CN105413717B - A kind of preparation method and applications of Ag/AgCl nanocatalysts - Google Patents
A kind of preparation method and applications of Ag/AgCl nanocatalysts Download PDFInfo
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- CN105413717B CN105413717B CN201510744800.9A CN201510744800A CN105413717B CN 105413717 B CN105413717 B CN 105413717B CN 201510744800 A CN201510744800 A CN 201510744800A CN 105413717 B CN105413717 B CN 105413717B
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- 229910021607 Silver chloride Inorganic materials 0.000 title claims abstract description 43
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 title claims abstract description 43
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002608 ionic liquid Substances 0.000 claims abstract description 26
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 25
- 238000006731 degradation reaction Methods 0.000 claims abstract description 24
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- 241000251468 Actinopterygii Species 0.000 claims abstract description 19
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 93
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 26
- AMFMJCAPWCXUEI-UHFFFAOYSA-M 1-ethylpyridin-1-ium;chloride Chemical compound [Cl-].CC[N+]1=CC=CC=C1 AMFMJCAPWCXUEI-UHFFFAOYSA-M 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
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- 239000003054 catalyst Substances 0.000 abstract description 28
- 230000012010 growth Effects 0.000 abstract description 4
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- 238000006303 photolysis reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 3
- 239000000356 contaminant Substances 0.000 abstract 1
- 230000005284 excitation Effects 0.000 abstract 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 22
- 239000000047 product Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical class C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 2
- 241001523601 Gyrodactylus Species 0.000 description 2
- 208000030852 Parasitic disease Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000418 atomic force spectrum Methods 0.000 description 2
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- 241000238631 Hexapoda Species 0.000 description 1
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- 241001500087 Trichodina Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000842 anti-protozoal effect Effects 0.000 description 1
- 239000003904 antiprotozoal agent Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The present invention relates to a kind of preparation method and applications of Ag/AgCl nanocatalysts, the preparation of involved nanometer Ag/AgCl photochemical catalysts is Ag/AgCl nanocatalyst of the synthesis with strip pattern using ionic liquid [Epy] Cl as presoma and style control agent.Under conditions of using ionic liquid [Epy] Cl as presoma and style control agent so that the crystal face longitudinal growth of cube crystal seed obtains the strip nanocatalyst of shape uniqueness.This catalyst has very strong photocatalytic activity, target contaminant methylene blue in fish medicine can be carried out decoloration photodissociation under the excitation of visible ray.This characteristic greatly promotes the photoresponse of catalyst, compared with the Ag/AgCl nanocatalysts with cube crystal form, it greatly promotes the catalytic degradation performance of methylene blue in fish medicine, degradation rate is up to 91% in 40min, the 5% of significantly larger than cubical Ag/AgCl, with the characteristics of efficient degradation, practicability is high.
Description
Technical field
The invention belongs to nanomaterial sciences and environmental science, and in particular to a kind of system of Ag/AgCl nanocatalysts
Preparation Method and its application.
Technical background
Nano silver brief introduction：Nano silver (NanoSilver) is that grain size is accomplished nano level metallic silver simple substance.Nanometer silver granuel
In 25 rans, there is strong suppression in footpath to the tens of kinds of pathogenic microorganisms such as Escherichia coli, gonococcus, chlamydia trachomatis mostly
System and killing effect, and drug resistance will not be generated.
There is article expression, AgCl has larger specific surface area, but catalyst easy in inactivation is easy in experiment as photochemical catalyst
Cohesion and difficult separation.
The defects of Ag/AgCl is as photochemical catalyst, active not high, Morphological control problem after reuse.
