of out-phase Fenton reagent, and reaction rate is relatively slow；
(3) out-phase Fenton reagent is susceptible to clustering phenomena, and degrading activity is caused to decline.
Invention content
The present invention is to solve existing out-phase Fenton reagent H2O2Utilization ratio is low, Fenton's reaction rate is slow and Fenton examination
There is provided a kind of preparation side of the yolk type Fenton microreactor of inner surface supported precious metal nano-particle the problem of agent is easily reunited
Method.H is assisted by noble metal nano particles2O2It decomposes and means such as " confinement effects " of microreactor, the traditional out-phase Fenton of solution
It is insufficient existing for reagent.
The preparation method of the yolk type Fenton microreactor of inner surface supported precious metal nano-particle of the present invention, including it is following
Step：
One, magnetic nano-particle is distributed in water, ethyl orthosilicate is then added to final concentration of 1mg/mL~30mg/
ML stirs 2-3min, adds ammonium hydroxide to final concentration of 0.01mg/mL~1mg/mL, reacts 6-12h, obtain product A；
Two, product A is added in precious metal salt solution, wherein final concentration of 0.1mg/mL~10mg/mL of precious metal salt,
After stirring 10min~30min, reducing agent is added to final concentration of 1mg/mL~50mg/mL, reacts 10min~60min, obtains
Product B；
Three, product B is scattered in conductive high polymer monomer, wherein the final concentration of 10mg/mL of conductive high polymer monomer
~100mg/mL is added initiator to final concentration of 10mg/mL~300mg/mL, causes and polymerize, and reaction 3h~for 24 hours, it is produced
Object C；
Four, product C is put into etching agent, etching 10h~for 24 hours, obtain final product.
Further, the magnetic nano-particle described in step 1 is ferroso-ferric oxide, di-iron trioxide or hydroxyl oxidation
Iron；
Further, the precious metal salt in precious metal salt solution described in step 2 be silver nitrate, gold chloride, chloroplatinic acid,
One or more of palladium bichloride, silver ammino solution, potassium chloroplatinate, sub- potassium chloroplatinate；
Further, the reducing agent described in step 2 is sodium borohydride, hydrazine or glucose；
Further, the conductive high polymer monomer described in step 3 is aniline, pyrroles, thiophene, acetylene, 3- hexyl thiophenes
One or more of pheno, 3,4- ethene dioxythiophenes press a mixture of arbitrary proportions.
Further, the initiator described in step 3 is ferric trichloride, ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.
Further, the etching agent described in step 4 is hydrofluoric acid, sodium hydroxide solution, potassium hydroxide solution or ammonia
Water, wherein hydrofluoric acid, sodium hydroxide solution, potassium hydroxide solution and ammonia concn are 0.5-3mol/L.
Fenton microreactor prepared by the present invention is yolk type microreactor, and inner surface load has noble metal nano grain
Son.First using magnetic nano-particle as kernel templates, upper complete titanium dioxide is coated on its surface by hydrolyzing tetraethoxy orthosilane
Silicon shell；Later, noble metal nano particles are deposited on silica shell layer surface；Then, continue in outer surface aggregate conduction
High polymer monomer forms complete conducting high polymers object shell；Finally, by intermediate silica shell selective etch
Fall, has just obtained yolk type microreactor.In the microreactor, magnetic nano-particle is " core "；Conductive high polymer monomer is poly-
It is " shell " to close object, and noble metal nano particles are embedded in the inner surface of shell.
The invention has the advantages that：
The yolk type Fenton microreactor of inner surface supported precious metal nano-particle prepared by the present invention is received than traditional
Rice corpuscles is to H2O2Utilization ratio higher, it is cost-effective.In Fenton's reaction, H2O2It decomposes and generates with high oxidative
OH is come dirty organic pollutants of degrading.The metal nanoparticle of microreactor inner surface load prepared by the present invention is to H2O2's
Decomposing has catalytic action, is conducive to accelerate H2O2Decomposition, thus H can be improved2O2Decomposition rate, and then improve its utilization
Efficiency and degradation rate.
" confinement effect " is property specific to microreactor.It is different from external solution, reaction is happened in microreactor
Portion.Due to the presence of " confinement effect ", contribute to the enrichment of dirty Organic substance in water, improves out-phase Fenton's reaction rate.