Methylene blue is a kind of heteroaromatic compound, in terms of being widely used in fish medicine, first, and it can when salt is used together
To prevent mildew of harnessing the river, second can prevent tail；3rd is that can treat some parasitic diseases, such as Trichodina, small melonworm, mouth
The parasitic disease of the anti-protozoal diseases such as filaria, oblique tube insect and Gyrodactylus, Dactylogyrus and skin and gill portion, it can in addition contain treat
Mucus dermatoses caused by Gyrodactylus.The survival rate of fish is greatly improved, is widely used in aquaculture.And water pollution caused by it
It is very important.According to ecological data, the substance is harmful to environment.
The content of the invention
For in the prior art the defects of and deficiency, present invention aims at provide a kind of strip Ag/AgCl nano-catalytics
The preparation method of agent and its application in degradation fish medicine Methylene Blue pollutant, involved nanometer Ag/AgCl photochemical catalysts
Preparation be using N-ethylpyridinium chloride ionic liquid (referred to as [Epy] Cl) as presoma and style control agent, synthesis has
The Ag/AgCl nanocatalysts of strip pattern.
Realize that the specific technical solution of the present invention is as follows：
A kind of preparation method of Ag/AgCl nanocatalysts, including using N-ethylpyridinium chloride ionic liquid as presoma
Ag/AgCl nanocatalysts are synthesized with style control agent.
Specifically, including using N-ethylpyridinium chloride ionic liquid as presoma and style control agent, Ag-containing compound is
Raw material, dihydric alcohol are solvent, and Ag/AgCl nanocatalysts are synthesized using the precipitation method.
More specifically, the dihydric alcohol is ethylene glycol, and the ratio of N-ethylpyridinium chloride ionic liquid and ethylene glycol is
1mol:100~300ml.
Again specifically, the Ag-containing compound is AgNO3, N-ethylpyridinium chloride ionic liquid and AgNO3Molar ratio
For 1:2.
Further, comprise the following steps：
Step 1：N-ethylpyridinium chloride ionic liquid is dissolved in dihydric alcohol and obtains storing solution A；
Step 2：Ag-containing compound is dissolved in dihydric alcohol and obtains storing solution B；
Storing solution A and storing solution B are uniformly mixed at room temperature and obtain mixed liquor, mixed liquor is after 140~160 DEG C of reactions
Obtain sediment to obtain the final product.
Specifically, the dihydric alcohol is ethylene glycol, Ag-containing compound AgNO3, N-ethylpyridinium chloride in storing solution A
The ratio of ionic liquid and ethylene glycol is 1mol:50~250ml；AgNO in storing solution B3Ratio with ethylene glycol is 2mol:
50ml。
Again specifically, after mixed liquor is stirred at room temperature 15~30min, then by mixed liquor in 140~160 DEG C of guarantors of oil bath
It holds after 2h postcoolings to room temperature centrifugal drying to obtain the final product.
The Ag/AgCl nanocatalysts that the preparation method is prepared are for catalytic degradation fish medicine Methylene Blue
Using.
Advantages of the present invention is：
(1) strip Ag/AgCl nanocatalysts of the invention mainly use N-ethylpyridinium chloride ionic liquid conduct
Presoma and style control agent make the pattern of catalyst become a plurality of shape from cube, considerably increase the specific surface of catalyst
Product, it will be apparent that improve degradation efficiency；
(2) catalyst for the strip pattern that the present invention is prepared can have very strong photoresponse energy under visible light
Power for catalytic degradation fish medicine Methylene Blue, breaches sulphadiazine class substance in fish medicine and inhibits general catalyst activity
It influences, this provides a kind of new photochemical catalyst for the processing of the methylene blue waste water of fish medicine；
(3) present invention prepares Ag/AgCl nanocatalysts method it is simple, two kinds of storing solutions can be prepared in advance, use
When two kinds of storing solutions are mixed again, and reacted under 140~160 DEG C of relatively low mixing temperature to obtain the final product.
Description of the drawings
Fig. 1 is the electron-microscope scanning figure that product is prepared：Wherein (a), (b), (c) are respectively 1 intermediate ion liquid of embodiment
Ratio with ethylene glycol is 1mol:10mL；1mol:100mL；1mol：The electron-microscope scanning figure of product obtained by 300mL；
Fig. 2 is the X ray diffracting spectrum (XRD) on the surface that product is prepared：From bottom to top be respectively embodiment 1 in from
The ratio of sub- liquid and ethylene glycol is respectively 1mol:10mL；1mol:100mL；1mol:The X-ray of product obtained by 300mL is spread out
Penetrate collection of illustrative plates；
Fig. 3 is the electron-microscope scanning figure for the product being prepared under the different reaction time：Wherein, (a), (b), (c) point
It is the electron-microscope scanning figure of the catalyst obtained under 5,15 and 120min not correspond to the reaction time in embodiment 2；
Fig. 4 is to react the Ag/ prepared under the conditions of 120min in the Ag/AgCl catalyst and embodiment 2 prepared with embodiment 4
AgCl catalyst is research object, and to the catalytic degradation ability under the visible light conditions of fish medicine Methylene Blue, Fig. 4 a are implementation
Ag/AgCl catalyst degradation force curve figures prepared by example 4, Fig. 4 b are that the Ag/ prepared under the conditions of 120min is reacted in embodiment 2
AgCl catalyst degradation force curve figures；
Fig. 5 is the electron-microscope scanning figure that Ag/AgCl catalyst is prepared in embodiment 4
The present invention is illustrated below in conjunction with specification drawings and specific embodiments.
Specific embodiment
Since, there are particular matter sulphadiazine class, this substance can inhibit generally to urge in the methylene blue pollutant of fish medicine
The activity of agent, thus strip Ag/AgCl nanocatalysts very low to fish medicine Methylene Blue degradation rate, of the invention, master
N-ethylpyridinium chloride ionic liquid (referred to as [Epy] Cl) of the purity more than 0.99 to be used to be controlled as presoma and shape
Agent makes the pattern of catalyst become strip from cube, avoids the generation of agglomeration, considerably increases the ratio table of catalyst
Area, it will be apparent that degradation efficiency is improved, and the catalyst of the pattern can have very strong photoresponse ability under visible light,
For catalytic degradation fish medicine Methylene Blue, the shadow that sulphadiazine class substance in fish medicine inhibits general catalyst activity is breached
It rings.
Specifically, the preparation process of the strip Ag/AgCl nanocatalysts of the present invention includes：
[Epy] Cl is dissolved in ethylene glycol first, stirs to being uniformly mixed, makes ionic liquid [Epy] Cl and ethylene glycol ratio
Example is respectively 1mol:50ml、1mol:150ml、1mol:250ml is uniformly mixed, and is stored respectively as storing solution A1, A2, A3；
By AgNO3It is dissolved in ethylene glycol, stirs to being uniformly mixed, make AgNO3It is 2mol with ethylene glycol ratio:50ml, as
Storing solution B is stored；
Above-mentioned storing solution A1, storing solution A2 and storing solution A3 are mixed with storing solution B during use so that in mixed liquor
The ratio of [Epy] Cl and ethylene glycol is respectively 1mol:100mL, 1mol:200mL and 1mol:It is heavy to quickly form white by 300mL
It forms sediment, 15~30min is stirred at room temperature, reaction product is cooled to room temperature, it is dry to carry out centrifugation by 140~160 DEG C of holding 2h of oil bath
It is dry.
The present invention is illustrated with following embodiment, but the present invention is not limited to the following embodiments, is not departing from the front and rear ancestor
Under the scope of purport, change is included in the technical scope of the present invention.
Sample obtained carries out the characterization of pattern and structure by the following means in following embodiment：Obtained nanometer
The SEM figures of Ag/AgCl photochemical catalyst products are obtained by Philips.XL.30 scanning electron microscope；XRD spectrum is by X'Pert
Pro x-ray powder diffraction instruments (Dandong ray instrument limited company) measure, (Cu K α, 40kV, 20mA), Cu K α radiations
Scanning range is that 2 θ are 10 ° -80 °.