The yolk type Fenton microreactor of inner surface supported precious metal nano-particle prepared by the present invention is than traditional magnetic
Property nano-particle have higher stability, be not susceptible to assemble.Since magnetic nano-particle is in the inside of microreactor, at this
It, can be to avoid the erosion of extraneous solution under a microenvironment protection.Further, since the shell protection of microreactor, magnetic nano particle
It is separated between son, can effectively avoid the aggregation of out-phase Fenton reagent (i.e. magnetic nano-particle) during use, thus
Stability can be improved.
Description of the drawings
Fig. 1 is ferriferrous oxide nano-particle stereoscan photograph in embodiment one；
Fig. 2 is that the scanning electron microscope of the yolk type microreactor of inner surface supported precious metal nano-particle in embodiment one is shone
Piece；
Fig. 3 is that the transmission electron microscope of the yolk type microreactor of inner surface supported precious metal nano-particle in embodiment one shines
Piece；
Fig. 4 is that the yolk type microreactor of inner surface supported precious metal nano-particle in embodiment one and initial four aoxidize three
Iron carries out the comparison diagram of Fenton's reaction degradation of methylene blue；
Fig. 5 be inner surface supported precious metal nano-particle in embodiment one yolk type microreactor and ferroso-ferric oxide into
H during row Fenton's reaction degradation of methylene blue2O2Utilization ratio comparison diagram；
Fig. 6 is after the yolk type microreactor of inner surface supported precious metal nano-particle in embodiment one carries out Fenton's reaction
Transmission electron microscope photo；
Fig. 7 is the scanning of the yolk type Fenton microreactor of inner surface supported precious metal nano-particle prepared by embodiment two
Electromicroscopic photograph.
Specific implementation mode
Technical solution of the present invention is not limited to act specific implementation mode set forth below, further includes between each specific implementation mode
Arbitrary combination.
Specific implementation mode one：The yolk type Fenton microreactor of present embodiment inner surface supported precious metal nano-particle
Preparation method, include the following steps：
One, magnetic nano-particle is distributed in water, ethyl orthosilicate is then added to final concentration of 1mg/mL~30mg/
ML stirs 2-3min, adds ammonium hydroxide to final concentration of 0.01mg/mL~1mg/mL, reacts 6-12h, obtain product A；
Two, product A is added in precious metal salt solution, wherein final concentration of 0.1mg/mL~10mg/mL of precious metal salt,
After stirring 10min~30min, reducing agent is added to final concentration of 1mg/mL~50mg/mL, reacts 10min~60min, obtains
Product B；
Three, product B is scattered in conductive high polymer monomer, wherein the final concentration of 10mg/mL of conductive high polymer monomer
~100mg/mL is added initiator to final concentration of 10mg/mL~300mg/mL, causes and polymerize, and reaction 3h~for 24 hours, it is produced
Object C；
Four, product C is put into etching agent, etching 10h~for 24 hours, obtain final product.
Specific implementation mode two：The present embodiment is different from the first embodiment in that：Magnetism described in step 1
Nano-particle is ferroso-ferric oxide, di-iron trioxide or FeOOH.It is other same as the specific embodiment one.
Specific implementation mode three：The present embodiment is different from the first and the second embodiment in that：It is added just in step 1
Silester is to final concentration of 5mg/mL~25mg/mL.It is other the same as one or two specific embodiments.
Specific implementation mode four：The present embodiment is different from the first and the second embodiment in that：It is added just in step 1
Silester is to final concentration of 10mg/mL~20mg/mL.It is other the same as one or two specific embodiments.
Specific implementation mode five：Unlike one of present embodiment and specific implementation mode one to four：Add in step 1
Enter ammonium hydroxide to final concentration of 0.05mg/mL~0.9mg/mL.It is other identical as one of specific implementation mode one to four.
Specific implementation mode six：Unlike one of present embodiment and specific implementation mode one to four：Add in step 1
Enter ammonium hydroxide to final concentration of 0.1mg/mL~0.8mg/mL.It is other identical as one of specific implementation mode one to four.
Specific implementation mode seven：Unlike one of present embodiment and specific implementation mode one to four：Add in step 1
Enter ammonium hydroxide to final concentration of 0.3mg/mL~0.6mg/mL.It is other identical as one of specific implementation mode one to four.
Specific implementation mode eight：Unlike one of present embodiment and specific implementation mode one to four：Add in step 1
Enter ammonium hydroxide to final concentration of 0.4mg/mL~0.5mg/mL.It is other identical as one of specific implementation mode one to four.