Embodiment 1：
Step 1：[Epy] Cl is dissolved in the ethylene glycol of certain volume, makes [Epy] Cl and the ethylene glycol ratio be respectively
1mol:50ml、1mol:150ml、1mol:250ml is uniformly mixed, and is stored respectively as storing solution A1, A2, A3；
Step 2：By AgNO3It is dissolved in certain volume ethylene glycol, stirs to being uniformly mixed, make AgNO3With ethylene glycol ratio
For 2mol:50ml is stored as storing solution B；
Step 3：Above-mentioned storing solution A1, storing solution A2 and storing solution A3 are mixed respectively with storing solution B so that [Epy] Cl
Ratio with ethylene glycol is respectively 1mol:100mL、1mol:200mL and 1mol:300mL obtains the liquid of three kinds of different ratios；
Step 4：15~30min, 140~160 DEG C of guarantors of oil bath are stirred at room temperature in the liquid of three kinds of different ratios respectively
Hold 2h；
Step 5：Three kinds of reaction products are cooled to room temperature, carry out centrifugal drying.
Obtained product SEM figures and XRD diagram is respectively Fig. 1 and Fig. 2.As seen from the figure, the ratio of ionic liquid and ethylene glycol
Respectively 1mol:100mL；1mol:200mL；1mol:During 300mL, the longitudinal growth of gained Ag/AgCl nanocatalysts is increasingly
It is prominent, when the ratio of ionic liquid and ethylene glycol is 1mol:During 300mL, the strip pattern of obtained Ag/AgCl nanocatalysts
It is optimal.
Embodiment 2：
Step 1：[Epy] Cl is dissolved in the ethylene glycol of certain volume, makes [Epy] C l ionic liquids and ethylene glycol ratio
For 1mol:250ml is uniformly mixed, and is stored as storing solution A；
Step 2：By AgNO3It is dissolved in certain volume ethylene glycol, stirs to being uniformly mixed, make AgNO3With ethylene glycol ratio
For 2mol:50ml is stored as storing solution B；
Step 3：Above-mentioned storing solution A and storing solution B is mixed so that the ratio of [Epy] Cl and ethylene glycol is in mixed liquor
1mol:300ml；
Step 4：Mixing liquid in step 3 is divided into three parts, 15~30min is being stirred at room temperature respectively, oil
It is respectively 5,15 and 120min to bathe 140~160 DEG C of retention times.
Step 5：Reaction product is cooled to room temperature, carries out centrifugal drying.
The SEM figures for obtaining product are shown in Fig. 3.As seen from the figure, it is respectively 5,15 and when 140~160 DEG C of retention times of oil bath
During 120min, the longitudinal growth of gained Ag/AgCl nanocatalysts is more and more prominent, obtained when the retention time is 120min
The strip pattern of Ag/AgCl nanocatalysts is optimal.
Embodiment 3：
Ratio by 1 intermediate ion liquid of embodiment and ethylene glycol is respectively 1mol:100mL and 1mol:Prepared by 300mL urges
Agent is used for the light degradation process of fish medicine Methylene Blue contaminated liquid.
Step 1：500mg catalyst is taken to be dissolved in the methylene blue solution that 10mL concentration is 20mg/L, carries out 45min's
Dark adsorption treatment process；
Step 2：The photolysis step that methylene blue is carried out under visible ray is put into after adsorption equilibrium.
Its light degradation curve is as shown in Figure 4.From Fig. 4 a, the ratio of ionic liquid and ethylene glycol is 1mol:100mL's
Ag/AgCl is little to the photocatalytic degradation effect of methylene blue, and only 5% methylene blue is by light degradation after 40min；And Fig. 4 b
(ratio of ionic liquid and ethylene glycol is 1mol to middle strip pattern preferably Ag/AgCl:300mL) to the photocatalysis of methylene blue
Degradation is preferable, and degradation rate is high by 91% after degrading 19%, 40min in 10min, significantly larger than 1mol:The Ag/ of 100mL
AgCl catalyst.
Embodiment 4：
Preparation method in the present embodiment is same as Example 2, and the condition differed only in preparation process is different, this reality
It applies example and [Epy] Cl ionic liquids in embodiment 1 is replaced with into 1- butyl -3- methylimidazole chlorination ionic liquids, and by oil
The bath retention time is set to 120min, remaining condition is constant.
The SEM figures for obtaining product are shown in Fig. 5.As seen from the figure, 1- butyl -3- methylimidazole chlorinations ionic liquid synthesizes
Ag/AgCl nanocatalyst longitudinal growths are poor.Product obtained by the reaction is dropped for the light of fish medicine Methylene Blue contaminated liquid
Solution preocess, only 18% methylene blue is by light degradation after 40min, and degradation effect is well below by [Epy] Cl ionic liquids
The Ag/AgCl nanocatalysts of synthesis.
Embodiment 5：
The titanium dioxide optical catalyst of 500mg is taken to be dissolved in the methylene blue solution of 10mL 20mg/L, first carries out 45min
Dark adsorption treatment process, the photolysis step that methylene blue is carried out under visible ray is put into after adsorption equilibrium.Due to sulphadiazine class
The presence of substance, for only 5% methylene blue by light degradation, degradation effect is little after 40min.
Embodiment 6：
Research institute obtains the catalytic life of strip Ag/AgCl catalyst.By the photochemical catalyst Jing Guo 3 catalytic process of embodiment into
Row centrifugation recycling, carries out light degradation experiment to fish medicine Methylene Blue again.Experiment draws it in fish medicine after repeating 4 times
The disposal efficiency of methylene blue is respectively 69%, 65%, 57%, 45%.
Claims (5)
1. a kind of preparation method of Ag/AgCl nanocatalysts, which is characterized in that including with N-ethylpyridinium chloride ionic liquid
Ag/AgCl nanocatalysts are synthesized for presoma and style control agent；
The preparation method, comprises the following steps：
Step 1：N-ethylpyridinium chloride ionic liquid is dissolved in dihydric alcohol and obtains storing solution A；
Step 2：Ag-containing compound is dissolved in dihydric alcohol and obtains storing solution B；
Storing solution A and storing solution B are uniformly mixed at room temperature and obtain mixed liquor, mixed liquor obtains after reacting 2h at 140~160 DEG C
To obtain the final product to sediment；
The dihydric alcohol be ethylene glycol, N-ethylpyridinium chloride ionic liquid in storing solution A and storing solution B ethylene glycol it is total
The ratio of amount is 1mol:300ml；
The molar ratio of N-ethylpyridinium chloride ionic liquid and Ag-containing compound is 1:2.
2. the preparation method of Ag/AgCl nanocatalysts as described in claim 1, which is characterized in that the argentiferous chemical combination
Object is AgNO3。
3. the preparation method of Ag/AgCl nanocatalysts as claimed in claim 1 or 2, which is characterized in that Ag-containing compound is
AgNO3, the ratio of N-ethylpyridinium chloride ionic liquid and ethylene glycol is 1mol in storing solution A:250ml；AgNO in storing solution B3
Ratio with ethylene glycol is 2mol:50ml.
4. the preparation method of Ag/AgCl nanocatalysts as claimed in claim 1 or 2, which is characterized in that by mixed liquor in room
After 15~30min of the lower stirring of temperature, then by mixed liquor after 140~160 DEG C of oil bath keeps 2h postcoolings to room temperature centrifugal dryings i.e.
.
5. the Ag/AgCl nanocatalysts that the preparation method described in claim 1,2,3 or 4 is prepared are used for catalytic degradation fish
The application of medicine Methylene Blue.
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