Specific implementation mode nine：Unlike one of present embodiment and specific implementation mode one to eight：Institute in step 2
It is silver nitrate, gold chloride, chloroplatinic acid, palladium bichloride, silver ammino solution, potassium chloroplatinate, Asia to state the precious metal salt in precious metal salt solution
One or more of potassium chloroplatinate.It is other identical as one of specific implementation mode one to eight.
Specific implementation mode ten：Unlike one of present embodiment and specific implementation mode one to nine：It is expensive in step 2
Final concentration of 0.5mg/mL~9mg/mL of metal salt.It is other identical as one of specific implementation mode one to nine.
Specific implementation mode 11：Unlike one of present embodiment and specific implementation mode one to nine：In step 2
Final concentration of 1mg/mL~7mg/mL of precious metal salt.It is other identical as one of specific implementation mode one to nine.
Specific implementation mode 12：Unlike one of present embodiment and specific implementation mode one to nine：In step 2
Final concentration of 3mg/mL~5mg/mL of precious metal salt.It is other identical as one of specific implementation mode one to nine.
Specific implementation mode 13：Present embodiment is unlike specific implementation mode one to one of 12：Step 2
Described in reducing agent be sodium borohydride, hydrazine or glucose.It is other identical as specific implementation mode one to one of 12.
Specific implementation mode 14：Present embodiment is unlike specific implementation mode one to one of 13：Step 2
Middle addition reducing agent is to final concentration of 5mg/mL~45mg/mL.It is other identical as specific implementation mode one to one of 13.
Specific implementation mode 15：Present embodiment is unlike specific implementation mode one to one of 13：Step 2
Middle addition reducing agent is to final concentration of 10mg/mL~40mg/mL.It is other identical as specific implementation mode one to one of 13.
Specific implementation mode 16：Present embodiment is unlike specific implementation mode one to one of 13：Step 2
Middle addition reducing agent is to final concentration of 20mg/mL~30mg/mL.It is other identical as specific implementation mode one to one of 13.
Specific implementation mode 17：Present embodiment is unlike specific implementation mode one to one of 16：Step 3
Described in conductive high polymer monomer be aniline, pyrroles, thiophene, acetylene, 3- hexyl thiophenes, one in 3,4- ethene dioxythiophenes
Kind is several by a mixture of arbitrary proportions.It is other identical as specific implementation mode one to one of 16.
Specific implementation mode 18：Present embodiment is unlike specific implementation mode one to one of 17：Step 3
Described in initiator be ferric trichloride, ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.Other and specific implementation mode one to ten
One of seven is identical.
Specific implementation mode 19：Present embodiment is unlike specific implementation mode one to one of 18：Step 3
Final concentration of 20mg/mL~90mg/mL of middle conductive high polymer monomer.It is other with one to one of 18 phase of specific implementation mode
Together.
Specific implementation mode 20：Present embodiment is unlike specific implementation mode one to one of 18：Step 3
Final concentration of 40mg/mL~70mg/mL of middle conductive high polymer monomer.It is other with one to one of 18 phase of specific implementation mode
Together.
Specific implementation mode 21：Present embodiment is unlike specific implementation mode one to one of 18：Step
Final concentration of 50mg/mL~60mg/mL of conductive high polymer monomer in three.It is other with one to one of 18 phase of specific implementation mode
Together.
Specific implementation mode 22：Present embodiment is unlike specific implementation mode one to one of 21：Step
5h~20h is reacted in rapid three.It is other identical as specific implementation mode one to one of 21.
Specific implementation mode 23：Present embodiment is unlike specific implementation mode one to one of 21：Step
10h~15h is reacted in rapid three.It is other identical as specific implementation mode one to one of 21.
Specific implementation mode 24：Present embodiment is unlike specific implementation mode one to one of 23：Step
Etching agent described in rapid four is hydrofluoric acid, sodium hydroxide solution, potassium hydroxide solution or ammonium hydroxide, wherein hydrofluoric acid, hydroxide
Sodium solution, potassium hydroxide solution and ammonia concn are 0.5-3mol/L.Other and specific implementation mode one to one of 23
It is identical.
Elaborate below to the embodiment of the present invention, following embodiment under based on the technical solution of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment one：
The preparation method of the yolk type Fenton microreactor of the present embodiment inner surface supported precious metal nano-particle, including with
Lower step：
One, magnetic nano-particle ferroso-ferric oxide is distributed in water, is added just into 200mL ferroso-ferric oxide suspension
Silester stirs 2min, adds ammonium hydroxide to final concentration of 0.2mg/mL to final concentration of 30mg/mL；6.0h is reacted, by institute
Obtain product A separation.
Two, product A is added in 20mL potassium chloroplatinate solution, wherein the final concentration of 0.3mg/mL of potassium chloroplatinate
, 30min is stirred, sodium borohydride solution, the wherein final concentration of 2.0mg/mL of sodium borohydride is added；The reaction was continued 30min, will
Obtained product B washing separation.
Three, product B is scattered in the aniline solution of 20mL, wherein the final concentration of 15mg/mL of aniline, persulfuric acid is added
Ammonium is to final concentration of 10mg/mL；After reacting 5h, by products therefrom C washing separation.
Four, product C is added in 1mol/L sodium hydroxide solutions, after stirring etching 18h, obtains final product.
Initial ferroso-ferric oxide microballoon stereoscan photograph is as shown in Figure 1 in the present embodiment.Fig. 2 is the scanning of final product
Electromicroscopic photograph.Fig. 3 is the transmission electron microscope photo of final product, yolk type structure and is embedded in inner surface as we can see from the figure
Noble metal nano particles.
Fig. 4 is the yolk type microreactor of inner surface supported precious metal nano-particle and initial ferriferrous oxide nano-particle
The comparison figure for carrying out Fenton's reaction degradation of methylene blue, in Fig. 4-the initial ferriferrous oxide nano-particle of ■-expression ,-●-
Indicate yolk type microreactor.The degradation rate of microreactor is much larger than ferriferrous oxide nano-particle as we can see from the figure,
Microreactor to the conversion rate of methylene blue faster.In this experiment, the initial concentration of methylene blue is 30mg/mL, 2.0 hours
Afterwards, methylene blue realizes 98.7% degradation in yolk type microreactor, and ferriferrous oxide nano-particle is only 62.4%.
Fig. 5 is microreactor and Fe manufactured in the present embodiment during Fenton's reaction3O4Nano-particle is for H2O2It utilizes
The comparison diagram of efficiency, 1 indicates microreactor in Fig. 5, and 2 indicate Fe3O4Nano-particle.In an experiment, the concentration of initial methylene blue
Identical (30mg/mL), dioxygen water consumption is identical (5.0mL), and degradation time is identical (2.0h), it can be seen that methylene in microreactor
Base indigo plant degrades 98.7%；And Fe3O4Nano-particle only degrades 62.4%.It can be seen that microreactor is to H2O2Using effect
Rate higher.
Fig. 6 is the transmission electron microscope photo of microreactor, from the figure, it can be seen that relative to initial after the completion of Fenton's reaction
Microreactor (Fig. 3), there is no significant differences for structure.Ferriferrous oxide nano-particle is still present in inside microreactor,
Do not assemble.Thus prove that microreactor has excellent stability.
Embodiment two：
The preparation method of the yolk type Fenton microreactor of the present embodiment inner surface supported precious metal nano-particle, including with
Lower step：
One, magnetic nano-particle ferroso-ferric oxide is distributed in water, positive silicon is added into 100mL ferroso-ferric oxide solution
Acetoacetic ester stirs 5min to final concentration of 20mg/mL, and ammonium hydroxide is added to final concentration of 0.4mg/mL；After reacting 8.0h, by gained
Product A separation.
Two, product A is added in 10mL potassium chloroplatinate solution, wherein the final concentration of 0.5mg/mL of potassium chloroplatinate,
20min is stirred, sodium borohydride solution, the wherein final concentration of 1.0mg/mL of sodium borohydride is added；It, will after the reaction was continued 10min
Obtained product B washings separation.
Three, product B is scattered in the aniline solution of 30mL, wherein the final concentration of 25mg/mL of aniline, persulfuric acid is added
Ammonium is to final concentration of 20mg/mL；After reacting 6.0h, by products therefrom C washing separation.
Four, product C is added in 1mol/L sodium hydroxide solutions, after stirring etching 24.0h, obtains final product.
Fig. 7 is the scanning of the yolk type Fenton microreactor of inner surface supported precious metal nano-particle manufactured in the present embodiment
Electromicroscopic photograph.
Fenton's reaction degradation is carried out using the yolk type microreactor and initial ferriferrous oxide nano-particle of the present embodiment
The concentration of methylene blue, initial methylene blue is identical (30mg/mL), and dioxygen water consumption is identical (5.0mL), and degradation time is identical
(2.0h), the present embodiment microreactor Methylene Blue degrade 99.2%；And Fe3O4Nano-particle only degrades 62.8%.By
This is as it can be seen that the degradation rate of microreactor is much larger than ferriferrous oxide nano-particle, and microreactor is to H2O2Utilization ratio more
It is high.
After the completion of Fenton's reaction, relative to initial microreactor, there is no significant differences for the structure of microreactor.Four oxidations
Three Fe nanometer particles are still present in inside microreactor, do not assemble.Thus it is excellent steady to prove that microreactor has
It is qualitative.
Claims (10)
1. a kind of preparation method of the yolk type Fenton microreactor of inner surface supported precious metal nano-particle, it is characterised in that should
Method includes the following steps：
One, magnetic nano-particle is distributed in water, then addition ethyl orthosilicate to final concentration of 1mg/mL~30mg/mL,
2-3min is stirred, ammonium hydroxide is added to final concentration of 0.01mg/mL~1mg/mL, reacts 6-12h, obtain product A；
Two, product A is added in precious metal salt solution, wherein final concentration of 0.1mg/mL~10mg/mL of precious metal salt, stirring
After 10min~30min, reducing agent is added to final concentration of 1mg/mL~50mg/mL, reacts 10min~60min, obtains product
B；
Three, product B is scattered in conductive high polymer monomer, the wherein final concentration of 10mg/mL of conductive high polymer monomer~
100mg/mL is added initiator to final concentration of 10mg/mL~300mg/mL, causes and polymerize, and reaction 3h~for 24 hours, obtain product
C；
Four, product C is put into etching agent, etching 10h~for 24 hours, obtain final product；
First using magnetic nano-particle as kernel templates, upper complete titanium dioxide is coated on its surface by hydrolyzing tetraethoxy orthosilane
Silicon shell；Later, noble metal nano particles are deposited on silica shell layer surface；Then, continue in outer surface aggregate conduction
High polymer monomer forms complete conducting high polymers object shell；Finally, by intermediate silica shell selective etch
Fall, has just obtained yolk type microreactor.
2. the preparation method of yolk type Fenton microreactor according to claim 1, it is characterised in that described in step 1
Magnetic nano-particle be ferroso-ferric oxide, di-iron trioxide or FeOOH.
3. the preparation method of yolk type Fenton microreactor according to claim 1, it is characterised in that be added in step 1
Ammonium hydroxide is to final concentration of 0.1mg/mL~0.8mg/mL.
4. the preparation method of yolk type Fenton microreactor according to claim 1, it is characterised in that described in step 2
Precious metal salt in precious metal salt solution is silver nitrate, gold chloride, chloroplatinic acid, palladium bichloride, silver ammino solution, potassium chloroplatinate, sub- chlorine
One or more of potassium platinate.
5. the preparation method of yolk type Fenton microreactor according to claim 1, it is characterised in that your gold in step 2
Belong to final concentration of 1mg/mL~7mg/mL of salt.
6. the preparation method of yolk type Fenton microreactor according to claim 1, it is characterised in that described in step 2
Reducing agent be sodium borohydride, hydrazine or glucose.
7. the preparation method of yolk type Fenton microreactor according to claim 1, it is characterised in that described in step 3
Conductive high polymer monomer be aniline, pyrroles, thiophene, acetylene, 3- hexyl thiophenes, one kind in 3,4- ethene dioxythiophenes or several
Kind presses a mixture of arbitrary proportions.
8. the preparation method of yolk type Fenton microreactor according to claim 1, it is characterised in that described in step 3
Initiator be ferric trichloride, ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.
9. the preparation method of yolk type Fenton microreactor according to claim 1, it is characterised in that conductive in step 3
Final concentration of 20mg/mL~90mg/mL of high polymer monomer.
10. the preparation method of yolk type Fenton microreactor according to claim 1, it is characterised in that described in step 4
Etching agent be hydrofluoric acid, sodium hydroxide solution, potassium hydroxide solution or ammonium hydroxide, wherein hydrofluoric acid, sodium hydroxide solution, hydrogen-oxygen
It is 0.5-3mol/L to change potassium solution and ammonia concn.
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| CN109692970A (en) * | 2018-11-26 | 2019-04-30 | 合肥学院 | A kind of quick method for preparing Fe/Ag composite nano powder |
| CN110560166B (en) * | 2019-09-25 | 2020-12-25 | 燕山大学 | Magnetic core-shell structure space confinement type platinum catalyst and preparation method thereof |
| CN114749172B (en) * | 2022-04-21 | 2023-06-27 | 清华大学 | Continuous preparation method of carbon nanomaterial loaded with small-particle-size noble metal |
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